CN104789771A - Valuable metal separation method for complex copper, lead, zinc and silver mixed concentrates - Google Patents
Valuable metal separation method for complex copper, lead, zinc and silver mixed concentrates Download PDFInfo
- Publication number
- CN104789771A CN104789771A CN201510225942.4A CN201510225942A CN104789771A CN 104789771 A CN104789771 A CN 104789771A CN 201510225942 A CN201510225942 A CN 201510225942A CN 104789771 A CN104789771 A CN 104789771A
- Authority
- CN
- China
- Prior art keywords
- zinc
- copper
- obtains
- concentrate
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a valuable metal separation method for complex copper, lead, zinc and silver mixed concentrates and belongs to the technical field of metal separation and recovery. The method disclosed by the invention comprises four steps, namely carrying out thermal activation, carrying out oxidizing leaching, separating copper, lead, silver and zinc, and replacing copper and settling zinc. The method disclosed by the invention is wide in practicability and is applicable to the separation of a variety of polymetallic mixed concentrates; due to the realization of the method disclosed by the invention, polymetallic ores need mixed separation only and do not need sorting, so that mine enterprises have no need of sorting equipment, sorting sites and the like, the investment is reduced by about 30%, the production cost is reduced by 20%, the waste of mineral resources is lowered, the ore dressing recovery percentage is increased by over 25%, the cycle is shortened by 1/3, workers are reduced by 1/3, and the power consumption is lowered by 1/3. Meanwhile, compared with the present processes at home and abroad, the method has the advantages of small investment, short production cycle, high valuable metal recovery rate and easiness in popularization and application.
Description
Technical field
The invention belongs to metal separation recovery technology field, be specifically related to a kind of complicated copper-lead zinc-silver collective concentrate valuable metal novel method for separating.
Background technology
Ground, Yunnan Three River Region, the billows Yangtze valley and the Laos of Burma such as China Sichuan, Xinjiang the domestic Mekong River valley to store the polymetallic ore of a large amount of copper-lead zinc-silvers, the comprehensive utilization in this type of multi-metal complex mineral deposit has two kinds of operational paths, one is sorting torpedo, namely select lead ore concentrate, zinc ore concentrate and copper ore concentrates respectively by ore dressing, then process respectively to extract lead, zinc and copper.The difficult point of this technique is ore dressing.Due to sorting difficulty, not only recovery rate in ore-dressing is low, and Er Qieqian, zinc and copper are mutually containing high, and concentrate quality is poor.Such as Sichuan white jade sips village's copper mine, and the situation of the glutinous military copper mine in Lincang all demonstrates this point.
Another kind of operational path is that process integration is controlled in choosing, and ore dressing not sorting, only selects collective concentrate, then with controlling golden means process collective concentrate.Its advantage is that recovery rate in ore-dressing increases substantially, and ore-dressing practice is simple.This kind of operational path problem is the activation of copper, lead, zinc and silver-colored collective concentrate.Complicated copper-lead zinc-silver many metals mineral intergrowth storage number is large, and valuable metal is wide in variety, and separating technology difficulty is large, and separation method current situation has several as follows both at home and abroad at present:
1, wet separation technique
1. potassium cloride
Some insoluble metallic sulfides leach under acid chlorine salts solution condition, can the complexing ion form stripping of chlorine, as [PbCl
4 -]
2-, [ZnCl
4 -]
2-deng.This provides Thermodynamic Basis for acid chlorine salts solution Selectively leaching metallic sulfide.Conventional potassium cloride agent is hydrochloric acid, villaumite and chlorine etc.
Gan Nan scalds copper-lead zinc composite sulfuration ore deposit, level ground, temperature 105 DEG C, and solid-to-liquid ratio 1:4, Fe
3+leach 3 hours under the condition of concentration 192 grams/t, the leaching yield of copper, lead and zinc is respectively 99.5%, 98.6% and 99.6%, and sulphur is that elementary sulfur or pyrite form are enriched in slag.
But during due to potassium cloride polymetallic ore, exist with ZnCl
2it is more difficult that solution produces electric zinc, with PbCl
2for the technical process of waste metallic lead is longer, more difficult in leaching and the linking of follow-up electrodeposition process, the existence of chlorion is to environment and the problem such as equipment requirements is higher.Therefore, the industrial implementation of the method is comparatively difficult.
