CN218048363U - Gold, silver and copper-containing pyrite roasting slag water washing liquid treatment system - Google Patents

Gold, silver and copper-containing pyrite roasting slag water washing liquid treatment system Download PDF

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CN218048363U
CN218048363U CN202222303412.5U CN202222303412U CN218048363U CN 218048363 U CN218048363 U CN 218048363U CN 202222303412 U CN202222303412 U CN 202222303412U CN 218048363 U CN218048363 U CN 218048363U
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stirring barrel
flotation
unit
copper
silver
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段胜红
姜亚雄
高起方
谢恩龙
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Yunnan Gold Mining Group Co ltd
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Yunnan Gold Mining Group Co ltd
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Abstract

The utility model relates to a pyrite roasting slag washing liquid treatment system containing gold, silver and copper, which comprises a plurality of mixing tanks, wherein 3 mixing tanks are sequentially connected through an ore pulp pump, an overflow outlet of the mixing tank A is connected with a mixing tank E, and an overflow outlet of the mixing tank E is connected with a mixing tank B; the overflow outlet of the stirring barrel B is connected with a thickener A, and the lower end of the thickener A is connected with a pulp settling discharge port of the filter press A; an overflow outlet at the upper end of the thickener A and a filtrate outlet of the thickener A are connected with a stirring barrel C, an overflow outlet of the stirring barrel C is connected with a thickener B, and a discharge port of the thickener B is connected with a filter press B; filter cake outlets of the filter press A and the filter press B are connected with the stirring barrel D; the discharge hole of the stirring barrel D is connected with the feed inlet of the flotation unit; the flotation unit comprises a roughing unit, a scavenging unit I, a scavenging unit II, a cleaning unit I and a cleaning unit II. The utility model discloses can retrieve valuable component to the auriferous silver pyrite roasting slag washing liquid high efficiency that contains a small amount of gold, silver and copper.

Description

Pyrite roasting slag washing liquid treatment system containing gold, silver and copper
Technical Field
The utility model relates to a pyrite roasting slag washing liquid processing system containing gold, silver and copper, belonging to the mineral separation field, relating to the chemical mineral separation technical field containing gold, silver and pyrite in gold mineral separation.
Background
At present, in order to comprehensively utilize resources, most gold enterprises at home and abroad adopt a method of oxidizing roasting in a fluidized bed furnace, water washing pretreatment and leaching of gold and silver for treating fine-grain dip-dyeing type gold-silver-containing pyrite, and the roasting temperature is generally higher and is about 750-900 ℃. The gold, silver and pyrite in the mine generally contains trace elements such as copper and zinc, the grade of the gold, silver and pyrite is improved after roasting, gold and silver are directly leached, serious harmful effects are generated, and in order to eliminate the effects and improve the quality of iron ore concentrate, water washing pretreatment is carried out on roasting slag. The pretreatment water washing liquid is directly discharged without treatment, so that the serious environmental pollution is caused, and the problem of treatment of the waste liquid is involved. At present, methods for treating the copper-containing acidic waste liquid comprise a lime neutralization method, an ion exchange resin method, a single vulcanization precipitation method, an iron replacement method, a solvent extraction method and the like, but the methods have inevitable limitations in industrial application, and are difficult to effectively treat the acidic waste liquid, thereby causing resource waste and environmental pollution. The lime neutralization method is to utilize lime to neutralize sulfuric acid to produce gypsum, but the waste liquor contains more kinds of metals or non-metalsThe waste residues generated by ion generation can generate reverse dissolution along with the infiltration of rainwater in the stacking process, so that the harmful metal ions exceed the standard, the potential safety hazard is large, and valuable elements are not comprehensively utilized; the ion exchange resin method is that heterogeneous double decomposition reaction is carried out between a target component in a solution and a solid ion exchanger, so that the target component is preferentially transferred to the exchanger from a liquid phase, and then the ion exchanger saturated by the target component is leached by a proper reagent, so that the target component is transferred to the solution again, but the method has the advantages of low adsorption rate, long adsorption period and long process, so that the method is replaced by an organic solvent extraction method in many fields, and the gold and silver in the solution cannot be recovered; the single sulfide precipitation method is to precipitate copper, zinc and other ions by using sodium hydrosulfide, but when the method is used for treating waste liquid with low copper content, copper sulfide is fine in granularity, poor in particle hydrophobicity, easy to suspend in water, slow in precipitation speed, low in mineral concentration, difficult to precipitate in time in cooperation with fine gold and silver particles, and influences comprehensive recovery rate, so that heavy metal ion copper in slag exceeds the standard after sulfuric acid neutralization and precipitation, and does not reach safe discharge standard; the iron displacement method is characterized in that under an acidic condition, metallic iron is used for reducing and displacing copper ions to generate sponge copper, but the water washing liquid has low copper content, insufficient copper ion activity and low reduction displacement rate, soluble copper ions in waste residues exceed the standard after sulfuric acid neutralization and precipitation, the environment is polluted, and gold and silver in the solution are not effectively recovered; the solvent extraction method is based on that organic solvent has different dissolution to different metal ions, so that the metal in the solution can be enriched and separated, and the nonferrous metal copper adopts LL X However, the method has high cost for treating waste liquid with low copper content, is easy to cause secondary pollution of organic matters, and in addition, gold and silver in the solution are not effectively recovered. In conclusion, some methods do not consider valuable elements or effectively utilize valuable elements comprehensively, some methods are easy to cause secondary pollution, the amount of waste liquid to be treated is large, the cost is high, and resources cannot be effectively utilized comprehensively.
