CN104278159A - Method for recovering metals by pyrometallurgical and hydrometallurgical joint processing of lead-bismuth-silver sulfide ores - Google Patents

Method for recovering metals by pyrometallurgical and hydrometallurgical joint processing of lead-bismuth-silver sulfide ores Download PDF

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CN104278159A
CN104278159A CN201310292258.9A CN201310292258A CN104278159A CN 104278159 A CN104278159 A CN 104278159A CN 201310292258 A CN201310292258 A CN 201310292258A CN 104278159 A CN104278159 A CN 104278159A
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bismuth
lead
silver
soda ash
coal dust
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李飞
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WUXI CHENGBO TECHNOLOGY DEVELOPMENT Co Ltd
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WUXI CHENGBO TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

The invention relates to a method for recovering metals by pyrometallurgical and hydrometallurgical joint processing of lead-bismuth-silver sulfide ores. The method comprises the following steps: mixing lead-bismuth sulfide ores, soda ash and coal powder for granulation, smelting for producing a lead-bismuth-silver alloy, dross and sodium matte, and recovering flue gas to obtain zinc existing in a secondary zinc oxide form; performing electrolysis on the lead-bismuth-silver alloy to obtain electric lead and silver-rich anode slime; and performing hot ball milling and leaching on the sodium matte to obtain a silver copper concentrate, and further recovering molybdenum from a leaching solution. The 'pyrometallurgical and hydrometallurgical joint process' provided by the invention is suitable for the mixed sulfide ores with lead, bismuth and precious metals and scattered metals, and the comprehensive recovery effect of the valuable metals is good; furthermore, the method is environment-friendly, has the advantages of low energy consumption and consumption of raw materials and relatively high comprehensive recovery rate of the metals, and is a green and clean production process.

Description

The method of a kind of pyrogenic process-wet method combined process Pb Bi Ag sulfide ore Footwall drift
Technical field
The present invention relates to field of metallurgy, particularly, the present invention relates to the pyrogenic process-wet method combined field of metallurgy of complicated sulfuration mine.
Background technology
Certain plumbous bismuth silver mixing complicated sulfuration mine domestic, weight, precious metal and dissipated metal coexist, and Qi Zhongqian, bismuth, silver, copper, molybdenum, zinc have higher recovery value, smelting process more complicated, there is certain difficulty.Various tradition refining method that is plumbous and bismuth is all difficult to reclaim valuable metal comprehensively, causes certain financial loss.
Pyrometallurgy refers to the various operations of at high temperature applying metallurgical furnace and a large amount of gangues in valuable metal and concentrate being separated.Ancient, the most the most frequently used method of pure metal is extracted in pyrometallurgy.The step that pyrometallurgical smelting adopts has roasting, melting, blowing, pyrorefining, electrorefining and chemical refining.The metal that electrorefining can use pyrometallurgy to produce reaches higher purity.
The process of hydrometallurgy to be exactly metalliferous mineral raw material at the aqueous solution of acidic medium or alkaline medium carry out chemical treatment or organic solvent extraction, separating impurity, extraction metal and compound thereof.Hydrometallurgy as one independently technology develop rapidly period in World War II, traditional pyrometallurgy can not be adopted when some mineral substance such as extraction uranium, and with chemical solvents, they can only be separated, the method for this extracting metals is exactly hydrometallurgy.
Modern hydrometallurgy almost covers all metal smeltings except iron and steel, its whole smelting technology of some metals belongs to hydrometallurgy, but great majority are mineral to be decomposed, extract and removal of impurities adopts wet processing, is finally reduced into metal and adopts pyrometallurgical smelting or powder metallurgy to complete.Typical hydrometallurgy has tungsten, molybdenum, tantalum, niobium, cobalt, nickel, rare earth, uranium, thorium, bismuth, tin, copper, lead, zinc, titanium, manganese, vanadium, Au Ag Pt Pd, indium, ruthenium, osmium, iridium, germanium, gallium etc.
Any one adopting pyrometallurgy or hydrometallurgy all can not reclaim valuable metal in complicated sulfuration mine comprehensively, therefore causes great waste.Therefore, the technical barrier of this area is a kind of method that comprehensively can reclaim the valuable metal in complicated sulfuration mine of exploitation.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the method providing a kind of pyrogenic process-wet method combined process Pb Bi Ag sulfide ore Footwall drift.