2. sulfurization roasting Selectively leaching
Multi-metal sulfide, under suitable atmosphere and temperature, carries out sulfurization roasting in atmosphere, makes iron main transition become Fe
2o
3, and copper zinc etc. are transformed into vitriol, realize selective sulfate roasting, gained calcining leaches with dilute sulphuric acid again, reaches the object of Selectively leaching.As the Na with 2%
2sO
4making additive, at 550 DEG C of roasting lh, is then the H of 9.5% to calcining with weight fraction
2sO
4as leaching agent, be leach 30min under the condition of 2.5 in liquid-solid ratio, copper, zinc leaching rate are respectively 95% and 90%.
But due to baking acid immersion technique adopt first roasting after the operation that leaches, make the tediously long leaching yield of integrated artistic flow process low, equipment running maintenance cost improves, and the low concentration SO of calcining process output
2there is more difficult recovery and heavy-polluted shortcoming in gas, is unfavorable for that current smelter carries out the needs of green production.
3. alkaline leaching
Domestic employing vulcanised ore concentrate ammonia soaking technology: at NH
4 +concentration is 300g/L, and oxygenant SN22 concentration is 60kg/t, and catalysis AN31 consumption is 0.12kg/t, and liquid-solid ratio is under the condition of 5, stirring at normal temperature 4h, and the leaching yield of copper can reach 80.25%.
Alkaline leaching technique is adopted to have the strong feature of leaching process selectivity.But for existing technique, there is some problems in the linking effectively solving subsequent technique, and the existence of ammonia it is also proposed higher requirement to Working environment and physical environment.
4. direct weighting acidic leaching
Direct pickling process is a kind of employing acid is leaching agent (sulfuric acid etc.), and oxygen is the method that oxygenant directly leaches collective concentrate under a certain pressure.Its principal reaction formula is:
The pressurized acid leaching technique that have studied copper-lead zinc-silver polymetallic sulfide concentrate such as gram strong is thanked to by Kunming University of Science and Technology, temperature 145 ~ 150 DEG C, and granularity of concentrate <50 μm, initial acid H
2sO
4150g/t, total pressure 1.5MPa(oxygen partial pressure 1.1MPa), extraction time 2h, by liquid-solid ratio 8:1 processed, under stirring velocity 800r/min, pb, Ag of Zn leaching yield >99%, Cu leaching yield >91%, Pb, Fe leaching yield more than 95%, more than 98% enter leached mud.
Adopt direct weighting acidleach, its leach liquor can leach and electrodeposition procedure connection with existing neutralization, leached mud then with existing pyrometallurgical smelting procedure connection, achieve the comprehensive reutilization of Cu, Zn, Pb, Ag, S etc. in multi-metal sulfide.But exist following not enough:
(1) adopt one section of Leaching way, extract technology is long, and (as required, temperature is more than 140 DEG C to require higher temperature, pressure and sulfuric acid concentration, more than pressure 1.1MPa, acidity more than 150g/L), leach liquor is higher containing acid, need take measures to reduce sulfuric acid concentration, be beneficial to follow-up stripping process; There is technique to adopt two sections of counterflow leachings at present, namely adopt one section of pressurized acid leaching leach liquor to leach raw ore, and then one section of leached mud is carried out to the mode of pressurized acid leaching, improve acid-utilising rate, reduce the acidity of leach liquor, the Zn in rich leachate
2+.
(2) villaumite is adopted to do the technique of leaching agent, Cl
-although existence can improve sulphur membrane permeability, be beneficial to the oxidation dissolution of mineral, direct weighting acidleach process can be carried out under lower temperature, acidity and pressure, Cl
-existence can bring impact to follow-up electrodeposition, also can heavy corrosion metallurgical equipment.
(3) to obtain good leaching yield, especially improving the leaching yield of copper, needing to carry out Ultra-fine grinding, causing power consume to increase.
(4), in reaction process, the elementary sulfur that system generates can cover on mineral particle surface, hinder solvent to surface transport and product by surface diffusion to bulk solution, affect reaction and carry out.Need to adopt low, the effective sweetening agent of cost or sulfur method to improve oxidation and leaching efficiency.
2, bioleaching process
The Microorganism Leaching technology of metal sulfide is study hotspot in recent years, to with the unmanageable complex ore of conventional art (monometallic ore deposit and many metal composite ore deposit as multiple combined form), low-grade unbalanced-ore, abandoned mine etc., with bioleaching process process have pollution less, the feature such as working conditions gentle, flow process is short, cost is low, less investment.Bacterial leaching mechanism utilizes the oxidation of bacterium self or reductibility to make some component in mineral be oxidized or reduce, and then with solvable or precipitation forms and former separating substances; Or rely on the meta-bolites (organic acid, mineral acid and ferric ion) of bacterium and mineral to react, make useful component enter solution.