SUMMERY OF THE UTILITY MODEL
In order to overcome prior art not enough and solve the problem effectively, the utility model provides a contain the pyrite roasting slag washing liquid processing system of gold silver copper, the technical problem of solution is that the valuable composition is retrieved to high efficiency in the contain gold silver pyrite roasting slag washing liquid of a small amount of gold silver copper, makes the waste liquid reach industrial emission standard simultaneously, gains to increase resource comprehensive utilization ratio promptly, also reduces the purpose of gold mine production safety risk.
The specific technical scheme is as follows: a pyrite roasting slag washing liquid treatment system containing gold, silver and copper comprises a stirring barrel, a thickener and a flotation unit, wherein the stirring barrel comprises a stirring barrel A, a stirring barrel E, a stirring barrel B, a stirring barrel C and a stirring barrel D, the stirring barrel A, the stirring barrel E and the stirring barrel B are sequentially connected through a slurry pump, an overflow outlet of the stirring barrel A is connected with a feed inlet of the stirring barrel E through a slurry pump, and an overflow outlet of the stirring barrel E is connected with a feed inlet of the stirring barrel B through the slurry pump; an overflow outlet of the stirring barrel B is connected with a feed inlet at the upper end of the thickener A through an ore pulp pump, and a slurry sinking discharge outlet at the lower end of the thickener A is connected with a feed inlet of the filter press A; an overflow outlet at the upper end of the thickener A and a filtrate outlet of the thickener A are connected with a feed inlet of a stirring barrel C through an ore pulp pump, an overflow outlet of the stirring barrel C is connected with a feed inlet of a thickener B through the ore pulp pump, and a pulp sinking discharge outlet at the lower end of the thickener B is connected with a feed inlet of a filter press B; an overflow outlet at the upper end of the thickener B and a filtrate outlet of the thickener B are discharged; filter cake outlets of the filter press A and the filter press B are connected with a feed inlet of the stirring barrel D; the discharge hole of the stirring barrel D is connected with the feed inlet of the flotation unit; the flotation unit comprises a roughing unit, a scavenging unit I, a scavenging unit II, a fine selection unit I and a fine selection unit II; adding sodium hydrosulfide into the stirring barrel A, adding butylammonium black powder into the stirring barrel E, adding calcium carbonate into the stirring barrel B, and adding lime into the stirring barrel C.
Further, the roughing unit is formed by sequentially connecting 5 flotation machines in series from right to left; the scavenging machine set I is formed by sequentially connecting 4 flotation machines in series from right to left; the second scavenging machine set is formed by sequentially connecting 4 flotation machines in series from right to left; the first concentration unit is formed by sequentially connecting 4 flotation machines in series from right to left; the second selection unit is formed by connecting 3 flotation machines in series from right to left; a discharge port of the stirring barrel D is connected with a feeding port of a first flotation machine in the roughing unit, a tailing outlet of a last flotation machine in the roughing unit is connected with a feeding port of a first flotation machine in the scavenging unit, a tailing outlet of a last flotation machine in the scavenging unit is connected with a feeding port of a first flotation machine in the scavenging unit II, and a tailing outlet of a last flotation machine in the scavenging unit II is flotation tailings; the concentrate outlets of all the flotation machines in the first scavenging machine set are gathered and then connected with the feed inlet of the first flotation machine in the roughing machine set, and the concentrate outlets of all the flotation machines in the second scavenging machine set are gathered and then connected with the feed inlet of the first flotation machine in the first scavenging machine set; the concentrate outlets of all the flotation machines in the roughing unit are gathered and then connected with the feed inlet of the first flotation machine in the first concentration unit, the concentrate outlets of all the flotation machines in the first concentration unit are gathered and then connected with the feed inlet of the first flotation machine in the second concentration unit, the tailing outlet of the last flotation machine in the second concentration unit is connected with the feed inlet of the first flotation machine in the first concentration unit, the tailing outlet of the last flotation machine in the first concentration unit is connected with the feed inlet of the first flotation machine in the roughing unit, and the concentrate outlets of all the flotation machines in the second concentration unit are gathered into gold-containing silver-copper concentrate.
