CN102230083A - Method for separating copper from lead copper matte - Google Patents

Abstract

The invention relates to a method for separating copper from lead copper matte, and belongs to the field of the wet-process metallurgy of non-ferrous metal. In the method, the lead copper matte is subjected to oxygen pressure leaching by adopting an NH3-(NH4)2SO4 alkalescent composite system at the temperature of between 110 and 200 DEG C; copper and NH3 undergo a coordination chemical reaction to enter solution, and other metal sulfides are converted into oxides/hydroxides and a sulfur element, the oxides/hydroxides and the sulfur element; and the copper and gold and silver are reserved in leaching residues, and the leaching residues return to a pyrometallurgical lead refining system and are subjected to batching to recover valuable elements such as lead, noble metal, simple substance sulfur. In copper-ammonia coordination solution, copper sulfate enrichment solution is obtained by the selective extraction of LiX84I and reextraction, and qualified cathode electrolytic copper is obtained by the conventional electrodeposition process of copper sulfate. By the method, the copper can be separated from the lead copper matte in one step, and the method is simple in a process, high in recovery rate of valuable metal, less in discharge of waste gas, waste water and waste residues, environment-friendly, low in requirement on equipment materials and safe and reliable in actual operation.

Description

A kind of from lead matte the method for separating copper

Technical field

The present invention relates to a kind of from lead matte the method for separating copper, belong to non-ferrous metal hydrometallurgy field.

Background technology

Copper is one of associated element the most common in the concentrate of lead sulfide ore.In concentrate of lead sulfide ore bottom convertor oxygen-enriched air smelting process, copper can be made the sulfonium reaction by oxidation and form independent matte phase, is commonly called as lead matte.Lead matte is the eutectic of metallic sulfides such as Cu, Pb, Fe, As, Sb, also is dissolved with Cu, Pb, Fe, Au, Ag, Se, Te and the Fe of metallic state ₃O ₄For the higher lead matte of cupric, (cupric weight ratio Cu 〉=30%), generally be to bessemerize the output blister copper as the copper metallurgy raw material, lead then volatilizees and enters gas phase and obtain the oxide compound flue dust, many drawbacks such as the ubiquity technical process is long, metal recovery rate is low, environmental pollution is big, production cost height.For the lower lead matte of cupric (cupric weight ratio Cu＜30%), then at first carry out the oxidizing roasting desulfurization, make copper be converted into cupric oxide or copper sulfate, calcining carries out sulfuric acid again and leaches, copper-bath can obtain electrolytic copper through electrodeposition, and the lead sulfate leached mud then returns the lead system batching.The subject matter that this technology exists is the low concentration SO that the oxidizing roasting operation produces ₂Flue gas is difficult to relieving haperacidity, serious pollution of ecological environment.And maturing temperature control is improper, very easily causes the material sintering, and calcining residual rate height, metal recovery rate significantly reduce thereupon.

On July 23rd, 2008, Chinese invention patent application publication number CNl01225476A discloses a kind of technology that reclaims copper from lead matte, be in sulfuric acid system, to press acid leaching process to realize the direct leaching of lead matte by oxygen, copper-bath carries out electrodeposition and reclaims electrolytic copper, plumbous silver-colored slag then returns the pyrometallurgical smelting of lead system, whole flow process is brief, three waste discharge is few, but the problem that acid pressurization leaching system ubiquity equipment corrosion is big, maintenance cost is high, and the leaching process poor selectivity causes the dispersion to a certain extent of valuable metal.

In 5 days January in 2011 state's invention public announcement of a patent application CN101935761A disclose a kind of from lead copper matte the method for separating copper and selen-tellurjum, this method is at first lead matte to be carried out oxygen to press alkali to soak desulfurization, selenium is oxidized to enter alkaline leach liquor, copper, lead and tellurium be oxidized to enter alkaline leached mud, the alkalescence leached mud is used dilution heat of sulfuric acid selective leaching copper and tellurium again, and lead is enriched in the acid leached mud.The subject matter that this technology exists is that the oxygen depletion amount is big, the sodium sulfate waste liquid that output is a large amount of, and the Si in the raw material also in a large number stripping cause liquid-solid separation difficulty.

