CN105132692A - Method for recovering valuable metal from secondary copper electrolysis anode mud - Google Patents
Method for recovering valuable metal from secondary copper electrolysis anode mud Download PDFInfo
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Abstract
The invention relates to a method for recovering valuable metal from secondary copper electrolysis anode mud. The method comprises the following steps that water at the normal temperature is added into the anode mud with the mass ratio of solid to liquid being 1: (3-5), the mixture is reacted at the normal temperature and normal pressure, and solid and liquid are separated to obtain washed residues and washed liquid; the washed residues are mixed with solid sodium carbonate according to the ratio of 1: (0.75-1.5), and the mixture is roasted for 1-5 h to obtain roasted materials; hot water is added into the roasted materials with the mass ratio of solid to liquid being 1: (3-5), the mixture is reacted for 1-5 h, solid and liquid are separated to obtain leached residues and leached liquid, and arsenic enters the leached liquid; and sulfuric acid is added into the washed liquid to prepare a sulfuric acid solution, the sulfuric acid solution is added into the leached residues with the mass ratio of solid to liquid being 1: (3-5), and the reaction is performed for 1-4 h at the temperature of 50-80 DEG C to obtain pickle liquid and pickle residues. According to the method, arsenic and tin in the anode mud can be separated and recovered at the same time, and the recovery rate is high.
Description
Technical field
The present invention relates to recycling of recyclable waste technical field, be specifically related to a kind of method reclaiming valuable metal in reclaimed copper electrolysis anode sludge.
Background technology
Reclaim all kinds of composition brass, copper-contained sludge is main reclaimed copper manufacturing enterprise, the raw material of regeneration mainly comprises the sludge containing heavy metal of the various complexity such as composition brass, copper-contained sludge, electroplating sludge, surface treatment waste and circuit board plant mud.Regenerative raw materials obtains electrolytic copper by pyrometallurgical smelting and electrorefining, can produce a large amount of anode sludge in electrolytic process in bottom of electrolytic tank deposition, containing various metals in the anode sludge, arsenic and Theil indices higher.For the reclaimed copper smelting enterprise being raw material with complicated copper-bearing waste material, often produce 1 ton of electrolytic copper, can output 50-100kg height arsenic height tin anode mud.In recent years, China's regeneration refined matte Industry Quick Development, the environmental protection treatment of the anode sludge that reclaimed copper electrolysis produces and comprehensive reutilization problem more and more receive publicity.
Reclaimed copper electrolysis anode sludge is different from raw ore blister copper electrolysis anode sludge, the raw material sources used due to this kind of reclaimed copper enterprise are numerous and diverse, all containing certain density tin in most electroplating sludge, copper-contained sludge, surface treatment waste, circuit board plant mud, and arsenic often by the conditioning agent as copper electrolyte self-purification impel remove deposition other metallic impurity, essential in cupric electrolysis technique, therefore a large amount of tin, arsenic is enriched in this kind of reclaimed copper electrolysis anode sludge, simultaneously containing the metal such as copper, lead, and composition fluctuation is larger.In such anode sludge, metal content is tin 19% ~ 45%, arsenic 4% ~ 13%, copper 5% ~ 10%, plumbous 7% ~ 17%.
Because the character of tin and arsenic is closely similar, while tin, arsenic, there is the difficulty increasing this kind of ANODE SLIME TREATMENT and utilize; In the conventional recycling processes of tin, High Concentration of Arsenic companion deposits the rate of recovery that not only can reduce tin, and arsenic is easily dispersed in each process procedure, and risk of environmental pollution is large.At present, do large quantifier elimination respectively to high arsenic content anode slurry or containing the extraction and isolation of tin anode mud both at home and abroad, and proposed much feasible processing method, but the comprehensive reutilization of the anode sludge simultaneously containing High Concentration of Arsenic, tin and process there is not yet.
Summary of the invention
Based on this, the invention provides a kind of separable go out the method for arsenic and tin in reclaimed copper electrolysis anode sludge, and the rate of recovery is high.