Described method comprises: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, melting, output plumbous bismuth silver alloy, scum silica frost and sodium matte, and recovered flue gas obtains the zinc that secondary zinc oxide form exists; Plumbous bismuth silver alloy electrolysis obtains electric lead and rich silver anode slime, and copper, molybdenum then enter in sodium matte slag, and matte heated ball-milling and leaching obtains silver-bearing copper concentrate, and molybdenum is reclaimed further in infusion solution.Add excessive soda ash owing to smelting in batching, sulphur can be combined completely with sodium, hardly containing sulfurous gas in tail gas, and only 300 ~ 400mg/m under the concentration standard state of sulfurous gas after testing 3, sulfur-fixing rate is more than 96%.
Preferably, said method comprising the steps of:
(1) alkali smelting: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, melting, output plumbous bismuth silver alloy, scum silica frost and sodium matte, recovered flue gas obtains the zinc of secondary zinc oxide form;
(2) process of sodium matte: matte also claims sodium matte, except containing except the valuable metal such as copper, silver, also containing Na 2s and Na 2the water-soluble alkali such as O and slag making material, the object of process sodium matte is the intermediates also regeneration alkali wherein of output cupric, silver and sulphur, comprising:
(2-1) sodium matte heated ball-milling and leaching: due to dissolution process heat release, process energy consumption is not high; Extraction temperature 50 ~ 70 DEG C, solid-to-liquid ratio 1:3 ~ 3:1,0.5 ~ 2 hour time, oxidizer; React the Na in the NaOH and sodium matte generated 2cO 3all soluble in water, most sodium salt proceeds to solution, and leached mud is sized mixing by solid-to-liquid ratio 1:100 ~ 1:120 water of 35 ~ 90 DEG C again, washing 2 ~ 3h, further recovery solvend, the copper of enrichment 99.2% and the zinc of 98.9% in washed-residue, the molybdenum of more than 95% enters solution;
(2-2) the hot carbonating of leach liquor: still have part Na in sodium matte heated ball-milling and leaching liquid 2s, need pass into CO in leach liquor 2, by Na 2s changes Na into 2cO 3return use, the operational condition of hot carbonating is: temperature 70 ~ 90 DEG C; Flue gas for carbonating contains CO 27% ~ 8%; Reaction times 3 ~ 5h;
(2-3) cold carbonating: the object of cold carbonic acid is the Na making solubleness in solution larger 2cO 3change the NaHCO that solubleness is less into 3; CO is passed into again in solution after thermotropism carbonating 2, Na 2cO 3change NaHCO into 3crystallization, mother liquor is back to hot water leaching operation and recycles; The operational condition of cold carbonating is: temperature 10 ~ 30 DEG C, time 1 ~ 4h, and the flue gas for carbonating contains 7% ~ 8%CO 2; The NaHCO of cold carbonation crystallization 3, directly can return use, also can become Na at the temperature lower calcination of 350 ~ 400 DEG C 2cO 3, calcining tail gas can be back to carbonation and use; Sodium carbonate regenerate that recyclable part accounts for whole alkaline consumption 83% ~ 90%; Soda ash after calcining is containing Na 2cO 377.5% ~ 99.9%, moisture 0.0% ~ 22.4%;
(2 ') electrolysis: by caustic fusion gained lead-bismuth alloy in the silicofluoric acid electrolysis of solutions, anode is plumbous bismuth silver alloy, and negative electrode is pure lead flake, and electrolytic solution is made up of silicofluoric acid and fluosilicic lead plumbate; In electrolytic process, plumbous in negative electrode precipitation, bismuth, silver then remain in the anode sludge, thus realize the separation of plumbous bismuth; During electrolysis, current potential, than plumbous negative metal, as zinc etc., from anode dissolution together with lead, enters electrolytic solution, can not separate out under normal circumstances at cathodic discharge; Current potential is than plumbous positive metal, as bismuth, silver, gold, copper etc., stay during electrolysis in the anode sludge, seldom enter electrolytic solution, but usually pollute electrolytic solution because the anode sludge comes off, larger on electrolytic process impact, for guaranteeing that cathode quality and electrolytic process carry out smoothly, will have a definite limitation