Summary of the invention

Technical problem to be solved by this invention is: at the variety of problems and the deficiency of above lead matte treatment situation, provide a kind of from lead matte the method for separating copper.Can realize the step separation of copper in the lead matte, flow process is brief, the recovery rate of valuable metals height, and three waste discharge is few, environmental friendliness, and low to the equipment material requirement, actual motion is safe and reliable.

Technical thought of the present invention is: at NH ₃-(NH ₄) ₂SO ₄In the system lead matte is carried out oxygen and press leaching, copper and NH ₃Coordination chemistry takes place enter solution, other metallic sulfide then is converted into oxide/hydroxide and elementary sulfur, it remaines in leached mud with gold and silver, and it is recyclable elemental sulfur and valuable elements such as lead, gold and silver that leached mud returns pyrometallurgical smelting of lead system batching.Copper-ammonia conjugate solutions adopts LiX84I selective extraction free state cupric ion, can obtain the copper sulfate pregnant solution through the sulfuric acid back extraction again; Raffinate is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust can to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles.

The present invention a kind of from lead matte the method for separating copper, can be by following method steps specific implementation:

1. lead matte piece material fragmentation uses the ball mill ball milling to granularity 100 orders;

2. the lead matte powder behind the ball milling is used NH in autoclave ₃-(NH ₄) ₂SO ₄The weakly alkaline composite solution leaches, continuous aerating oxygen in the leaching process; The processing condition of this step are: liquid-solid ratio 3～10:1; NH ₃With (NH ₄) ₂SO ₄Mol ratio n _NH3: n _{(NH4) 2SO4}=3～6:1; Total ammonia and copper mol ratio n _{[NH3] r}: n _[Cur]=5～10:1; Oxygen partial pressure 0.3～2MPa; 110～200 ℃ of extraction temperatures; Extraction time 2～8h; Main chemical reactions is as follows:

2Cu+O ₂+2iNH ₃+2H ₂O=2Cu(NH ₃) _i ²⁺+4OH ^-

Cu ₂S+O ₂+2iNH ₃+2H ₂O=2Cu(NH ₃) _i ²⁺+S+4OH ^-

4FeS+3O ₂=2Fe ₂O ₃+4S

2PbS+O ₂=2PbO+2S

PbS+2O ₂=2PbSO ₄

Above-mentioned i is a ligancy;

3. after leaching process is finished, carry out liquid-solid separation, obtain leached mud respectively and contain Cu (NH ₃) _i ²⁺Leach liquor, leached mud returns the pyrometallurgical smelting of lead system recoveries and utilizes valuable elements such as elemental sulfur and lead, silver;

4. with step 3. contain Cu (NH ₃) _i ²⁺Leach liquor, with LiX84I selective extraction copper, extraction conditions is: the composition of organic phase is LiX84I/ semi-annular jade pendant kerosene=1:4～19 by volume; Compare O/A=1:3～8,10～40 ℃ of extraction temperature, duration of oscillation 5～10min, clarification separation time 5～10min, 2～4 grades of extraction progression; Load organic phases adopts 150～200g/L H again ₂SO ₄The solution back extraction can obtain the copper sulfate pregnant solution, and the back extraction condition is: compare O/A=1～6:1,10～40 ℃ of back extraction temperature; 1～3 grade of progression; Raffinate is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles;

5. 4. the copper sulfate pregnant solution of gained is as the electrolytic solution of the heavy copper of electrodeposition with step, and being coated with ruthenium titanium plate is anode, and stainless steel plate is a negative electrode, obtains qualified negative electrode electrolytic copper through conventional copper sulfate electrodeposition process; The processing condition of this step are: current density 150～320A/m ², electrodeposition time 8～12h, 30～50 ℃ of temperature.

In the above-mentioned technology, soak system oxidisability intensity,, be oxidized to sulfate radical, therefore need control oxygen partial pressure well with regard to some elemental sulfur if when 2. the step oxygen partial pressure is too high according to ammonia.