Bioleaching process is adopted to have good cost advantage, but long for the work period, and leaching yield is low, and coenosis waits deficiency by Environmental Factors is large, also needs further strengthening research and is effectively solved.At present, the separating technology of Complicated Copper, lead, zinc-silver concentrate is not reported.
In sum: 1. adopt potassium cloride, the existence of chlorion brings impact not only can to the linking of subsequent technique, but also corrosive equipment, contaminate environment; 2. same alkaline leaching brings impact also can to the connecting of subsequent technique, and the existence of ammonia also all proposes high requirement to Working environment and physical environment; 3. baking acid immersion is adopted then to there is technical process long, the low concentration SO of calcining process output
2the weakness of the more difficult recovery of gas; 4. the work period is long, leaching yield is low, coenosis is subject to the drawbacks such as Environmental Factors is large to adopt Bioleaching then to exist.5. adopt direct weighting acid leaching process, requires higher temperature, pressure, sulfuric acid concentration, and require that the sulphur of generation can cover mineral on the surface, affects and carries out to reaction.
Therefore, for the feature of complex multi-metal, develop the breach that efficient collective concentrate clean metallurgical technology is process multi-metal complex sulphide ores.And have broad application prospects.From the feature of technique, how to realize environment more friendly, separation condition is gentleer, and as lower extraction temperature, lower leaching pressure and lower leaching agent sulfuric acid concentration are the targets of Future Development.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, a kind of complicated copper-lead zinc-silver collective concentrate valuable metal separation method is provided, the method copper leaching rate >=99%, zinc leaching rate >=98.5%, plumbous silver enter enrichment slag, accumulation rate >=99%, reach the advanced level of domestic and international technique
The technical solution used in the present invention is as follows:
Unless there are specified otherwise, percentage sign of the present invention is all mass percent.
The ratio of the volume (ml) of the quality (g) that solid-to-liquid ratio (W/V) is solid and liquid.
A kind of complicated copper-lead zinc-silver collective concentrate valuable metal separation method, comprises the steps:
Step (1), thermal activation: rotary kiln is heated to 300-650 DEG C, slowly adds concentrate and sulphur-fixing agent, then constant temp. heating activation 3.5-4.5h, and the quality added of sulphur-fixing agent is the 20-50% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and activation concentrate;
The gas that described flue gas obtains after gathering dust first passes into first step scavenging solution and carries out first step spray cleaning, then passes in the scavenging solution of the second stage and carry out second stage spray cleaning, and the gas of the purification obtained directly is disposed in air; Add NaOH to the liquid after I and II purification spray and (precipitate mainly oxyhydroxide, as calcium hydroxide, ferrous hydroxide etc.) till not producing precipitation, filter, filtrate condensing crystal, obtain S-WAT solid, S-WAT solid after drying, take out by packaging; This purifying step is called as " one washes two absorptions ";
Described first step scavenging solution to be mass concentration be 40% aqueous sodium carbonate, second stage scavenging solution to be mass concentration be 40% aqueous sodium hydroxide solution; Gathering dust, what receive is zinc oxide fumes;
Step (2), Oxidation Leaching: the activation concentrate that step (1) obtains, after being milled to 200 orders, in dissolution kettle, joins in the vitriolated aqueous solution, in this aqueous solution, the mass percentage of sulfuric acid is 15%, activation concentrate and the solid-to-liquid ratio of the vitriolated aqueous solution are 1:3, then by steam heating to more than 85 DEG C time, add oxidizing, the consumption of oxygenant is 1.1-1.2 times of the quality of sulphur in activation concentrate, then azeotropic 3-4h, then after filtration, obtains leached mud and leach liquor;
Step (3), copper, lead, silver are separated with zinc: after the leached mud that step (2) obtains is washed with water to neutrality, obtain leaded and silver-colored slag, and this leaded and silver-colored slag enters traditional plumbous silver recovery technique or directly takes out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil;
Manganse Dioxide is added to Fe in the leach liquor that step (2) obtains
2+all be oxidized to Fe
3+after, adding sulfuric acid to pH is 1.5, and be then hydrolyzed removing Fe
3+(use conventional methods and be hydrolyzed), filters, obtains filter residue and the filtrate (filtrate is the mixing solutions of copper sulfate and zinc sulfate) of iron content; Filter residue is directly taken out or is separately used it for anything else;
Step (4), displacement copper and heavy zinc: in the filtrate that step (3) obtains, add iron replace, the add-on of iron is the 1.2-1.3 quality times of copper content in filtrate, filters, obtains filtrate and filter residue; It is 7 that filter residue is washed with water to pH, obtains blister copper powder; Blister copper powder is taken out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil; Filtrate is sent into conventional electrowinning zinc electrodeposition and is obtained zinc product.