The invention provides a kind of method reclaiming valuable metal in reclaimed copper electrolysis anode sludge, comprise the steps:
First step: add normal-temperature water according to the ratio of solid-liquid mass ratio 1:3-5 in the anode sludge, react 5min-30min under normal temperature and pressure, solid-liquid separation, slag and water lotion must be washed;
Second step: described washing slag mixes with the ratio of solid sodium carbonate according to 1:0.75-1.5, at 600 DEG C-750 DEG C roasting temperature 1h-5h, obtains roasting material;
Third step: add the hot water of 80-90 DEG C according to solid-liquid mass ratio 1:3-5 in described roasting material or add normal-temperature water and be heated to 80 DEG C-90 DEG C, reaction 1h-5h, solid-liquid separation, obtains leached mud and leach liquor, and arsenic enters in described leach liquor;
4th step: add sulfuric acid in described water lotion, be mixed with sulphuric acid soln, described sulphuric acid soln adds in described leached mud according to solid-liquid mass ratio 1:3-5,1h-4h is reacted under temperature 50 C-80 DEG C of conditions, solid-liquid separation, obtain pickling liquor and acid leaching residue, most copper enters in described pickling liquor, and tin and lead enter in described acid leaching residue.
Reclaim the method for valuable metal in described reclaimed copper electrolysis anode sludge, also comprise the steps: that described leach liquor is high density arsenic containing solution, can be used as and produce arsenic product containing arsenic raw material, or adopt the heavy arsenic method of open report to reclaim arsenic.
Reclaim the method for valuable metal in described reclaimed copper electrolysis anode sludge, also comprise the steps: that described pickling liquor is mixed with electrolytic solution, return electrowinning process and reclaim copper.
Wherein in an embodiment, the concentration of described sulphuric acid soln is 1mol/L-4mol/L.
Wherein in an embodiment, in described first step, the described reaction times is 5min-10min.
Wherein in an embodiment, in described second step, described roasting time is 1.5h-2.5h.
Wherein in an embodiment, in described third step, the described reaction times is 1.5h-2h.
Wherein in an embodiment, in described 4th step, the described reaction times is 1h-2h.
Wherein in an embodiment, described solid-liquid separating method is filtering separation.
Reclaim the method for valuable metal in reclaimed copper electrolysis anode sludge of the present invention, its compared with prior art:
The method that the present invention adopts washing, basic roasting and pickling to combine, successively can isolate the arsenic in the anode sludge and tin metal, then reclaim other valuable metals, arsenic and tin good separating effect, the rate of recovery is high, and " three wastes " generation is few, easy improvement, and can not secondary pollution be produced.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method reclaiming valuable metal in reclaimed copper electrolysis anode sludge described in the embodiment of the present invention.
Embodiment
For the ease of understanding the present invention, will be described more fully the present invention below.But the present invention can realize in many different forms, is not limited to embodiment described herein.On the contrary, provide the object of these embodiments be make the understanding of disclosure of the present invention more comprehensively thorough.
Unless otherwise defined, all technology used herein and scientific terminology are identical with belonging to the implication that those skilled in the art of the present invention understand usually.The object of term used in the description of the invention herein just in order to describe specific embodiment, is not intended to be restriction the present invention.
The invention provides a kind of method reclaiming valuable metal in reclaimed copper electrolysis anode sludge, comprise the steps:
First step: add normal-temperature water according to the ratio of solid-liquid mass ratio 1:3-5 in the anode sludge, react 5min-30min under normal temperature and pressure, solid-liquid separation, slag and water lotion must be washed;
Second step: described washing slag mixes with the ratio of solid sodium carbonate according to 1:0.75-1.5, at 600 DEG C-750 DEG C roasting temperature 1h-5h, obtains roasting material;
Third step: add the hot water of 80-90 DEG C according to solid-liquid mass ratio 1:3-5 in described roasting material or add normal-temperature water and be heated to 80 DEG C-90 DEG C, reaction 1h-5h, solid-liquid separation, obtains leached mud and leach liquor, and arsenic enters in described leach liquor;
4th step: add sulfuric acid in described water lotion, be mixed with sulphuric acid soln, described sulphuric acid soln adds in described leached mud according to solid-liquid mass ratio 1:3-5,1h-4h is reacted under temperature 50 C-80 DEG C of conditions, solid-liquid separation, obtain pickling liquor and acid leaching residue, most copper enters in described pickling liquor, and tin and lead enter in described acid leaching residue.