Compare with prior art, the present invention has following outstanding advantage: adopt full wet processing flow process, and leach liquor uses NH ₃-(NH ₄) ₂SO ₄The weakly alkaline compound system, realized that the selectivity of copper leaches, and valuable elements such as lead, gold and silver are highly enriched in leached mud, also can avoid the liquid-solid separation difficulty that a large amount of stripping of Si is caused in the NaOH strong basicity system; Aerating oxygen of the present invention utilizes oxygen to make oxygenant, utilizes the pure oxygen of high flow capacity, to strengthen oxidizing condition, improves the metal leaching rate.The present invention can realize the step separation of copper in the lead matte, and flow process is brief, the recovery rate of valuable metals height, and three waste discharge is few, and environmental friendliness belongs to the clean metallurgical technology; And low to the equipment material requirement, actual motion is safe and reliable.

Description of drawings

Fig. 1 is a process flow sheet of the present invention.

Embodiment

Describe the present invention below in conjunction with accompanying drawing in detail with specific embodiment

Embodiment 1

A kind of from lead matte the method for separating copper, can be by following method steps specific implementation:

1. the chemical constitution of lead matte is (%): Cu 44.13, Pb 18.21, Fe 4.68, S 15.80, As 0.94, Zn 0.16, Si 0.16, Ag 0.166, with this lead matte piece material fragmentation, uses the ball mill ball milling to granularity 140 orders;

2. behind the ball milling with lead matte powder NH ₃-(NH ₄) ₂SO ₄Leach continuous aerating oxygen in leaching process; The processing condition of this step are: liquid-solid ratio 10:1; NH ₃With (NH ₄) ₂SO ₄Mol ratio n _[NH3]: n _{[(NH4) 2SO4]}=5:1; Total ammonia and copper mol ratio n _{[(NH3) T]}: n _[CuT]=8:1; Oxygen partial pressure 1.5Mpa; 120 ℃ of extraction temperatures; Extraction time 7h;

3. after leaching process is finished, carry out liquid-solid separation; Get leached mud and contain Cu (NH ₃) _i ²⁺Leach liquor, leached mud returns the pyrometallurgical smelting of lead system recoveries and utilizes plumbous, silver, elemental sulfur valuable element;

4. with step 3. contain Cu (NH ₃) _i ²⁺Leach liquor is used the LiX84I selective extraction, and the composition of organic phase by volume per-cent is: LiX84I 10%, semi-annular jade pendant kerosene 90%; Extraction conditions is: compare O/A=1:7; 10 ℃ of extraction temperature, duration of oscillation 10min, clarification separation time 6min, 4 grades of extraction progression; Through the load organic phases of extraction gained, be the H of 150g/L again through weight percent concentration ₂SO ₄The solution back extraction can obtain the copper sulfate pregnant solution; The back extraction condition is: compare O/A=1:1; 30 ℃ of extraction temperature; 2 grades of progression; The raffinate of gained is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles;

5. 4. the copper sulfate pregnant solution of gained is as the electrolytic solution of the heavy copper of electrodeposition with step, and being coated with ruthenium titanium plate is anode, and stainless steel plate is a negative electrode, obtains qualified negative electrode electrolytic copper through conventional copper sulfate electrodeposition process; The processing condition of this step are: current density 300A/m ², electrodeposition time 8h, 50 ℃ of temperature.

Embodiment 2

A kind of from lead matte the method for separating copper, can be by following method steps specific implementation:

1. the chemical constitution of lead matte is (%): Cu 30.65, Pb 5.89, Fe 28.12, S 21.72, As 0.85, Zn 0.36, Si 3.25, Ag 0.085, Au 36g/t, with this lead matte piece material fragmentation, uses the ball mill ball milling to granularity 100 orders;

2. behind the ball milling with lead matte powder NH ₃-(NH ₄) ₂SO ₄Leach continuous aerating oxygen in leaching process; The processing condition of this step are: liquid-solid ratio 3:1; NH ₃With (NH ₄) ₂SO ₄Mol ratio n _[NH3]: n _{[(NH4) 2SO4]}=6:1; Total ammonia and copper mol ratio n _{[(NH3) T]}: n _[CuT]=7:1; Oxygen partial pressure 1.0Mpa; 200 ℃ of extraction temperatures; Extraction time 2h;