Further, preferably described step (1) rotary kiln heating adopts heated by gas mode.
Further, the sulphur-fixing agent preferably described in step (1) is sodium hydroxide, calcium hydroxide, magnesium hydroxide or ironic hydroxide.
Further, the oxygenant preferably described in step (2) is the combination of any two kinds in hydrogen peroxide, sodium chlorate, chlorinated lime and air, and the ratio between composition does not do requirement.
compared with prior art, its beneficial effect is in the present invention:
1, warm activation in this employing, the crystalline network of copper mineral in concentrate is distorted, or " Fe and S is oxidized; make stable Cu-Fe-S key or Cu-S key become unstable; make the metal in concentrate generate other easy materials leached; to carry out at this process heat activation temperature <650 DEG C; sulphur, zinc, lead volatility amount reduce; flue gas is through gathering dust due to mineral surface part, " one washes two absorptions ", not only purified waste gas, and the treated generation S-WAT of scavenging solution is as by-product sale, produces very large economic benefit.In concentrate, the existence of sulphur plays combustion-supporting effect, has saved fuel, has reduced energy consumption.
2, Oxidation Leaching under this project employing low-temperature atmosphere-pressure, gentleer than the atmosphere leached under traditional High Temperature High Pressure, and produce safer, and only equipment investment cost reduces more than 3 times.
3, practicality of the present invention is wide, and the separation being applicable to various Complex metal bulk concentrates comprises the copper-contained materials such as copper ore concentrates, lead ore concentrate, zinc ore concentrate, brings new change again to the floatation process of the multiple metallic ore of complicated copper-lead zinc-silver.Past, general employing first mixed choosing to the flotation in this ore deposit, rear sorting process, and the realization of present invention process makes this polymetallic ore only need mix choosing, did not just need sorting.Like this, make bargh not need size separation equipment and sorting place etc., reduce investment about 30% and reduce production cost 20%, reduce the waste of Mineral resources, recovery rate in ore-dressing improves more than 25%, cycle time 1/3rd, personnel decrease 1/3rd, and power consumption decreases 1/3rd.
4, the present invention meets country, economizes related industries development policies and encourage direction.Project implementation is that the ore dressing of Complicated Copper Pb-Zn-Ag ore from now on and corresponding concentrate valuable metal hydrometallurgy process for separating and recovering thereof open a new technological approaches, facilitate the technical progress of industry, improve the aspects such as comprehensive resource utilization rate and all there is great economic implications.
5, the present invention than current technique both domestic and external have investment little, with short production cycle, recovery rate of valuable metals is high, due to leach be carry out under low-temperature atmosphere-pressure, therefore production atmosphere milder, more easily realizes industrialization.Copper leaching rate >=99%, zinc leaching rate >=98.5%, plumbous silver enter enrichment slag, accumulation rate >=99%.Therefore, the technology of the present invention feasible route, novel process reaches the advanced level of domestic and international technique.
6, the factory effluent that the present invention produces all recycles through purifying, and accomplishes zero release.The generation waste gas produced is through gathering dust, and secondary purification, i.e. " one washes two absorptions ", can not only produce valency byproduct.And waste gas is accomplished qualified discharge.This project realizes, and greatly reducing energy consumption, is therefore environment-friendly type, energy-saving project.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by buying the conventional products obtained.