With reference to Fig. 1, in above-mentioned reclaimed copper electrolysis anode sludge, reclaim the method for valuable metal specifically:
Roughly containing, for example the component of lower content in reclaimed copper electrolysis anode sludge: Sn30%-40%, As4%-13%, Pb5%-15%, Cu6%-8%, the above-mentioned anode sludge is respectively by washing, roasting, hot water leaching and acid pickling step, isolate arsenic and tin and other valuable metal respectively, as plumbous and copper, tin is separated by the separation method of routine again with plumbous, or prepares terne metal.
Washing step is wherein: wash high arsenic height tin anode mud with clear water normal temperature, washing deviates to be attached to sulfuric acid and the copper sulfate on anode sludge surface, tentatively reclaims copper, and the acid that wash-out is carried secretly, reduce the acidic substance in the anode sludge, to reduce the consumption of alkali in follow-up basic roasting.Water-washing step is specifically: in the anode sludge, add normal-temperature water, react, solid-liquid separation under normal temperature and pressure, must wash slag and water lotion, wherein the solid-liquid mass ratio of normal-temperature water and the anode sludge is 1:3-5, reaction times 5min-30min.In this step, in the anode sludge, the copper of 50%-56% enters water lotion, and water lotion is certain acidity, can be used for follow-up acidleach operation and reclaims copper further.Tin in the anode sludge, arsenic and lead not stripping, stay in washing slag.
Basic roasting operation is wherein: the washing slag after washing mixes with the ratio of solid, powdery sodium carbonate in 1:0.75-1.5, roasting 1h-5h under 600 DEG C of-750 DEG C of temperature condition.Under this condition, the arsenic in the anode sludge keeps higher reactive behavior, and preferential conversion is sodium arseniate; And under this condition, the reactive behavior of tin is less, only have a small amount of tin (<5%) to be converted into sodium stannate, product of roasting is roasting material simultaneously.
Water logging wherein goes out operation: roasting material hot water leaching, leaching condition is: solid-liquid mass ratio 1:3-5, temperature 80 DEG C-90 DEG C, reaction times 1h-5h, solid-liquid separation, obtain leached mud and leach liquor, in fired slags, the arsenic of 90%-95% enters leach liquor with sodium arseniate form, and the tin being about less than 5% enters leach liquor with sodium stannate form simultaneously, this leach liquor main component is: arsenic 10.0g/L-20.0g/L, tin 0.2g/L-0.7g/L, plumbous 0g/L-0.2g/L, can as the raw material for extracting arsenic.And the copper of 99%-100% and the lead of 98%-99% are stayed in leached mud.
Pickling process is wherein: alkaline leaching slag tin-dominant, lead and copper after dearsenification.The water lotion adopting washing step to produce is mixed with the sulphuric acid soln of 1mol/L-4mol/L concentration, carries out acidic leaching, solid-liquid separation, obtain pickling liquor and acid leaching residue to leached mud.Leaching condition: the solid-liquid mass ratio 1:3-5 of leached mud and sulphuric acid soln, temperature 50 C-80 DEG C, reaction times 1h-4h, in leached mud, the copper of 70%-80% enters pickling liquor, and in acid leaching residue, the content of copper is lower than 1.5%, does not affect follow-up tin, plumbous recovery.The keto-acid containing immersion liquid of acidic leaching can return reclaimed copper enterprise cupric electrolysis operation and be mixed with electrolytic solution, reclaims copper wherein, or adopts the usual way such as extraction, ion-exchange of open report to reclaim copper.Acid leaching residue tin-dominant 45%-55%, plumbous 14%-17%, arsenic 0.8%-1.5%, can be used as tin leady raw materials and produce tin and lead by Xi Qian smelting enterprise, or for the production of terne metal.