The specific technical steps comprise:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once in 10 minutes, stirring for 20-30 minutes, then adding 10-20 mg/l of butyl ammonium black drug into a stirring barrel E, and stirring for 5 minutes. The pH value of sodium hydrosulfide is increased more slowly than that of sodium sulfide, and the theoretical dosage of sodium hydrosulfide is based on the chemical reaction formula Cu 2+ +HS - =CuS↓+H + Calculating;
generally, the natural pH value of the pyrite roasting slag water washing liquid is about 1.5 to 3, so that the basic conditions of the sulfide precipitation can be met by adopting the natural pH value after water washing without specially adjusting the pH value in the sulfide precipitation process. The sodium hydrosulfide is slowly added, so that the phenomenon that excessive sodium hydrosulfide can cause the formation of water and polymeric sulfide complexes to influence metal separation is effectively avoided; because the vulcanization precipitation speed is high, the generated particles are relatively fine, the precipitation speed is low, the particles are easy to suspend in a solution, and in addition, the gold and silver particles in the water washing liquid belong to fine particles and are difficult to precipitate, so the hydrophobicity of valuable components is enhanced by adding the butyl ammonium black powder, the precipitation effect of the fine particles of the gold, silver and copper particles is improved, meanwhile, because the difference of the surface properties of the particles and gypsum is large, the occlusion and inclusion of the particles in the subsequent gypsum precipitation process are greatly reduced, monomer minerals with high dissociation property are generated, and the subsequent link can also be assisted in filtration.
The ammonium butyl black is added, the hydrophobicity of the vulcanized precipitate particles is microscopically increased, the particles can be promoted to grow up, the flocculation and sedimentation of the particles are facilitated, and the generation of the vulcanized precipitate in a suspension state can be avoided, so that the vulcanized precipitate generates occlusion and inclusion conditions in the subsequent gypsum precipitation process; macroscopically, a self-flocculating, settling, and isolating effect from other particles is produced.
(3) And (3) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and filtrate (discharge waste liquid);
in the precipitation processes in the steps (3) and (4), calcium carbonate is adopted, the pH value of the ore pulp is slowly adjusted to be 4-5, most iron ions and sulfuric acid generate particles with larger particles and better concentration and filtration performance, lime is adopted to adjust the pH value of the ore pulp to be 7-9, and ions which are difficult to precipitate are further precipitated. Through two-stage gradual precipitation, concentration and filtration, the pre-waste slag with complete crystal form, larger granularity and better concentration and filtration performance is obtained, the phenomenon that precipitator lime is added too fast, the precipitation generation speed is too fast, and finer particles are generated is avoided, the phenomenon that valuable components are occluded and included in waste slag is also avoided, meanwhile, stage mixing concentration and filtration are adopted, and the loss of micro-fine gold and silver in concentration and filtration is reduced to the maximum extent through synergistic effect. Because a large amount of gypsum enhances the filtration resistance, the useful minerals in the fine particle fraction are difficult to pass through the medium, and the recovery rate of the useful minerals in the filtration link is ensured. In the link, valuable components such as gold, silver, copper and the like can be effectively enriched in advance, and favorable conditions are provided for the next treatment.
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time concentration, namely first concentration and second concentration, and two-time scavenging, namely first scavenging and second scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosages of the butyl xanthate as the collecting agents of roughing, scavenging and scavenging are respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer 2# oil is 40g/t and 20g/t respectively, and the concentration of roughing ore pulp is 20%.
The process skillfully adopts sodium hydrosulfide to precipitate copper ions firstly, and then adds the ammonium butyl black powder to enhance the hydrophobicity of copper sulfide precipitate and fine gold and silver particles and improve the precipitation effect of the fine gold, silver and copper particles. Then, the iron ions and sulfuric acid are precipitated with calcium carbonate and lime, respectively. The selective precipitation is carried out in a classified sequence, so that the phenomena that valuable components such as copper, gold, silver and the like are occluded and clamped in a precipitation process to influence the further recovery of the valuable components are reduced or avoided, and meanwhile, the waste components are gradually precipitated in a stepped mode, so that the material with complete crystal form, large granularity and good concentration and filtration performance is obtained. And then stage mixing concentration and filtration are adopted, and loss of the micro-fine gold and silver in the concentration and filtration is reduced to the maximum extent through a synergistic effect. Then, a dispersant sodium hexametaphosphate is adopted for size mixing, and valuable components are floated in a low-concentration environment, so that a good flotation separation effect is obtained. Aiming at the treatment of the washing liquid of the pyrite concentrate roasting slag with different contents of gold, silver and copper, the high-quality gold-containing silver and copper concentrate and the high-safety discharged waste slag and waste liquid are obtained, and the harmless treatment and the valuable component recovery are completed at one time. The process is environment-friendly, safe and reliable, the resources are efficiently and comprehensively utilized, the comprehensive economic benefit of the gold mine is improved, and the method has wide industrial application and popularization value.