to these impurity, generally control below 0.06% by anode cupric, the lead bismuth alloy of alkali smelting can meet the demands; The control of the technical qualification of plumbous bismuth silver alloy electrolysis comprises anode surface situation and composition, bath composition, processing parameter etc., anode: cast with flat-die, surfacing, bright and clean, not slag inclusion and foreign material; Anode components (%), Pb58 ~ 70, Bi30 ~ 40, Ag0.9 ~ 2, Cu0.001 ~ 0.002; Electrolytic solution composition (g/L): total acid concentration 140 ~ 180; Pb80 ~ 100; Cu≤0.002; Ag≤0.001; Bi≤0.003; Sb≤0.8; F≤3; Processing parameter: current density 60 ~ 80A/m 2; Bath voltage 0.4 ~ 0.7V; With pole span 90mm; 19, every groove anode, 20, negative electrode; Electrolyte temperature is room temperature; Circulation of elecrolyte amount is 20 ~ 30L/min; Electrolysing period 3d; Additive gelatine 0.5 ~ 0.8kg/t, 2-Naphthol 5 ~ 8g/t; Cathode lead is carried out pyrorefining and is obtained 1# lead; Negative electrode is filled pot and be warmed up to 460 ~ 500 DEG C, black slag is pulled out after fusing, continue to be warmed up to more than 500 DEG C, in stirring, add solid soda ash, continue stirring 0.2 ~ 1h, drag for lixiviating slag, add NaOH again and continue stirring 0.2 ~ 1h, peace and quiet pot limit alkaline residue, cools to 460 ~ 500 DEG C of ingot castings, and product is that 1# is plumbous; The anode sludge is dry through centrifuge dehydration washing, and load the interior fusing of the pot filling melting NaOH melt, cast anode after thick bismuth tentatively removes the gred, electrolysis obtains smart bismuth and silver preparation concentrate, and silver preparation concentrate obtains product silver through melting electrolysis.
Preferably, lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is (90 ~ 110): (40 ~ 60): (5 ~ 10), more preferably (95 ~ 105): (45 ~ 55): (6 ~ 9), are particularly preferably 100:50:7.
Preferably, the mixture of lead sulfide bismuth mineral, soda ash and coal dust adds in batches.
Preferably, the smelting temperature of lead sulfide bismuth mineral, soda ash and coal dust is 1000 ~ 1200 DEG C, is particularly preferably 1100 DEG C.
Preferably, the smelting time of lead sulfide bismuth mineral, soda ash and coal dust is at least 0.5 hour, more preferably 0.8 ~ 2 hour, is particularly preferably 1 hour.
Fusion process terminates, and scum silica frost, sodium matte, plumbous bismuth silver alloy are divided into three layers, are clawed by upper strata scum silica frost, and the plumbous bismuth silver alloy of sodium matte and lower floor is released respectively, and the general proportions of output object is alloy: matte: scum silica frost=300: 600: 100.
In whole fusion process, plumbous bismuth direct yield is all greater than 98%, silver-colored direct yield about 85%, the silver of 5% is in scum silica frost, and 10% enters matte can reclaim in subsequent processing, silver-colored total yield about 95%, the copper of more than 95% and the molybdenum of 90% reclaim in the lump at sodium matte and silver, and scum silica frost mainly water glass discards.
Preferably, described oxygenant is MnO 2.
Alkali smelting is similar to precipitation melting, Pb Bi Ag sulfide ore at high temperature with soda ash and coal dust effect output lead bismuth alloy.During reaction, soda ash decomposes, and sodium is combined with sulphur and forms sodium sulphite, and form low melting point matte with the sulfide of copper iron molybdenum etc., plumbous bismuth silver then generates lead bismuth alloy in reducing atmosphere.The silver of plumbous bismuth silver alloy energy enrichment 85%, alloy is electrolysis in silicofluoric acid system as lead, obtains electric lead and rich silver anode slime.Matte heated ball-milling and leaching obtains silver-bearing copper concentrate, and molybdenum reclaims from solution.The present invention can be combined with prior art, is separated silver-bearing copper, silver-colored bismuth further, and extracts molybdenum etc. from solution.
Compared with prior art, advantage of the present invention is:
(1) " pyrogenic process-wet method combined flow process " of the present invention is suitable for the mixing sulphide ores of lead, bismuth, precious metal and dissipated metal, and the synthetical recovery of valuable metal is respond well.