Below will by several embodiment come the present invention is described further.
Embodiment one
Reclaim the method for valuable metal in reclaimed copper electrolysis anode sludge of the present invention, comprise the steps:
In the present embodiment, high arsenic height tin anode mud dries rear sample composition Sn32.30%, As8.50%, Pb9.53%, Cu7.14%, Ni1.72%, get anode sludge dry sample 229.43g, the anode sludge mixes by solid-liquid mass ratio 1:5 with normal-temperature water, mixed solution is stirring reaction 30min in beaker, mixing speed 250rpm.After reaction terminates, solid-liquid filtration is separated, and must wash slag and water lotion, and water lotion is retained for subsequent use.Comprise in washing slag: As10.32%, Sn38.84%, Cu4.17%, Pb12.37%.Washing slag is ground to 80 orders after drying, according to washing slag: sodium carbonate is that the mass ratio of 1:1 adds solid powdery sodium carbonate in the washing slag of drying, and mix, at 720 DEG C of temperature, basic roasting reacts 4 hours, obtains roasting material.Roasting material adds normal-temperature water by solid-liquid mass ratio 1:5, is heated to temperature of reaction 90 DEG C, 4 hours reaction times, stirring intensity 250rpm.After having reacted, solid-liquid filtration is separated, and obtain leached mud and leach liquor, wherein leach liquor comprises: As21.69g/L, Sn1.01g/L, Pb0.07g/L, Cu and Ni not stripping; Above-mentioned leach liquor, containing High Concentration of Arsenic, can adopt the conventional method Separation and Recovery arsenic from leach liquor adding the heavy arsenic such as molysite, calcium salt.Leached mud comprises: Sn48.34%, As0.61%, Pb17.35%, Cu5.71%, Ni0.47%.Roasting-leaching experiment the results are shown in Table 1, and the solubility rate of this step arsenic is the rate of recovery of 95.30%, Sn is 98.82%.Then, with above-mentioned water lotion preparation sulphuric acid soln, above-mentioned sulphuric acid soln in leached mud, is added, leach copper, the concentration of sulphuric acid soln is 2mol/L, temperature of reaction 60 DEG C, reaction times 4h, obtains pickling liquor and acid leaching residue, and above-mentioned pickling liquor is containing Cu6.40g/L, Ni0.33g/L.Pickling liquor can return to cupric electrolysis workshop, is mixed with electrolytic solution, reclaims copper.Acid leaching residue contains: Sn51.69%, As0.64%, Pb16.40%, Cu1.47%, Ni0.37%.Acid leaching residue can be used as Tin concentrate product, for reclaiming tin lead or preparing tinsel.Table one is the result reckoner of a kind of example utilizing the recovery method described in embodiment one.Wherein
Table 1: case one roasting-extracting stage experiment analysis results
The Sn rate of recovery=(335.92 × 48.34%)/(423.07 × 38.84%) × 100%=98.82%.
As solubility rate=(1918.32 × 21.69/1000)/(423.07 × 10.32%) × 100%=95.30%.