Compared with the prior method, has the advantages and positive effects
(1) Through the sequential comprehensive application of sodium hydrosulfide and butylammonium black powder, the precipitation effect of micro-fine-particle gold, silver and copper particles is improved, and the occlusion and inclusion of gypsum on the micro-fine-particle gold, silver and copper particles are greatly reduced; the method has the advantages that through the sequential comprehensive application of calcium carbonate and lime, the pre-waste slag with complete crystal form, large particle size and good concentration and filtration performance is obtained, the phenomenon that precipitator lime is added too fast, the precipitation generation speed is too fast, fine particles are generated, valuable components are prevented from being occluded and included in waste slag, meanwhile, stage mixing concentration and filtration are adopted, and through synergistic effect, the loss of micro-fine gold and silver in concentration and filtration is reduced to the maximum extent. The effective recovery rate of the valuable components of gold, silver and copper is obtained, and the recovery rate is greatly improved;
(2) The discharged waste residue has low content of soluble components, is green and environment-friendly, has good safety and discharge reliability, and avoids secondary pollution caused by the soluble components and organic matters;
(3) The harmless treatment and the valuable component recovery are completed at one time, the process is simple, and the treatment cost is low;
(4) The method has strong adaptability, and is suitable for treating the washing liquid of the oxidizing roasting slag of the gold-silver-containing sulfur concentrate with different contents to obtain high-quality gold-silver-copper concentrate and safely discharge waste slag and waste liquid. The method has wide industrial application and popularization values for the production of the gold mine.
Drawings
FIG. 1 is a connection diagram of a processing system for water washing liquid of pyrite roasting slag containing gold, silver and copper;
wherein, 1: agitator a (copper sulphide precipitate agitator), 2: slurry pump, 3, agitator E (hydrophobic agitator), 4, agitator B (one section deposits the agitator), 5: thickener a (primary thickener), 6: filter press a (one-stage filter press); 7: agitator C (two-stage precipitation agitator), 8: thickener B (secondary thickener), 9: filter press B (two-stage filter press), 10: agitator D (flotation size mixing agitator), 11: flotation unit, 12: roughing train, 13: first scavenging machine set, 14: a second scavenging machine set, 15: a first selection unit, 16: and a second fine selection unit.
Detailed Description
The system comprises a stirring barrel, a thickener and a flotation unit, wherein the stirring barrel comprises a stirring barrel A1, a stirring barrel E3, a stirring barrel B4, a stirring barrel C7 and a stirring barrel D10, the stirring barrel A1, the stirring barrel E2 and the stirring barrel B4 are sequentially connected through a slurry pump, an overflow outlet of the stirring barrel A1 is connected with a feed inlet of the stirring barrel E3 through the slurry pump, and an overflow outlet of the stirring barrel E3 is connected with a feed inlet of the stirring barrel B4 through the slurry pump; an overflow outlet of the stirring barrel B4 is connected with a feed inlet at the upper end of a thickener A5 through an ore pulp pump, and a slurry sinking discharge outlet at the lower end of the thickener A5 is connected with a feed inlet of a filter press A6; an overflow outlet at the upper end of the thickener A5 and a filtrate outlet of the thickener A6 are connected with a feed inlet of a stirring barrel C7 through an ore pulp pump, an overflow outlet of the stirring barrel C7 is connected with a feed inlet of a thickener B8 through the ore pulp pump, and a slurry sinking discharge outlet at the lower end of the thickener B8 is connected with a feed inlet of a filter press B9; an overflow outlet at the upper end of the thickener B8 and a filtrate outlet of the thickener B9 are discharged; filter cake outlets of the filter press A6 and the filter press B9 are connected with a feed inlet of a stirring barrel D10; the discharge hole of the stirring barrel D10 is connected with the feed inlet of the flotation unit; the flotation unit comprises a roughing unit, a scavenging unit I, a scavenging unit II, a fine selection unit I and a fine selection unit II; sodium hydrosulfide is added into a stirring barrel A1, butylammonium black powder is added into a stirring barrel E3, calcium carbonate is added into a stirring barrel B4, and lime is added into a stirring barrel C7.