(2) " pyrogenic process-wet method combined flow process " environmentally safe of the present invention, energy consumption and raw materials consumption few, metal comprehensive recovery is higher, is green process for cleanly preparing.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
(1) alkali smelting: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, wherein lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is 90:60:10, adds in batches, 1000 DEG C of meltings 10 hours, output plumbous bismuth silver alloy, scum silica frost and sodium matte, recovered flue gas obtains the zinc of secondary zinc oxide form; Fusion process terminates, and scum silica frost, sodium matte, plumbous bismuth silver alloy are divided into three layers, are clawed by upper strata scum silica frost, and the plumbous bismuth silver alloy of sodium matte and lower floor is released respectively, and the general proportions of output object is alloy: matte: scum silica frost=300: 600: 100; In whole fusion process, plumbous bismuth direct yield is all greater than 98%, silver-colored direct yield about 85%, the silver of 5% is in scum silica frost, and 10% enters matte can reclaim in subsequent processing, silver-colored total yield about 95%, the copper of more than 95% and the molybdenum of 90% reclaim in the lump at sodium matte and silver, and scum silica frost mainly water glass discards;
(2) process of sodium matte: matte also claims sodium matte, except containing except the valuable metal such as copper, silver, also containing Na 2s and Na 2the water-soluble alkali such as O and slag making material, the object of process sodium matte is the intermediates also regeneration alkali wherein of output cupric, silver and sulphur, comprising:
(2-1) sodium matte heated ball-milling and leaching: due to dissolution process heat release, process energy consumption is not high; Extraction temperature 50 DEG C, solid-to-liquid ratio 3:1, time 2 h, adds MnO 2; React the Na in the NaOH and sodium matte generated 2cO 3all soluble in water, most sodium salt proceeds to solution, and leached mud is sized mixing by the solid-to-liquid ratio 1:100 water of 35 DEG C again, washing 3h, and reclaim solvend further, the copper of enrichment 99.2% and the zinc of 98.9% in washed-residue, the molybdenum of more than 95% enters solution;
(2-2) the hot carbonating of leach liquor: still have part Na in sodium matte heated ball-milling and leaching liquid 2s, need pass into CO in leach liquor 2, by Na 2s changes Na into 2cO 3return use, the operational condition of hot carbonating is: temperature 90 DEG C; Flue gas for carbonating contains CO 27%; Reaction times 3h;
(2-3) cold carbonating: the object of cold carbonic acid is the Na making solubleness in solution larger 2cO 3change the NaHCO that solubleness is less into 3; At normal temperatures, CO is passed into again in the solution after thermotropism carbonating 2, Na 2cO 3change NaHCO into 3crystallization, mother liquor is back to hot water leaching operation and recycles; The operational condition of cold carbonating is: temperature 10 DEG C, time 4h, and the flue gas for carbonating contains 8%CO 2; The NaHCO of cold carbonation crystallization 3, directly return use; Sodium carbonate regenerate that recyclable part accounts for whole alkaline consumption 83% ~ 90%;
(2 ') electrolysis: by caustic fusion gained lead-bismuth alloy in the silicofluoric acid electrolysis of solutions, anode is plumbous bismuth silver alloy, and negative electrode is pure lead flake, and electrolytic solution is made up of silicofluoric acid and fluosilicic lead plumbate; In electrolytic process, plumbous in negative electrode precipitation, bismuth, silver then remain in the anode sludge, thus realize the separation of plumbous bismuth; During electrolysis, current potential, than plumbous negative metal, as zinc etc., from anode dissolution together with lead, enters electrolytic solution, can not separate out under normal circumstances at cathodic discharge; Current potential is than plumbous positive metal, as bismuth, silver, gold, copper etc., stay during electrolysis in the anode sludge, seldom enter electrolytic solution, but usually pollute electrolytic solution because the anode sludge comes off, larger on electrolytic process impact, for guaranteeing that cathode quality and electrolytic process carry out smoothly, will have a definite limitation to these impurity, generally control below 0.06% by anode cupric, the lead bismuth alloy of alkali smelting can meet the demands; The control of the technical qualification of plumbous bismuth silver alloy electrolysis comprises anode surface situation and composition, bath composition, processing parameter etc., anode: cast with flat-die, surfacing, bright and clean, not slag inclusion and foreign material; Anode components (%), Pb58, Bi40, Ag0.9, Cu0.001; Electrolytic solution composition (g/L): total acid concentration 140; Pb80; Cu0.002; Ag0.001; Bi0.003; Sb0.8; F3; Processing parameter: current density 60A/m 2; Bath voltage 0.7V; With pole span 90mm; 19, every groove anode, 20, negative electrode; Electrolyte temperature is room temperature; Circulation of elecrolyte amount is 20L/min; Electrolysing period 3d; Additive gelatine 0.8kg/t, 2-Naphthol 5g/t; Cathode lead is carried out pyrorefining and is obtained 1# lead; Negative electrode is filled pot and be warmed up to 460 DEG C, after fusing, pull black slag out, continue to be warmed up to more than 500 DEG C, in stirring, add solid soda ash, continue to stir 0.2h, drag for lixiviating slag, then add NaOH continuation stirring 1h, peace and quiet pot limit alkaline residue, cools to 460 DEG C of ingot castings, and product is that 1# is plumbous; The anode sludge is dry through centrifuge dehydration washing, and load the interior fusing of the pot filling melting NaOH melt, cast anode after thick bismuth tentatively removes the gred, electrolysis obtains smart bismuth and silver preparation concentrate, and silver preparation concentrate obtains product silver through melting electrolysis.