Embodiment two
In the present embodiment, high arsenic height tin anode mud dries rear sample composition Sn30.75%, As8.50%, Pb9.53%, Cu7.14%, Ni1.72%, the anode sludge mixes by solid-liquid mass ratio 1:5 with normal-temperature water, mixed solution is stirring reaction 30min in beaker, mixing speed 250rpm.After reaction terminates, solid-liquid filtration is separated, and must wash slag and water lotion, and water lotion is retained for subsequent use.Comprise in washing slag: As10.32%, Sn36.54%, Cu4.10%, Pb12.05%.Washing slag is ground to 80 orders after drying.According to washing slag: sodium carbonate is that the mass ratio of 1:1 adds solid powdery sodium carbonate in the washing slag of drying, and mix, at 650 DEG C of temperature, basic roasting reacts 4 hours, obtains roasting material.Roasting material adds the hot water of 90 DEG C by solid-liquid mass ratio 1:5,4 hours reaction times, stirring intensity 250rpm, after having reacted, solid-liquid filtration is separated, and obtains leached mud and leach liquor, wherein leach liquor comprises: As11.64g/L, Sn1.82g/L, Pb0.30g/L, Cu and Ni not stripping; Above-mentioned leach liquor, containing High Concentration of Arsenic, can adopt the conventional method Separation and Recovery arsenic from leach liquor adding the heavy arsenic such as molysite, calcium salt.Leached mud comprises: Sn50.51%, As0.53%, Pb16.70%, Cu5.66%, Ni0.60%.As calculated, the solubility rate of this step arsenic is the rate of recovery of 96.41%, Sn is 95.77%, and method of calculation, with embodiment one, do not repeat them here.Then, with above-mentioned water lotion preparation sulphuric acid soln, above-mentioned sulphuric acid soln in leached mud, is added, leach copper, the concentration of sulphuric acid soln is 2mol/L, temperature of reaction 50 DEG C, reaction times 2h, obtains pickling liquor and acid leaching residue, and above-mentioned pickling liquor is containing Cu5.35g/L, Ni0.33g/L.Pickling liquor can return to cupric electrolysis workshop, is mixed with electrolytic solution, reclaims copper.Acid leaching residue contains: Sn52.73%, As0.25%, Pb16.89%, Cu1.42%, Ni0.40%.Acid leaching residue can be used as Tin concentrate product, for reclaiming tin lead or preparing tinsel.
Embodiment three
In the present embodiment, high arsenic height tin anode mud dries rear sample composition Sn31.41%, As7.28%, Pb8.86%, Cu7.17%, Ni1.79%, the anode sludge mixes by solid-liquid mass ratio 1:5 with normal-temperature water, mixed solution is stirring reaction 20min in beaker, mixing speed 250rpm.After reaction terminates, solid-liquid filtration is separated, and must wash slag and water lotion, and water lotion is retained for subsequent use, comprises: As9.52%, Sn37.64%, Cu4.20%, Pb10.52% in washing slag.Washing slag is ground to 80 orders after drying.According to washing slag: sodium carbonate is that the mass ratio of 1:1.25 adds solid powdery sodium carbonate in the washing slag of drying, and mix, at 620 DEG C of temperature, basic roasting reacts 4 hours, obtains roasting material.Roasting material adds the hot water of 80 DEG C by solid-liquid mass ratio 1:5,4 hours reaction times, stirring intensity 250rpm, after having reacted, solid-liquid filtration is separated, and obtains leached mud and leach liquor, wherein leach liquor comprises: As20.18g/L, Sn0.69g/L, Pb0.16g/L, Cu and Ni not stripping; Above-mentioned leach liquor, containing High Concentration of Arsenic, can adopt the conventional method Separation and Recovery arsenic from leach liquor adding the heavy arsenic such as molysite, calcium salt.Leached mud comprises: Sn49.47%, As1.03%, Pb15.15%, Cu4.70%, Ni0.47%.The solubility rate of this step arsenic is the rate of recovery of 95.23%, Sn is 96.71%.Then, with above-mentioned water lotion preparation sulphuric acid soln, above-mentioned sulphuric acid soln in leached mud, is added, leach copper, the concentration of sulphuric acid soln is 2mol/L, temperature of reaction 60 DEG C, reaction times 2h, obtains pickling liquor and acid leaching residue, and above-mentioned pickling liquor is containing Cu5.46g/L, Ni0.33g/L.Pickling liquor can return to cupric electrolysis workshop, is mixed with electrolytic solution, reclaims copper.Acid leaching residue contains: Sn48.88%, As1.02%, Pb16.74%, Cu1.69%, Ni0.35%.Acid leaching residue can be used as Tin concentrate product, for reclaiming tin lead or preparing tinsel.