Further, the roughing unit 12 is formed by connecting 5 flotation machines in series from right to left; the scavenging machine set I13 is formed by sequentially connecting 4 flotation machines in series from right to left; the second scavenging machine set 14 is formed by sequentially connecting 4 flotation machines in series from right to left; the first selection unit 15 is formed by sequentially connecting 4 flotation machines in series from right to left; the second selection unit 16 is formed by sequentially connecting 3 flotation machines in series from right to left; a discharge hole of the stirring barrel D10 is connected with a feed hole of a first flotation machine in the roughing unit 12, a tailing outlet of a last flotation machine in the roughing unit 12 is connected with a feed hole of a first flotation machine in the scavenging unit I13, a tailing outlet of the last flotation machine in the scavenging unit I13 is connected with a feed hole of a first flotation machine in the scavenging unit II 14, and a tailing outlet of the last flotation machine in the scavenging unit II 14 is flotation tailings; the concentrate outlets of all the flotation machines in the first scavenging machine set 13 are gathered and then connected with the first flotation machine feed inlet in the roughing machine set 12, and the concentrate outlets of all the flotation machines in the second scavenging machine set 14 are gathered and then connected with the first flotation machine feed inlet in the first scavenging machine set 13; the concentrate outlets of all the flotation machines in the roughing unit 12 are gathered and then connected with the first flotation machine feed inlet in the first concentrating unit 15, the concentrate outlets of all the flotation machines in the first concentrating unit 15 are gathered and then connected with the feed inlet of the first flotation machine in the second concentrating unit 16, the tailing outlet of the last flotation machine in the second concentrating unit 16 is connected with the first flotation machine feed inlet in the first concentrating unit 15, the tailing outlet of the last flotation machine in the first concentrating unit 15 is connected with the first flotation machine feed inlet in the roughing unit 12, and the concentrate outlets of all the flotation machines in the second concentrating unit 16 are gathered into gold-containing silver-copper concentrate.
Example 1:
the pyrite roasting slag washing liquid containing gold, silver and copper has natural pH =1.7, and the stock solution mainly comprises: contains gold 0.027mg/L, silver 0.062mg/L, copper 216mg/L, sulfur 4127mg/L, iron 604mg/L, and small amount of suspended substances and trace elements such as lead, zinc, calcium, and magnesium.
The invention is adopted to implement the water washing liquid of the pyrite roasting slag containing gold, silver and copper, and the technical steps comprise:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once every 10 minutes on average, stirring for 20-30 minutes, and then adding 10mg/l of ammonium butyl black into a stirring barrel E20mg/l, stirring for 5 minutes. Theoretical amount of sodium hydrosulfide based on chemical reaction formula Cu 2+ +HS - =CuS↓+H + Calculating;
(3) And (3) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of the balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and a filtrate (discharge waste liquid);
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time fine concentration and two-time scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosage of collecting agent butyl xanthate in roughing, scavenging and scavenging is respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer 2# oil is 40g/t and 20g/t respectively, and the concentration of roughing ore pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 35.26 percent, the gold grade is 46.73g/t, the silver grade is 107.35g/t, the copper recovery rate is 87.56 percent, the gold recovery rate is 85.25 percent, and the silver recovery rate is 89.38 percent; the discharged waste slag reaches the superior industrial discharge standard.
Example 2:
a pyrite roasting slag washing liquid containing gold, silver and copper has natural pH =2.2, and the stock solution mainly comprises: gold content is 0.022mg/L, silver content is 0.045mg/L, copper content is 208mg/L, sulfur content is 4648mg/L, iron content is 643mg/L, in addition, a small amount of suspended matters and trace elements such as lead, zinc, calcium, magnesium and the like are also contained.
The invention is adopted to implement the washing liquid of the pyrite roasting slag containing gold, silver and copper, and the technical steps comprise:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide according to 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once in about 10 minutes on average, stirring for 20-30 minutes, then adding 10-20 mg/l of ammonium buthylate black powder into a stirring barrel E, and stirring for 5 minutes. Theoretical amount of sodium hydrosulfide based on chemical reaction formula Cu 2+ +HS - =CuS↓+H + Calculating;
(3) And (3) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and filtrate (discharge waste liquid);
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time fine concentration and two-time scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosages of the butyl xanthate as the collecting agents of roughing, scavenging and scavenging are respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer 2# oil is 40g/t and 20g/t respectively, and the concentration of roughing ore pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 34.86 percent, the gold grade is 37.78g/t, the silver grade is 81.55g/t, the copper recovery rate is 86.72 percent, the gold recovery rate is 86.93 percent, and the silver recovery rate is 84.49 percent; the discharged waste slag reaches the superior grade industrial discharge standard.