3. after leaching process is finished, carry out liquid-solid separation; Get leached mud and contain Cu (NH ₃) _i ²⁺Leach liquor, leached mud returns the pyrometallurgical smelting of lead system recoveries and utilizes plumbous, silver, elemental sulfur valuable element;

4. with step 3. contain Cu (NH ₃) _i ²⁺Leach liquor is used the LiX84I selective extraction, and the composition of organic phase by volume per-cent is: LiX84I 15%, semi-annular jade pendant kerosene 90%; Extraction conditions is: compare O/A=1:5; 40 ℃ of extraction temperature, duration of oscillation 5min, clarification separation time 6min, 3 grades of extraction progression; Through the load organic phases of extraction gained, be the H of 200g/L again through weight percent concentration ₂SO ₄The solution back extraction can obtain the copper sulfate pregnant solution; The back extraction condition is: compare O/A=6:1; 20 ℃ of extraction temperature; 3 grades of progression; The raffinate of gained is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles;

5. 4. the copper sulfate pregnant solution of gained is as the electrolytic solution of the heavy copper of electrodeposition with step, and being coated with ruthenium titanium plate is anode, and stainless steel plate is a negative electrode, obtains qualified negative electrode electrolytic copper through conventional copper sulfate electrodeposition process; The processing condition of this step are: current density 320A/m ², electrodeposition time 9h, 40 ℃ of temperature.

Embodiment 3

A kind of from lead matte the method for separating copper, can be by following method steps specific implementation:

1. the chemical constitution of lead matte is (%): Cu 26.21, Pb 8.04, Fe 15.70, S 9.02, As 2.72, Zn 0.65, Si 5.34, Ag 0.118, Au 18g/t, with the fragmentation of lead matte piece material, use the ball mill ball milling to granularity 120 orders this;

2. behind the ball milling with lead matte powder NH ₃-(NH ₄) ₂SO ₄Leach continuous aerating oxygen in leaching process; The processing condition of this step are: liquid-solid ratio 5:1; NH ₃With (NH ₄) ₂SO ₄Mol ratio n _[NH3]: n _{[(NH4) 2SO4]}=4:1; Total ammonia and copper mol ratio n _{[(NH3) T]}: n _[CuT]=10:1; Oxygen partial pressure 0.3Mpa; 150 ℃ of extraction temperatures; Extraction time 5h;

3. after leaching process is finished, carry out liquid-solid separation; Get leached mud and contain Cu (NH ₃) _i ²⁺Leach liquor, leached mud returns the pyrometallurgical smelting of lead system recoveries and utilizes plumbous, silver, elemental sulfur valuable element;

4. with step 3. contain Cu (NH ₃) _i ²⁺Leach liquor is used the LiX84I selective extraction, and the composition of organic phase by volume per-cent is: LiX84I 20%, semi-annular jade pendant kerosene 80%; Extraction conditions is: compare O/A=1:8; 20 ℃ of extraction temperature, duration of oscillation 8min, clarification separation time 5min, 4 grades of extraction progression; Through the load organic phases of extraction gained, be the H of 180g/L again through weight percent concentration ₂SO ₄The solution back extraction can obtain the copper sulfate pregnant solution; The back extraction condition is: compare O/A=3:1; 40 ℃ of extraction temperature; 1 grade of progression; The raffinate of gained is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles;

5. 4. the copper sulfate pregnant solution of gained is as the electrolytic solution of the heavy copper of electrodeposition with step, and being coated with ruthenium titanium plate is anode, and stainless steel plate is a negative electrode, obtains qualified negative electrode electrolytic copper through conventional copper sulfate electrodeposition process; The processing condition of this step are: current density 220A/m ², electrodeposition time 10h, 35 ℃ of temperature.