Embodiment 2
(1) alkali smelting: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, wherein lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is 110:40:5, add in batches, 1200 DEG C of meltings 0.5 hour, output plumbous bismuth silver alloy, scum silica frost and sodium matte, recovered flue gas obtains the zinc of secondary zinc oxide form; Fusion process terminates, and scum silica frost, sodium matte, plumbous bismuth silver alloy are divided into three layers, are clawed by upper strata scum silica frost, and the plumbous bismuth silver alloy of sodium matte and lower floor is released respectively, and the general proportions of output object is alloy: matte: scum silica frost=300: 600: 100; In whole fusion process, plumbous bismuth direct yield is all greater than 98%, silver-colored direct yield about 85%, the silver of 5% is in scum silica frost, and 10% enters matte can reclaim in subsequent processing, silver-colored total yield about 95%, the copper of more than 95% and the molybdenum of 90% reclaim in the lump at sodium matte and silver, and scum silica frost mainly water glass discards;
(2) process of sodium matte: matte also claims sodium matte, except containing except the valuable metal such as copper, silver, also containing Na 2s and Na 2the water-soluble alkali such as O and slag making material, the object of process sodium matte is the intermediates also regeneration alkali wherein of output cupric, silver and sulphur, comprising:
(2-1) sodium matte heated ball-milling and leaching: due to dissolution process heat release, process energy consumption is not high; Extraction temperature 70 DEG C, solid-to-liquid ratio 1:3,0.5 hour time, adds MnO 2; React the Na in the NaOH and sodium matte generated 2cO 3all soluble in water, most sodium salt proceeds to solution, and leached mud is sized mixing by the solid-to-liquid ratio 1:120 water of 90 DEG C again, washing 2h, and reclaim solvend further, the copper of enrichment 99.2% and the zinc of 98.9% in washed-residue, the molybdenum of more than 95% enters solution;
(2-2) the hot carbonating of leach liquor: still have part Na in sodium matte heated ball-milling and leaching liquid 2s, need pass into CO in leach liquor 2, by Na 2s changes Na into 2cO 3return use, the operational condition of hot carbonating is: temperature 70 C; Flue gas for carbonating contains CO 28%; Reaction times 5h;
(2-3) cold carbonating: the object of cold carbonic acid is the Na making solubleness in solution larger 2cO 3change the NaHCO that solubleness is less into 3; At normal temperatures, CO is passed into again in the solution after thermotropism carbonating 2, Na 2cO 3change NaHCO into 3crystallization, mother liquor is back to hot water leaching operation and recycles; The operational condition of cold carbonating is: temperature 30 DEG C, time 1h, and the flue gas for carbonating contains 7%CO 2; The NaHCO of cold carbonation crystallization 3, become Na at the temperature lower calcination of 350 ~ 400 DEG C 2cO 3, calcining tail gas can be back to carbonation use again, and the soda ash after calcining is containing Na 2cO 377.5% ~ 99.9%, moisture 0.0% ~ 22.4%;
(2 ') electrolysis: by caustic fusion gained lead-bismuth alloy in the silicofluoric acid electrolysis of solutions, anode is plumbous bismuth silver alloy, and negative electrode is pure lead flake, and electrolytic solution is made up of silicofluoric acid and fluosilicic lead plumbate; In electrolytic process, plumbous in negative electrode precipitation, bismuth, silver then remain in the anode sludge, thus realize the separation of plumbous bismuth; During electrolysis, current potential, than plumbous negative metal, as zinc etc., from anode dissolution together with lead, enters electrolytic solution, can not separate out under normal circumstances at cathodic discharge; Current potential is than plumbous positive metal, as bismuth, silver, gold, copper etc., stay during electrolysis in the anode sludge, seldom enter electrolytic solution, but usually pollute electrolytic solution because the anode sludge comes off, larger on electrolytic