Example 3:
a pyrite roasting slag washing liquid containing gold, silver and copper has natural pH =2.7, and the stock solution mainly comprises: gold content of 0.031mg/L, silver content of 0.067mg/L, copper content of 198mg/L, sulfur content of 4415mg/L, iron content of 617mg/L, and small amount of suspended matter and trace elements such as lead, zinc, calcium, magnesium, etc.
The invention is adopted to implement the washing liquid of the pyrite roasting slag containing gold, silver and copper, and the technical steps comprise:
(1) And (4) measuring the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide according to 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once in about 10 minutes on average, stirring for 20-30 minutes, then adding 10-20 mg/l of ammonium buthylate black powder into a stirring barrel E, and stirring for 5 minutes. Theoretical amount of sodium hydrosulfide based on chemical reaction formula Cu 2+ +HS - =CuS↓+H + Calculating;
(3) And (3) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and filtrate (discharge waste liquid);
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time fine concentration and two-time scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosage of collecting agent butyl xanthate in roughing, scavenging and scavenging is respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer 2# oil is 40g/t and 20g/t respectively, and the concentration of roughing ore pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 36.17 percent, the gold grade is 51.67g/t, the silver grade is 110.26g/t, the copper recovery rate is 88.11 percent, the gold recovery rate is 87.93 percent, and the silver recovery rate is 87.66 percent; the discharged waste slag reaches the superior grade industrial discharge standard.
Example 4:
a pyrite roasting slag washing liquid containing gold, silver and copper has natural pH =3.0, and the stock solution mainly comprises: gold content is 0.035mg/L, silver content is 0.059mg/L, copper content is 195mg/L, sulfur content is 5027mg/L, iron content is 662mg/L, in addition, a small amount of suspended matters and trace elements such as lead, zinc, calcium, magnesium and the like are also contained.
The invention is adopted to implement the water washing liquid of the pyrite roasting slag containing gold, silver and copper, and the technical steps comprise:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once every 10 minutes averagely, stirring for 20-30 minutes, adding 10-20 mg/l of ammonium butyl black drug into a stirring barrel E, and stirring for 5 minutes. The theoretical dosage of sodium hydrosulfide is based on the chemical reaction formula Cu 2+ +HS - =CuS↓+H + Calculating;
(3) And (3) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of the balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and a filtrate (discharge waste liquid);
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time fine concentration and two-time scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosages of the butyl xanthate as the collecting agents of roughing, scavenging and scavenging are respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer No. 2 oil is 40g/t and 20g/t respectively, and the concentration of roughing pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 37.58 percent, the gold grade is 58.33g/t, the silver grade is 98.47g/t, the copper recovery rate is 86.75 percent, the gold recovery rate is 87.24 percent, and the silver recovery rate is 86.27 percent; the discharged waste slag reaches the superior grade industrial discharge standard.
Example 5:
a pyrite roasting slag washing liquid containing gold, silver and copper has natural pH =3.5 or so, and a stock solution mainly comprises: gold content is 0.028mg/L, silver content is 0.057mg/L, copper content is 179mg/L, sulfur content is 4677mg/L, iron content is 702mg/L, in addition, a small amount of suspended matters and trace elements such as lead, zinc, calcium, magnesium and the like are also included.
The invention is adopted to implement the water washing liquid of the pyrite roasting slag containing gold, silver and copper, and the technical steps comprise:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A according to the theoretical dosageAdding sodium hydrosulfide 1.2 times, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once in 10 minutes, stirring for 20-30 minutes, then adding 10-20 mg/l of butyl ammonium black drug in a stirring barrel E, and stirring for 5 minutes. The theoretical dosage of sodium hydrosulfide is based on the chemical reaction formula Cu 2+ +HS - =CuS↓+H + Calculating;
(3) And (3) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of an equilibrium terminal to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and filtrate (discharge waste liquid);
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time fine concentration and two-time scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosages of the butyl xanthate as the collecting agents of roughing, scavenging and scavenging are respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer 2# oil is 40g/t and 20g/t respectively, and the concentration of roughing ore pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 37.15 percent, the gold grade is 54.71g/t, the silver grade is 101.63g/t, the copper recovery rate is 87.19 percent, the gold recovery rate is 86.44 percent, and the silver recovery rate is 87.15 percent; the discharged waste slag reaches the superior industrial discharge standard.
For example 5.1
A comparative test was carried out using the material of example (5), and the test results were represented by S 1 Represents;
the step of adding the ammonium butyrate black powder in the test is eliminatedTest and results with S 2 Represents;
namely, the technical steps include:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide according to 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once in about 10 minutes on average, and stirring for 20-30 minutes.