Embodiment four
In the present embodiment, high arsenic height tin anode mud dries rear sample composition Sn31.46%, As7.0%, Pb8.12%, Cu6.17%, Ni1.75%, the anode sludge mixes by solid-liquid mass ratio 1:3 with normal-temperature water, mixed solution is stirring reaction 5min in beaker, mixing speed 250rpm.After reaction terminates, solid-liquid filtration is separated, and must wash slag and water lotion, and water lotion is retained for subsequent use, comprises: As8.84%, Sn37.23%, Cu3.56%, Pb11.25% in washing slag.Washing slag is ground to 80 orders after drying.According to washing slag: sodium carbonate is that the mass ratio of 1:0.75 adds solid powdery sodium carbonate in the washing slag of drying, and mix, at 600 DEG C of temperature, basic roasting reacts 2.5 hours, obtains roasting material.Roasting material adds normal-temperature water by solid-liquid mass ratio 1:3, continue to be heated to temperature of reaction 90 DEG C, 1.5 hours reaction times, stirring intensity 250rpm, after having reacted, solid-liquid filtration is separated, and obtains leached mud and leach liquor, wherein leach liquor comprises: As18.18g/L, Sn0.5g/L, Pb0.1g/L, Cu and Ni not stripping; Above-mentioned leach liquor, containing High Concentration of Arsenic, can adopt the conventional method Separation and Recovery arsenic from leach liquor adding the heavy arsenic such as molysite, calcium salt.Leached mud comprises: Sn38.47%, As0.82%, Pb14.15%, Cu3.70%, Ni0.51%.The solubility rate of this step arsenic is the rate of recovery of 90.23%, Sn is 92.71%.Then, with above-mentioned water lotion preparation sulphuric acid soln, above-mentioned sulphuric acid soln in leached mud, is added, leach copper, the concentration of sulphuric acid soln is 2mol/L, temperature of reaction 60 DEG C, reaction times 2h, obtains pickling liquor and acid leaching residue, and above-mentioned pickling liquor is containing Cu5.60g/L, Ni0.23g/L.Pickling liquor can return to cupric electrolysis workshop, is mixed with electrolytic solution, reclaims copper.Acid leaching residue contains: Sn44.34%, As0.94%, Pb16.0%, Cu1.48%, Ni0.03g/L.Acid leaching residue can be used as Tin concentrate product, for reclaiming tin lead or preparing tinsel.
In above-described embodiment, pickling liquor is copper-bath, cupric 5g/L-8g/L, in addition containing the sulfuric acid of 1-4mol/L.In view of the sulfuric acid in electrolytic solution in copper electrolytic process can constantly consume, need supplementary sulphuric acid soln, therefore, pickling liquor is mixed with copper-containing sulfuric acid solution, then returns cupric electrolysis operation, the sulfuric acid of consumption can be supplemented.Copper is deposited as electrolytic copper and is recovered in electrowinning process.