process impact, for guaranteeing that cathode quality and electrolytic process carry out smoothly, will have a definite limitation to these impurity, generally control below 0.06% by anode cupric, the lead bismuth alloy of alkali smelting can meet the demands; The control of the technical qualification of plumbous bismuth silver alloy electrolysis comprises anode surface situation and composition, bath composition, processing parameter etc., anode: cast with flat-die, surfacing, bright and clean, not slag inclusion and foreign material; Anode components (%), Pb70, Bi30, Ag2, Cu0.002; Electrolytic solution composition (g/L): total acid concentration 180; Pb100; Ag0.001; Sb0.8; F3; Processing parameter: current density 80A/m 2; Bath voltage 0.4V; With pole span 90mm; 19, every groove anode, 20, negative electrode; Electrolyte temperature is room temperature; Circulation of elecrolyte amount is 30L/min; Electrolysing period 3d; Additive gelatine 0.5kg/t, 2-Naphthol 8g/t; Cathode lead is carried out pyrorefining and is obtained 1# lead; Negative electrode is filled pot and be warmed up to 500 DEG C, after fusing, pull black slag out, continue to be warmed up to more than 500 DEG C, in stirring, add solid soda ash, continue to stir 1h, drag for lixiviating slag, then add NaOH continuation stirring 0.2h, peace and quiet pot limit alkaline residue, cools to 500 DEG C of ingot castings, and product is that 1# is plumbous; The anode sludge is dry through centrifuge dehydration washing, and load the interior fusing of the pot filling melting NaOH melt, cast anode after thick bismuth tentatively removes the gred, electrolysis obtains smart bismuth and silver preparation concentrate, and silver preparation concentrate obtains product silver through melting electrolysis.
Embodiment 3
(1) alkali smelting: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, wherein lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is 100): 42:9, add in batches, 1100 DEG C of meltings 1 hour, output plumbous bismuth silver alloy, scum silica frost and sodium matte, recovered flue gas obtains the zinc of secondary zinc oxide form; Fusion process terminates, and scum silica frost, sodium matte, plumbous bismuth silver alloy are divided into three layers, are clawed by upper strata scum silica frost, and the plumbous bismuth silver alloy of sodium matte and lower floor is released respectively, and the general proportions of output object is alloy: matte: scum silica frost=300: 600: 100; In whole fusion process, plumbous bismuth direct yield is all greater than 98%, silver-colored direct yield about 85%, the silver of 5% is in scum silica frost, and 10% enters matte can reclaim in subsequent processing, silver-colored total yield about 95%, the copper of more than 95% and the molybdenum of 90% reclaim in the lump at sodium matte and silver, and scum silica frost mainly water glass discards;
(2) process of sodium matte: matte also claims sodium matte, except containing except the valuable metal such as copper, silver, also containing Na 2s and Na 2the water-soluble alkali such as O and slag making material, the object of process sodium matte is the intermediates also regeneration alkali wherein of output cupric, silver and sulphur, comprising:
(2-1) sodium matte heated ball-milling and leaching: due to dissolution process heat release, process energy consumption is not high; Extraction temperature 60 DEG C, solid-to-liquid ratio 1:1,1 hour time, adds MnO 2; React the Na in the NaOH and sodium matte generated 2cO 3all soluble in water, most sodium salt proceeds to solution, and leached mud is sized mixing by the solid-to-liquid ratio 1:110 water of 60 DEG C again, washing 2.5h, and reclaim solvend further, the copper of enrichment 99.2% and the zinc of 98.9% in washed-residue, the molybdenum of more than 95% enters solution;
(2-2) the hot carbonating of leach liquor: still have part Na in sodium matte heated ball-milling and leaching liquid 2s, need pass into CO in leach liquor 2, by Na 2s changes Na into 2cO 3return use, the operational condition of hot carbonating is: temperature 75 DEG C; Flue gas for carbonating contains CO 27.5%; Reaction times 5h;