Embodiment 1
A kind of complicated copper-lead zinc-silver collective concentrate valuable metal separation method, comprises the steps:
Step (1), thermal activation: rotary kiln is adopted heated by gas to 650 DEG C, slowly adds concentrate and sulphur-fixing agent, then constant temp. heating activation 4.5h, and the quality added of sulphur-fixing agent is 50% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and activation concentrate;
The gas that described flue gas obtains after gathering dust first passes into first step scavenging solution and carries out first step spray cleaning, then passes in the scavenging solution of the second stage and carry out second stage spray cleaning, and the gas of the purification obtained directly is disposed in air; Add NaOH to the liquid after I and II purification spray and (precipitate mainly oxyhydroxide, as calcium hydroxide, ferrous hydroxide etc.) till not producing precipitation, filter, filtrate condensing crystal, obtain S-WAT solid, S-WAT solid after drying, take out by packaging;
Described first step scavenging solution to be mass concentration be 40% aqueous sodium carbonate, second stage scavenging solution to be mass concentration be 40% aqueous sodium hydroxide solution; Gathering dust, what receive is zinc oxide fumes;
Step (2), Oxidation Leaching: the activation concentrate that step (1) obtains, after being milled to 200 orders, in dissolution kettle, joins in the vitriolated aqueous solution, in this aqueous solution, the mass percentage of sulfuric acid is 15%, activation concentrate and the solid-to-liquid ratio of the vitriolated aqueous solution are 1:3, then by steam heating to more than 85 DEG C time, add oxidizing, the consumption of oxygenant is 1.2 times of the quality of sulphur in activation concentrate, then azeotropic 4h, then after filtration, obtains leached mud and leach liquor;
Step (3), copper, lead, silver are separated with zinc: after the leached mud that step (2) obtains is washed with water to neutrality, obtain leaded and silver-colored slag, and this leaded and silver-colored slag enters traditional plumbous silver recovery technique or directly takes out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil;
Manganse Dioxide is added to Fe in the leach liquor that step (2) obtains
2+all be oxidized to Fe
3+after, adding sulfuric acid to pH is 1.5, and be then hydrolyzed removing Fe
3+(use conventional methods and be hydrolyzed), filters, obtains filter residue and the filtrate (filtrate is the mixing solutions of copper sulfate and zinc sulfate) of iron content; Filter residue is directly taken out or is separately used it for anything else;
Step (4), displacement copper and heavy zinc: in the filtrate that step (3) obtains, add iron replace, the add-on of iron is 1.3 quality times of copper content in filtrate, filters, obtains filtrate and filter residue; It is 7 that filter residue is washed with water to pH, obtains blister copper powder; Blister copper powder is taken out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil; Filtrate is sent into conventional electrowinning zinc electrodeposition and is obtained zinc product.
Sulphur-fixing agent in the present embodiment described in step (1) is sodium hydroxide.Oxygenant described in step (2) is the combination of hydrogen peroxide and sodium chlorate.
Embodiment 2
A kind of complicated copper-lead zinc-silver collective concentrate valuable metal separation method, comprises the steps:
Step (1), thermal activation: rotary kiln is adopted heated by gas to 300 DEG C, slowly adds concentrate and sulphur-fixing agent, then constant temp. heating activation 3.5h, and the quality added of sulphur-fixing agent is 20% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and activation concentrate;
The gas that described flue gas obtains after gathering dust first passes into first step scavenging solution and carries out first step spray cleaning, then passes in the scavenging solution of the second stage and carry out second stage spray cleaning, and the gas of the purification obtained directly is disposed in air; Add NaOH to the liquid after I and II purification spray and (precipitate mainly oxyhydroxide, as calcium hydroxide, ferrous hydroxide etc.) till not producing precipitation, filter, filtrate condensing crystal, obtain S-WAT solid, S-WAT solid after drying, take out by packaging;
Described first step scavenging solution to be mass concentration be 40% aqueous sodium carbonate, second stage scavenging solution to be mass concentration be 40% aqueous sodium hydroxide solution; Gathering dust, what receive is zinc oxide fumes;
Step (2), Oxidation Leaching: the activation concentrate that step (1) obtains, after being milled to 200 orders, in dissolution kettle, joins in the vitriolated aqueous solution, in this aqueous solution, the mass percentage of sulfuric acid is 15%, activation concentrate and the solid-to-liquid ratio of the vitriolated aqueous solution are 1:3, then by steam heating to more than 85 DEG C time, add oxidizing, the consumption of oxygenant is 1.1 times of the quality of sulphur in activation concentrate, then azeotropic 3h, then after filtration, obtains leached mud and leach liquor;
Step (3), copper, lead, silver are separated with zinc: after the leached mud that step (2) obtains is washed with water to neutrality, obtain leaded and silver-colored slag, and this leaded and silver-colored slag enters traditional plumbous silver recovery technique or directly takes out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil;
Manganse Dioxide is added to Fe in the leach liquor that step (2) obtains
2+all be oxidized to Fe
3+after, adding sulfuric acid to pH is 1.5, and be then hydrolyzed removing Fe
3+(use conventional methods and be hydrolyzed), filters, obtains filter residue and the filtrate (filtrate is the mixing solutions of copper sulfate and zinc sulfate) of iron content; Filter residue is directly taken out or is separately used it for anything else;
Step (4), displacement copper and heavy zinc: in the filtrate that step (3) obtains, add iron replace, the add-on of iron is 1.2 quality times of copper content in filtrate, filters, obtains filtrate and filter residue; It is 7 that filter residue is washed with water to pH, obtains blister copper powder; Blister copper powder is taken out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil; Filtrate is sent into conventional electrowinning zinc electrodeposition and is obtained zinc product.