In above-described embodiment, acid leaching residue prepares terne metal and recovery tin, plumbous method are: acid leaching residue can be produced by the method for retailoring obtain terne metal.Acid leaching residue can also adopt vacuum oven reduction furnace to make tin and lead be separated into metallic tin and lead at different volatilization temperature.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. reclaim the method for valuable metal in reclaimed copper electrolysis anode sludge, it is characterized in that, comprise the steps:
First step: add normal-temperature water according to the ratio of solid-liquid mass ratio 1:3-5 in the anode sludge, react 5min-30min under normal temperature and pressure, solid-liquid separation, slag and water lotion must be washed;
Second step: described washing slag mixes with the ratio of solid sodium carbonate according to 1:0.75-1.5, at 600 DEG C-750 DEG C roasting temperature 1h-5h, obtains roasting material;
Third step: add the hot water of 80-90 DEG C according to solid-liquid mass ratio 1:3-5 in described roasting material or add normal-temperature water and be heated to 80 DEG C-90 DEG C, reaction 1h-5h, solid-liquid separation, obtains leached mud and leach liquor, and arsenic enters in described leach liquor;
4th step: add sulfuric acid in described water lotion, be mixed with sulphuric acid soln, described sulphuric acid soln adds in described leached mud according to solid-liquid mass ratio 1:3-5,1h-4h is reacted under temperature 50 C-80 DEG C of conditions, solid-liquid separation, obtain pickling liquor and acid leaching residue, most copper enters in described pickling liquor, and tin and lead enter in described acid leaching residue.
2. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, also comprise the steps: that described leach liquor is high density arsenic containing solution, can be used as and produce arsenic product containing arsenic raw material, or adopt the heavy arsenic method of open report to reclaim arsenic.
3. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, also comprise the steps: that described pickling liquor is mixed with electrolytic solution, return electrowinning process and reclaim copper.
4. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, the concentration of described sulphuric acid soln is 1mol/L-4mol/L.
5. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, in described first step, the described reaction times is 5min-30min.
6. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, in described second step, described roasting time is 1h-5h.
7. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, in described third step, the described roasting material Leaching reaction time is 1h-5h.
8. reclaim the method for valuable metal according to claim 1 in reclaimed copper electrolysis anode sludge, it is characterized in that, in described 4th step, the described acid-leaching reaction time is 1h-4h.
9. reclaim the method for valuable metal in reclaimed copper electrolysis anode sludge according to any one of claim 1-9, it is characterized in that, described solid-liquid separating method is filtering separation, centrifugation or other solid-liquid separating methods.
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| CN108048666A (en) * | 2017-12-21 | 2018-05-18 | 广东环境保护工程职业学院 | Method and the application of metal are recycled in a kind of electric precipitator dusts from copper metallurgy |
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| CN106011930B (en) * | 2016-07-28 | 2018-09-25 | 河南豫光金铅股份有限公司 | A kind of continuous preparation method of cupric electrolysis refining electrolyte |
| CN107227466A (en) * | 2017-06-26 | 2017-10-03 | 郴州市金贵银业股份有限公司 | A kind of method that chlorine oxygen copper dechlorination carries copper |
| CN107619940A (en) * | 2017-09-28 | 2018-01-23 | 深圳万佳互动科技有限公司 | A kind of method that copper is reclaimed from metallurgical slag |
| CN107674984A (en) * | 2017-09-28 | 2018-02-09 | 深圳万佳互动科技有限公司 | The recovery method of valuable metal in a kind of metallurgical slag |
| CN107674984B (en) * | 2017-09-28 | 2019-09-06 | 河北纵横集团丰南钢铁有限公司 | The recovery method of valuable metal in a kind of metallurgical slag |
| CN107619940B (en) * | 2017-09-28 | 2019-10-29 | 广西盛畅物流有限公司 | A method of recycling copper from metallurgical slag |
| CN108048666A (en) * | 2017-12-21 | 2018-05-18 | 广东环境保护工程职业学院 | Method and the application of metal are recycled in a kind of electric precipitator dusts from copper metallurgy |
| CN108048664A (en) * | 2017-12-21 | 2018-05-18 | 广东环境保护工程职业学院 | The method of dearsenification and application in a kind of mud from black copper |
| CN108103320A (en) * | 2017-12-21 | 2018-06-01 | 广东环境保护工程职业学院 | Method and the application of metal are recycled in a kind of sack dust from reverberatory furnace |
| CN112441611A (en) * | 2020-12-07 | 2021-03-05 | 云南锡业锡化工材料有限责任公司 | Method for preparing tin dioxide by using sponge tin and anode mud |
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