(2-3) cold carbonating: the object of cold carbonic acid is the Na making solubleness in solution larger 2cO 3change the NaHCO that solubleness is less into 3; At normal temperatures, CO is passed into again in the solution after thermotropism carbonating 2, Na 2cO 3change NaHCO into 3crystallization, mother liquor is back to hot water leaching operation and recycles; The operational condition of cold carbonating is: temperature 15 DEG C, time 3h, and the flue gas for carbonating contains 7.4%CO 2; The NaHCO of cold carbonation crystallization 3, directly return use, sodium carbonate regenerate that recyclable part accounts for whole alkaline consumption 83% ~ 90%;
(2 ') electrolysis: by caustic fusion gained lead-bismuth alloy in the silicofluoric acid electrolysis of solutions, anode is plumbous bismuth silver alloy, and negative electrode is pure lead flake, and electrolytic solution is made up of silicofluoric acid and fluosilicic lead plumbate; In electrolytic process, plumbous in negative electrode precipitation, bismuth, silver then remain in the anode sludge, thus realize the separation of plumbous bismuth; During electrolysis, current potential, than plumbous negative metal, as zinc etc., from anode dissolution together with lead, enters electrolytic solution, can not separate out under normal circumstances at cathodic discharge; Current potential is than plumbous positive metal, as bismuth, silver, gold, copper etc., stay during electrolysis in the anode sludge, seldom enter electrolytic solution, but usually pollute electrolytic solution because the anode sludge comes off, larger on electrolytic process impact, for guaranteeing that cathode quality and electrolytic process carry out smoothly, will have a definite limitation to these impurity, generally control below 0.06% by anode cupric, the lead bismuth alloy of alkali smelting can meet the demands; The control of the technical qualification of plumbous bismuth silver alloy electrolysis comprises anode surface situation and composition, bath composition, processing parameter etc., anode: cast with flat-die, surfacing, bright and clean, not slag inclusion and foreign material; Anode components (%), Pb620, Bi34, Ag1.2, Cu0.0014; Electrolytic solution composition (g/L): total acid concentration 150; Pb90; Cu0.001; Ag0.0008; Bi0.0025; Sb0.6; F2; Processing parameter: current density 70A/m 2; Bath voltage 0.65V; With pole span 90mm; 19, every groove anode, 20, negative electrode; Electrolyte temperature is room temperature; Circulation of elecrolyte amount is 25L/min; Electrolysing period 3d; Additive gelatine 0.7kg/t, 2-Naphthol 6g/t; Cathode lead is carried out pyrorefining and is obtained 1# lead; Negative electrode is filled pot and be warmed up to 490 DEG C, after fusing, pull black slag out, continue to be warmed up to more than 520 DEG C, in stirring, add solid soda ash, continue to stir 0.6h, drag for lixiviating slag, then add NaOH continuation stirring 0.8h, peace and quiet pot limit alkaline residue, cools to 470 DEG C of ingot castings, and product is that 1# is plumbous; The anode sludge is dry through centrifuge dehydration washing, and load the interior fusing of the pot filling melting NaOH melt, cast anode after thick bismuth tentatively removes the gred, electrolysis obtains smart bismuth and silver preparation concentrate, and silver preparation concentrate obtains product silver through melting electrolysis.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. a method for pyrogenic process-wet method combined process Pb Bi Ag sulfide ore Footwall drift, comprising: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, melting, output plumbous bismuth silver alloy, scum silica frost and sodium matte, and recovered flue gas obtains the zinc that secondary zinc oxide form exists; Plumbous bismuth silver alloy electrolysis obtains electric lead and rich silver anode slime; Sodium matte heated ball-milling and leaching obtains silver-bearing copper concentrate, in infusion solution, reclaim molybdenum further.