Sulphur-fixing agent in the present embodiment described in step (1) is calcium hydroxide.Oxygenant described in step (2) is the combination of hydrogen peroxide and chlorinated lime.
Embodiment 3
A kind of complicated copper-lead zinc-silver collective concentrate valuable metal separation method, comprises the steps:
Step (1), thermal activation: rotary kiln is adopted heated by gas to 500 DEG C, slowly adds concentrate and sulphur-fixing agent, then constant temp. heating activation 4h, and the quality added of sulphur-fixing agent is 30% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and activation concentrate;
The gas that described flue gas obtains after gathering dust first passes into first step scavenging solution and carries out first step spray cleaning, then passes in the scavenging solution of the second stage and carry out second stage spray cleaning, and the gas of the purification obtained directly is disposed in air; Add NaOH to the liquid after I and II purification spray and (precipitate mainly oxyhydroxide, as calcium hydroxide, ferrous hydroxide etc.) till not producing precipitation, filter, filtrate condensing crystal, obtain S-WAT solid, S-WAT solid after drying, take out by packaging;
Described first step scavenging solution to be mass concentration be 40% aqueous sodium carbonate, second stage scavenging solution to be mass concentration be 40% aqueous sodium hydroxide solution; Gathering dust, what receive is zinc oxide fumes;
Step (2), Oxidation Leaching: the activation concentrate that step (1) obtains, after being milled to 200 orders, in dissolution kettle, joins in the vitriolated aqueous solution, in this aqueous solution, the mass percentage of sulfuric acid is 15%, activation concentrate and the solid-to-liquid ratio of the vitriolated aqueous solution are 1:3, then by steam heating to more than 85 DEG C time, add oxidizing, the consumption of oxygenant is 1.12 times of the quality of sulphur in activation concentrate, then azeotropic 3.6h, then after filtration, obtains leached mud and leach liquor;
Step (3), copper, lead, silver are separated with zinc: after the leached mud that step (2) obtains is washed with water to neutrality, obtain leaded and silver-colored slag, and this leaded and silver-colored slag enters traditional plumbous silver recovery technique or directly takes out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil;
Manganse Dioxide is added to Fe in the leach liquor that step (2) obtains
2+all be oxidized to Fe
3+after, adding sulfuric acid to pH is 1.5, and be then hydrolyzed removing Fe
3+(use conventional methods and be hydrolyzed), filters, obtains filter residue and the filtrate (filtrate is the mixing solutions of copper sulfate and zinc sulfate) of iron content; Filter residue is directly taken out or is separately used it for anything else;
Step (4), displacement copper and heavy zinc: in the filtrate that step (3) obtains, add iron replace, the add-on of iron is 1.25 quality times of copper content in filtrate, filters, obtains filtrate and filter residue; It is 7 that filter residue is washed with water to pH, obtains blister copper powder; Blister copper powder is taken out; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil; Filtrate is sent into conventional electrowinning zinc electrodeposition and is obtained zinc product.
Sulphur-fixing agent in the present embodiment described in step (1) is magnesium hydroxide.Oxygenant described in step (2) is the combination in dioxygen water and air.
Embodiment 4
Embodiment 4 is with the difference of embodiment 3: the sulphur-fixing agent described in step (1) is ironic hydroxide.Oxygenant described in step (2) is the combination of sodium chlorate and chlorinated lime.
Embodiment 5
The oxygenant that embodiment 5 and the difference of embodiment 3 are described in step (2) is the combination of sodium chlorate and air.