(3) And (4) carrying out primary precipitation treatment on sulfuric acid. Conveying the slurry obtained by the step (2) into a pretreatment stirring barrel B, adding calcium carbonate, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 4-5, concentrating, and filtering to obtain gypsum residue I and a filtrate;
(4) And (4) carrying out sulfuric acid secondary precipitation treatment. Conveying the filtrate obtained by the treatment in the step (3) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 7-9, concentrating, and filtering to obtain gypsum residue II and filtrate (discharge waste liquid);
(5) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (3) combining the gypsum slag I and the slag II obtained by the treatment in the steps (3) and (4), conveying the gypsum slag I and the slag II into a size mixing stirring barrel D, mixing size, conveying the gypsum slag I and the slag II into a flotation system, performing low-concentration flotation to enrich the gold, the silver and the copper, and obtaining high-quality gold-containing silver and copper concentrate and tailings (discharged waste slag) through one-time roughing, two-time fine concentration and two-time scavenging. In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosage of collecting agent butyl xanthate in roughing, scavenging and scavenging is respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer 2# oil is 40g/t and 20g/t respectively, and the concentration of roughing ore pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 26.87 percent, the gold grade is 29.69g/t, the silver grade is 51.87g/t, the copper recovery rate is 66.77 percent, the gold recovery rate is 68.42 percent, and the silver recovery rate is 50.37 percent.
For example 5.2
A comparative test was carried out using the material of example (5), and the test results were represented by S 1 Represents;
the step of adding calcium carbonate in the test is eliminated, and S is used for the test and the result 3 Represent
Namely, the technical steps include:
(1) And (4) determining the copper content of the waste liquid to be treated. Taking a certain amount of pretreated acidic waste liquid, and accurately determining the content of copper element by adopting a chemical analysis method;
(2) Copper sulfide precipitation and hydrophobic pretreatment. Conveying the acidic waste liquid to be treated into a vulcanization pretreatment stirring barrel A, adding sodium hydrosulfide according to 1.2 times of theoretical dosage, slowly adding the sodium hydrosulfide twice, adding the sodium hydrosulfide once in about 10 minutes on average, stirring for 20-30 minutes, then adding 10-20 mg/l of ammonium buthylate black powder into a stirring barrel E, and stirring for 5 minutes.
(3) And (5) carrying out sulfuric acid precipitation treatment. Conveying the slurry obtained by the treatment in the step (2) to a pretreatment stirring barrel C, adding lime, stirring for 20-30 minutes, controlling the pH value of a balance end point to be = 7-9, concentrating, and filtering to obtain gypsum slag and a filtrate (a discharged waste liquid);
(4) And (4) flotation, enrichment and recovery of valuable components of gold, silver and copper. And (4) conveying the gypsum slag obtained by the treatment in the step (3) into a size mixing stirring barrel D, mixing the gypsum slag, conveying the mixed gypsum slag to a flotation system, performing low-concentration flotation to enrich gold, silver and copper, and performing once roughing, twice fine concentration and twice scavenging to obtain high-quality gold-containing silver and copper concentrate and tailings (discharged waste residues). In the process, 300g/t of dispersing agent sodium hexametaphosphate is added in the pulp mixing procedure, and the dosages of the butyl xanthate as the collecting agents of roughing, scavenging and scavenging are respectively 50g/t, 30g/t and 10g/t; the dosage of roughing and scavenging foamer No. 2 oil is 40g/t and 20g/t respectively, and the concentration of roughing pulp is 20%.
The test results obtained were: the copper grade of the copper concentrate is 30.68 percent, the gold grade is 36.87g/t, the silver grade is 64.88g/t, the copper recovery rate is 76.55 percent, the gold recovery rate is 74.69 percent, and the silver recovery rate is 75.48 percent.
1 、S 2 、S 3 Comparative test results
Figure 644467DEST_PATH_IMAGE002
As can be seen from the above table, in step (2), when the butylammonium black is not added in step S2, the recovery rate of gold, silver and copper is reduced compared to that of step S1, because: the method does not add the butylammonium black powder, hydrophobic copper sulfide gold and silver flocs cannot be generated, and occlusion and entrapment are easily generated on the surface of calcium sulfate in the process of sulfuric acid precipitation, so that copper sulfide and gold and silver particles cannot become independent free particles, and the grade and recovery rate of the gold and silver-containing copper concentrate are influenced.
In S3, calcium carbonate is not added, and the lime is directly used for carrying out sulfuric acid precipitation treatment, so that the recovery rate of gold, silver and copper is better than that of the reference S2, but is reduced compared with that of S1, and the reasons are as follows: calcium carbonate is not added, lime is directly added, the lime solubility is high, the adding speed of calcium ions in the solution is too high, the generated gypsum particles are fine and difficult to precipitate and filter, the gold, silver and copper particles are easily adsorbed due to too large surface area, occlusion and inclusion are generated, the flotation separation of gold, silver and copper and gypsum is influenced, and the grade and the recovery rate of gold-containing silver and copper concentrate are reduced.