2. the method for claim 1, is characterized in that, said method comprising the steps of:
(1) alkali smelting: lead sulfide bismuth mineral, soda ash and coal dust mixing granulation, melting, output plumbous bismuth silver alloy, scum silica frost and sodium matte, recovered flue gas obtains the zinc of secondary zinc oxide form;
(2) process of sodium matte, comprising:
(2-1) sodium matte heated ball-milling and leaching: extraction temperature 50 ~ 70 DEG C, solid-to-liquid ratio 1:3 ~ 3:1,0.5 ~ 2 hour time, oxidizer; Sized mixing by solid-to-liquid ratio 1:100 ~ 1:120 water of 35 ~ 90 DEG C by leached mud, washing 2 ~ 3h, reclaims molybdenum in leach liquor and washings, reclaims copper and zinc at washed-residue;
(2-2) the hot carbonating of leach liquor: pass into CO at 70 ~ 90 DEG C in leach liquor 2, reaction 3 ~ 5h, by Na 2s changes Na into 2cO 3return use;
(2-3) cold carbonating: at 10 ~ 30 DEG C, passes into CO in the solution after thermotropism carbonating 2, reaction 1 ~ 4h, Na 2cO 3change NaHCO into 3crystallization, mother liquor is back to hot water leaching operation and recycles;
(2 ') electrolysis: by step (1) melting gained lead-bismuth alloy in the silicofluoric acid electrolysis of solutions, anode for comprising Pb58 ~ 70wt%, the plumbous bismuth silver alloy of Bi30 ~ 40wt%, Ag0.9 ~ 2wt%, Cu0.001 ~ 0.002wt%, negative electrode is pure lead flake; The total acid concentration of electrolytic solution is 140 ~ 180, is made up of, comprises Pb80 ~ 100g/L, Cu≤0.002g/L, Ag≤0.001g/L, Bi≤0.003g/L, Sb≤0.8g/L and F≤3g/L electrolytic solution silicofluoric acid and fluosilicic lead plumbate; Processing parameter: current density 60 ~ 80A/m 2; Bath voltage 0.4 ~ 0.7V; With pole span 90mm; 19, every groove anode, 20, negative electrode; Electrolyte temperature is room temperature; Circulation of elecrolyte amount is 20 ~ 30L/min; Electrolysing period 3d; Additive gelatine 0.5 ~ 0.8kg/t, 2-Naphthol 5 ~ 8g/t; Cathode lead is carried out pyrorefining and is obtained 1# lead; Negative electrode is filled pot and be warmed up to 460 ~ 500 DEG C, black slag is pulled out after fusing, continue to be warmed up to more than 500 DEG C, in stirring, add solid soda ash, continue stirring 0.2 ~ 1h, drag for lixiviating slag, add NaOH again and continue stirring 0.2 ~ 1h, peace and quiet pot limit alkaline residue, cools to 460 ~ 500 DEG C of ingot castings, and product is that 1# is plumbous; The anode sludge is dry through centrifuge dehydration washing, and load the interior fusing of the pot filling melting NaOH melt, cast anode after preliminary slagging-off, electrolysis obtains smart bismuth and silver preparation concentrate, and silver preparation concentrate obtains product silver through melting electrolysis.
3. method as claimed in claim 1 or 2, is characterized in that, lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is (90 ~ 110): (40 ~ 60): (5 ~ 10).
4. the method as described in any one of claim 1-3, is characterized in that, lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is (95 ~ 105): (45 ~ 55): (6 ~ 9).
5. the method as described in any one of claim 1-4, is characterized in that, lead sulfide bismuth mineral: soda ash: the mass ratio of coal dust is 100:50:7.
6. the method as described in any one of claim 1-5, is characterized in that, the mixture of lead sulfide bismuth mineral, soda ash and coal dust adds in batches.
7. the method as described in any one of claim 1-6, is characterized in that, the smelting temperature of lead sulfide bismuth mineral, soda ash and coal dust is 1000 ~ 1200 DEG C.
8. the method as described in any one of claim 1-7, is characterized in that, the smelting temperature of lead sulfide bismuth mineral, soda ash and coal dust is 1100 DEG C.
9. the method as described in any one of claim 1-8, is characterized in that, the smelting time of lead sulfide bismuth mineral, soda ash and coal dust is at least 0.5 hour.
10. the method as described in any one of claim 1-9, is characterized in that, the smelting time of lead sulfide bismuth mineral, soda ash and coal dust is 0.8 ~ 2 hour, is particularly preferably 1 hour.
CN201310292258.9A 2013-07-12 2013-07-12 Method for recovering metals by pyrometallurgical and hydrometallurgical joint processing of lead-bismuth-silver sulfide ores Pending CN104278159A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106637298A (en) * 2016-11-16 2017-05-10 昆明冶金研究院 Electrical lead deposition method of lead-containing multi-metal material
CN107828971A (en) * 2017-12-16 2018-03-23 郴州市金贵银业股份有限公司 A kind of method that valuable metal is separated and recovered from high bismuth copper ashes
CN117144425A (en) * 2023-10-26 2023-12-01 内蒙古兴安银铅冶炼有限公司 Lead bismuth alloy electrolysis process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106637298A (en) * 2016-11-16 2017-05-10 昆明冶金研究院 Electrical lead deposition method of lead-containing multi-metal material
CN107828971A (en) * 2017-12-16 2018-03-23 郴州市金贵银业股份有限公司 A kind of method that valuable metal is separated and recovered from high bismuth copper ashes
CN117144425A (en) * 2023-10-26 2023-12-01 内蒙古兴安银铅冶炼有限公司 Lead bismuth alloy electrolysis process

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