Embodiment 6
The oxygenant that embodiment 5 and the difference of embodiment 3 are described in step (2) is the combination of chlorinated lime and air.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (4)
1. a complicated copper-lead zinc-silver collective concentrate valuable metal separation method, is characterized in that, comprise the steps:
Step (1), thermal activation: rotary kiln is heated to 300-650 DEG C, slowly adds concentrate and sulphur-fixing agent, then constant temp. heating activation 3.5-4.5h, and the quality added of sulphur-fixing agent is the 20-50% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and activation concentrate;
The gas that described flue gas obtains after gathering dust first passes into first step scavenging solution and carries out first step spray cleaning, then passes in the scavenging solution of the second stage and carry out second stage spray cleaning, and the gas of the purification obtained directly is disposed in air; Add NaOH till not producing precipitation to the liquid after I and II purification spray, filter, filtrate condensing crystal, obtains S-WAT solid;
Described first step scavenging solution to be mass concentration be 40% aqueous sodium carbonate, second stage scavenging solution to be mass concentration be 40% aqueous sodium hydroxide solution;
Step (2), Oxidation Leaching: the activation concentrate that step (1) obtains is after being milled to 200 orders, join in the vitriolated aqueous solution, in this aqueous solution, the mass percentage of sulfuric acid is 15%, and the solid-to-liquid ratio of activation concentrate and the vitriolated aqueous solution is 1:3, then by steam heating to more than 85 DEG C time, add oxidizing, the consumption of oxygenant is 1.1-1.2 times of the quality of sulphur in activation concentrate, then azeotropic 3-4h, then after filtration, leached mud and leach liquor is obtained;
Step (3), copper, lead, silver are separated with zinc: after the leached mud that step (2) obtains is washed with water to neutrality, obtain leaded and silver-colored slag; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil;
Manganse Dioxide is added to Fe in the leach liquor that step (2) obtains
2+all be oxidized to Fe
3+after, adding sulfuric acid to pH is 1.5, and be then hydrolyzed removing Fe
3+, filter, obtain filter residue and the filtrate of iron content;
Step (4), displacement copper and heavy zinc: in the filtrate that step (3) obtains, add iron replace, the add-on of iron is the 1.2-1.3 quality times of copper content in filtrate, filters, obtains filtrate and filter residue; It is 7 that filter residue is washed with water to pH, obtains blister copper powder; Washings is back to the Oxidation Leaching process section of step (2), is mixed with the vitriolated aqueous solution, for Oxidation Leaching together with the vitriol oil; Filtrate is sent into conventional electrowinning zinc electrodeposition and is obtained zinc product.
2. complicated copper-lead zinc-silver collective concentrate valuable metal separation method according to claim 1, is characterized in that, described step (1) rotary kiln heating adopts heated by gas mode.
3. complicated copper-lead zinc-silver collective concentrate valuable metal separation method according to claim 1, it is characterized in that, the sulphur-fixing agent described in step (1) is sodium hydroxide, calcium hydroxide, magnesium hydroxide or ironic hydroxide.
4. complicated copper-lead zinc-silver collective concentrate valuable metal separation method according to claim 1, it is characterized in that, the oxygenant described in step (2) is the combination of any two kinds in hydrogen peroxide, sodium chlorate, chlorinated lime and air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510225942.4A CN104789771B (en) | 2015-05-06 | 2015-05-06 | Complicated copper-lead zinc-silver bulk concentrate valuable metal separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510225942.4A CN104789771B (en) | 2015-05-06 | 2015-05-06 | Complicated copper-lead zinc-silver bulk concentrate valuable metal separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104789771A true CN104789771A (en) | 2015-07-22 |
| CN104789771B CN104789771B (en) | 2017-06-16 |
Family
ID=53554960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510225942.4A Active CN104789771B (en) | 2015-05-06 | 2015-05-06 | Complicated copper-lead zinc-silver bulk concentrate valuable metal separation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104789771B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326190A (en) * | 2017-05-23 | 2017-11-07 | 西北矿冶研究院 | Resource utilization method of lead-zinc-silver-containing smelting slag |
| CN107723460A (en) * | 2017-10-23 | 2018-02-23 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN115232979A (en) * | 2022-08-16 | 2022-10-25 | 深圳市中金岭南有色金属股份有限公司 | Method for preparing zinc sulfate and recovering copper from low-grade copper-zinc sulfide ore through bioleaching |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126498A (en) * | 1993-05-04 | 1996-07-10 | 谢里特公司 | Recovery of metals from sulphidic material |