In conclusion, the washing liquid of the pyrite roasting slag containing gold, silver and copper is treated by adopting the method, so that high-quality gold, silver and copper-containing concentrate is obtained, valuable components such as gold, silver, copper and the like are comprehensively and well recovered, resources are comprehensively utilized in a high-efficiency manner, and the comprehensive economic benefit of a gold mine is improved; the discharged waste residues and waste liquid reach the industrial discharge standard of a better grade, and the safety risk brought to the generation of gold mines due to the discharge of the waste residues and waste liquid with high anti-dissolving components is avoided. The process has the advantages of good adaptability, simple process, environmental protection, safety and reliability, and has wide industrial application and popularization values.

Claims (2)

1. A system for treating washing liquid of pyrite roasting slag containing gold, silver and copper is characterized by comprising a stirring barrel, a thickener and a flotation unit;
the stirring barrel comprises a stirring barrel A, a stirring barrel E, a stirring barrel B, a stirring barrel C and a stirring barrel D, wherein the stirring barrel A, the stirring barrel E and the stirring barrel B are sequentially connected through a slurry pump, an overflow outlet of the stirring barrel A is connected with a feed inlet of the stirring barrel E through the slurry pump, and an overflow outlet of the stirring barrel E is connected with a feed inlet of the stirring barrel B through the slurry pump;
an overflow outlet of the stirring barrel B is connected with a feed inlet at the upper end of the thickener A through an ore pulp pump, and a slurry sinking discharge outlet at the lower end of the thickener A is connected with a feed inlet of the filter press A;
an overflow outlet at the upper end of the thickener A and a filtrate outlet of the thickener A are connected with a feed inlet of a stirring barrel C through an ore pulp pump, an overflow outlet of the stirring barrel C is connected with a feed inlet of a thickener B through the ore pulp pump, and a slurry sinking discharge outlet at the lower end of the thickener B is connected with a feed inlet of a filter press B;
an overflow outlet at the upper end of the thickener B and a filtrate outlet of the thickener B are discharged;
filter cake outlets of the filter press A and the filter press B are connected with a feed inlet of the stirring barrel D;
the discharge hole of the stirring barrel D is connected with the feed inlet of the flotation unit;
the flotation unit comprises a roughing unit, a scavenging unit I, a scavenging unit II, a fine selection unit I and a fine selection unit II;
adding sodium hydrosulfide into the stirring barrel A, adding butylammonium black powder into the stirring barrel E, adding calcium carbonate into the stirring barrel B, and adding lime into the stirring barrel C.
2. The system for treating the washing liquid of the pyrite roasting slag containing gold, silver and copper according to claim 1, wherein the roughing unit is composed of 5 flotation machines which are connected in series in sequence;
the scavenging machine set I is formed by sequentially connecting 4 flotation machines in series;
the second scavenging machine set is formed by sequentially connecting 4 flotation machines in series;
the first selection unit is formed by sequentially connecting 4 flotation machines in series;
the second fine selection unit is formed by sequentially connecting 3 flotation machines in series;
a discharge port of the stirring barrel D is connected with a feeding port of a first flotation machine in the roughing unit, a tailing outlet of a last flotation machine in the roughing unit is connected with a feeding port of a first flotation machine in the scavenging unit, a tailing outlet of a last flotation machine in the scavenging unit is connected with a feeding port of a first flotation machine in the scavenging unit II, and a tailing outlet of a last flotation machine in the scavenging unit II is flotation tailings;
the concentrate outlets of all the flotation machines in the first scavenging machine set are gathered and then connected with the first flotation machine feed inlet in the roughing machine set, and the concentrate outlets of all the flotation machines in the second scavenging machine set are gathered and then connected with the first flotation machine feed inlet in the first scavenging machine set;
the concentrate outlets of all the flotation machines in the roughing unit are gathered and then connected with the feed inlet of the first flotation machine in the first concentration unit, the concentrate outlets of all the flotation machines in the first concentration unit are gathered and then connected with the feed inlet of the first flotation machine in the second concentration unit, the tailing outlet of the last flotation machine in the second concentration unit is connected with the feed inlet of the first flotation machine in the first concentration unit, the tailing outlet of the last flotation machine in the first concentration unit is connected with the feed inlet of the first flotation machine in the roughing unit, and the concentrate outlets of all the flotation machines in the second concentration unit are gathered into gold-containing silver-copper concentrate.
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