Embodiment 4

A kind of from lead matte the method for separating copper, can be by following method steps specific implementation:

1. the chemical constitution of lead matte is (%): Cu 32.17, Pb 11.26, Fe 16.85, S 18.96, As 1.86, Zn 1.64, Si 2.29, Ag 0.231, Au 25g/t, with the fragmentation of lead matte piece material, use the ball mill ball milling to granularity 120 orders this;

2. behind the ball milling with lead matte powder NH ₃-(NH ₄) ₂SO ₄Leach continuous aerating oxygen in leaching process; The processing condition of this step are: liquid-solid ratio 8:1; NH ₃With (NH ₄) ₂SO ₄Mol ratio n _[NH3]: n _{[(NH4) 2SO4]}=3:1; Total ammonia and copper mol ratio n _{[(NH3) T]}: n _[CuT]=5:1; Oxygen partial pressure 2 Mpa; 180 ℃ of extraction temperatures; Extraction time 8h;

3. after leaching process is finished, carry out liquid-solid separation; Get leached mud and contain Cu (NH ₃) _i ²⁺Leach liquor, leached mud returns the pyrometallurgical smelting of lead system recoveries and utilizes valuable elements such as elemental sulfur and lead, silver, gold;

4. with step 3. contain Cu (NH ₃) _i ²⁺Leach liquor is used the LiX84I selective extraction, and the composition of organic phase by volume per-cent is: LiX84I 5%, semi-annular jade pendant kerosene 95%; Extraction conditions is: compare O/A=1:3; 30 ℃ of extraction temperature, duration of oscillation 7min, clarification separation time 10min, 2 grades of extraction progression; Through the load organic phases of extraction gained, be the H of 190g/L again through weight percent concentration ₂SO ₄The solution back extraction can obtain the copper sulfate pregnant solution; The back extraction condition is: compare O/A=4:1; 10 ℃ of extraction temperature; 3 grades of progression; The raffinate of gained is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles;

5. 4. the copper sulfate pregnant solution of gained is as the electrolytic solution of the heavy copper of electrodeposition with step, and being coated with ruthenium titanium plate is anode, and stainless steel plate is a negative electrode, obtains qualified negative electrode electrolytic copper through conventional copper sulfate electrodeposition process; The processing condition of this step are: current density 150A/m ², electrodeposition time 12h, 30 ℃ of temperature.

Claims (1)

1. the method for a separating copper from lead matte is characterized in that: by following step specific implementation:

1. lead matte piece material fragmentation uses the ball mill ball milling to granularity 100 orders;

2. the lead matte powder behind the ball milling is used NH in autoclave ₃-(NH ₄) ₂SO ₄The weakly alkaline composite solution leaches, continuous aerating oxygen in the leaching process; The processing condition of this step are: liquid-solid ratio 3～10:1; NH ₃With (NH ₄) ₂SO ₄Mol ratio n _NH3: n _{(NH4) 2SO4}=3～6:1; Total ammonia and copper mol ratio n _{[NH3] r}: n _[Cur]=5～10:1; Oxygen partial pressure 0.3～2MPa; 110～200 ℃ of extraction temperatures; Extraction time 2～8h;

3. after leaching process is finished, carry out liquid-solid separation, obtain leached mud respectively and contain Cu (NH ₃) _i ²⁺Leach liquor, leached mud returns the pyrometallurgical smelting of lead system recoveries and utilizes valuable elements such as elemental sulfur and lead, silver;

4. with step 3. contain Cu (NH ₃) _i ²⁺Leach liquor, with LiX84I selective extraction copper, extraction conditions is: the composition of organic phase is LiX84I/ semi-annular jade pendant kerosene=1:4～19 by volume; Compare O/A=1:3～8,10～40 ℃ of extraction temperature, duration of oscillation 5～10min, clarification separation time 5～10min, 2～4 grades of extraction progression; Load organic phases adopts 150～200g/L H again ₂SO ₄The solution back extraction can obtain the copper sulfate pregnant solution, and the back extraction condition is: compare O/A=1～6:1,10～40 ℃ of back extraction temperature; 1～3 grade of progression; Raffinate is NH ₃-(NH ₄) ₂SO ₄Mixing solutions adopts milk of lime to adjust to return behind the sulfate radical content oxygen to press ammonia to soak operation and recycles;

5. 4. the copper sulfate pregnant solution of gained is as the electrolytic solution of the heavy copper of electrodeposition with step, and being coated with ruthenium titanium plate is anode, and stainless steel plate is a negative electrode, obtains qualified negative electrode electrolytic copper through conventional copper sulfate electrodeposition process; The processing condition of this step are: current density 150～320A/m ², electrodeposition time 8～12h, 30～50 ℃ of temperature.

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