| CN1266908A (en) * | 1999-03-14 | 2000-09-20 | 龙诗明 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
| US20030041692A1 (en) * | 2001-03-28 | 2003-03-06 | Dowa Mining Co., Ltd. | Method and apparatus for leaching zinc concentrates |
| CN101914681A (en) * | 2010-07-27 | 2010-12-15 | 乐清市瑞集环保科技有限公司 | Pollution-free method for treating copper, lead and silver-containing material |
| CN102703694A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for treating low-grade zinc oxide ores by wet method |
| CN104278149A (en) * | 2013-07-12 | 2015-01-14 | 无锡成博科技发展有限公司 | Hydrometallurgy process of copper-lead-zinc symbiotic collective concentrate |
-
2015
- 2015-05-06 CN CN201510225942.4A patent/CN104789771B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126498A (en) * | 1993-05-04 | 1996-07-10 | 谢里特公司 | Recovery of metals from sulphidic material |
| CN1266908A (en) * | 1999-03-14 | 2000-09-20 | 龙诗明 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
| US20030041692A1 (en) * | 2001-03-28 | 2003-03-06 | Dowa Mining Co., Ltd. | Method and apparatus for leaching zinc concentrates |
| CN101914681A (en) * | 2010-07-27 | 2010-12-15 | 乐清市瑞集环保科技有限公司 | Pollution-free method for treating copper, lead and silver-containing material |
| CN102703694A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for treating low-grade zinc oxide ores by wet method |
| CN104278149A (en) * | 2013-07-12 | 2015-01-14 | 无锡成博科技发展有限公司 | Hydrometallurgy process of copper-lead-zinc symbiotic collective concentrate |
Non-Patent Citations (1)
| Title |
|---|
| 徐斌等: ""复杂银铜精矿的沸腾焙烧综合回收工艺"", 《北京科技大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326190A (en) * | 2017-05-23 | 2017-11-07 | 西北矿冶研究院 | Resource utilization method of lead-zinc-silver-containing smelting slag |
| CN107326190B (en) * | 2017-05-23 | 2019-09-20 | 西北矿冶研究院 | Resource utilization method of lead-zinc-silver-containing smelting slag |
| CN107723460A (en) * | 2017-10-23 | 2018-02-23 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN107723460B (en) * | 2017-10-23 | 2019-03-19 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN115232979A (en) * | 2022-08-16 | 2022-10-25 | 深圳市中金岭南有色金属股份有限公司 | Method for preparing zinc sulfate and recovering copper from low-grade copper-zinc sulfide ore through bioleaching |
| CN115232979B (en) * | 2022-08-16 | 2024-04-05 | 深圳市中金岭南有色金属股份有限公司 | Method for preparing zinc sulfate and recycling copper by bioleaching low-grade copper-zinc sulfide ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104789771B (en) | 2017-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104762466B (en) | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore | |
| CN100404708C (en) | Two-section roasting production process for recovering Au, Cu, Ag, As and S from As and C containing aurin ore | |
| CN104911359B (en) | A kind of process that cobalt and nickel are extracted from manganese waste slag | |
| CN103526024B (en) | Novel clean environment-friendly comprehensive recovery process for high-indium high-iron zinc concentrate | |
| CN102747226B (en) | Method for treating zinc hydrometallurgy waste residue by using alkali ammonium sulfur coupling method | |
| CN102876888A (en) | Zinc hydrometallurgy production process | |
| CN102031381B (en) | Process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash | |
| CN105567984B (en) | A kind of method that Bellamya aeruginosa control current potential selection is separate | |
| CN105950874B (en) | A kind of Copper making cigarette ash and the method for waste acid Combined Treatment | |
| CN105293564A (en) | Method for recycling zinc-containing dust ash in steel plant | |
| CN103740945B (en) | A kind of method of enriching and recovering cadmium from plumbous smelting system | |
| CN103695662B (en) | Comprehensive utilization method of slag iron concentrates of wet-type zinc smelting furnace | |
| CN101871046A (en) | Method for recycling heavy metal pollution wastes | |
| CN105543479B (en) | A kind of comprehensive recovering process of bismuth matte | |
| CN105463197A (en) | Method for recycling valuable metal from copper smelting white smoke | |
| CN104017991A (en) | Process for efficiently and selectively separating copper in lead copper matte | |
| CN106636656A (en) | Method for recovering valuable metal from copper smelting white smoke | |
| CN106048251A (en) | Technological method for cleaning and efficiently treating arsenic matte | |
| CN104451156A (en) | Comprehensive recovery method of lead copper matte | |
| CN103882236A (en) | Method for processing high-sulfur copper dust and recovering copper by employing a wet process | |
| Shamsuddin | Metal recovery from scrap and waste | |
| CN103952572A (en) | Method for optimizing zinc hydrometallurgy hot acid leaching process by pressure leaching | |
| CN108315553B (en) | Leaching method of copper-cobalt sulfide ore | |
| CN101565780B (en) | Smelting method of polymetallic lead-zinc sulfide ore | |
| CN105567983A (en) | Soot treatment process in copper smelting process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |