CN115572832A - Method for treating high-gold high-silver material containing copper, antimony, tin and lead - Google Patents
Method for treating high-gold high-silver material containing copper, antimony, tin and lead Download PDFInfo
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Abstract
The invention discloses a method for separating a copper-antimony-tin-lead-containing high-gold and high-silver material, which comprises the following steps of: (1) ball-milling the materials to obtain a material with a granularity of more than 80 meshes; (2) primary acid leaching: adding a mixed solution of hydrogen peroxide and hydrochloric acid into the ball-milled material obtained in the step (1), reacting for 2-6 hours at the temperature of 60-80 ℃, and adding a part of precipitator to precipitate lead 1 hour before filter pressing after the reaction is finished, so as to prevent the lead chloride from cooling, crystallizing and blocking pipelines, valves and delivery pumps; (3) secondary acid leaching; (4) carrying out primary acid liquor replacement; (5) hydrolyzing; (6) oxidizing; (7) neutralizing and depositing tin; (8) copper replacement. The method provided by the invention has the advantages of high recovery rate of the final precious metals of gold and silver, thorough hydrolysis of antimony, high copper purity and stable technological process.
Description
Technical Field
The invention belongs to the technical field of separation and enrichment of nonferrous metals, and particularly relates to a separation method of a high-gold high-silver material containing copper, antimony, tin and lead.
Background
In the technical field of separation and enrichment of nonferrous technologies, the precious metals are expensive, so that the precious metals are always important to be separated and purified. For the separation and enrichment of copper, antimony, tin, lead, gold and silver materials, the basic idea is that hydrochloric acid and oxidant are added to completely dissolve base metals, antimony, copper and tin are gradually separated from solution, and precious metals enter a pyrometallurgical smelting process. The main technical problems of the prior art are as follows: and (1) the gold and silver contained in the pickle liquor is high. (2) The hydrolysis is not thorough when antimony is hydrolyzed, the hydrolyzed solution contains 2 to 3g/l of antimony, the silver content in the antimony oxychloride is about 4000g/t, sometimes even up to 8000 to 9000g/t; the gold content is 8-10 g/t; the tin content is generally about 6 to 8%. (3) the copper powder produced by the substitution was mixed with 4% of tin. The recovery rate of metals such as gold, silver, tin, antimony and the like is not ideal due to the points, and the subsequent treatment and recovery are difficult and complicated.
Disclosure of Invention
The invention aims to provide a method for treating a high-gold high-silver material containing copper, antimony, tin and lead, and the method has the advantages of high recovery rate of precious metals of gold and silver, thorough hydrolysis of antimony, high copper purity and stable technological process.
The invention adopts the following technical scheme:
a method for separating a copper-antimony-tin-lead-containing high-gold high-silver material comprises the following steps:
(1) Ball milling the materials to obtain a particle size of more than 80 meshes;
(2) Primary acid leaching: adding a mixed solution of hydrogen peroxide and hydrochloric acid into the ball-milled material obtained in the step (1), reacting for 2-6 hours at the temperature of 60-80 ℃, and adding a part of precipitator to precipitate lead 1 hour before filter pressing after the reaction is finished, so as to prevent the lead chloride from cooling, crystallizing and blocking pipelines, valves and delivery pumps;
(3) Secondary acid leaching: after the precipitation is finished, filter-pressing the slurry to obtain primary filter residue and primary filtrate, adding hydrochloric acid into the filter residue to carry out secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out primary acid leaching at the same liquid-solid ratio, temperature and reaction time, after the secondary acid leaching is finished, separating to obtain secondary filtrate and secondary filter residue, cleaning the secondary filter residue, airing the secondary filter residue, entering a pyrogenic process section to recover gold and silver, and returning the secondary filtrate to the primary acid leaching;
copper and tin are further removed through a secondary acid leaching step, so that the separation efficiency is improved;
(4) Primary acid liquor replacement: adding fresh anode mud or crude antimony powder into the primary filtrate obtained in the step (2) to reduce free gold and silver in the solution into a simple substance state, and reducing Sb existing in the solution 5+ Conversion to Sb 3+ Obtaining a replacement solution after replacement;
(5) Hydrolysis: regulating the pH value of the replacement liquid obtained in the step (4) to 0.4-0.6 by using a pH value regulator, supplementing water with the volume being 3-4 times that of the replacement liquid, controlling the temperature to be 35-55 ℃, controlling the stirring speed to be 105-120 r/mjn, reacting for 20-40 min, and filtering and separating to obtain antimony oxychloride and antimony hydrolysate post-liquid;
(6) And (3) oxidation: adding oxidant into the antimony hydrolyzed liquid obtained in the step (5) to obtain Sn 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin deposition: neutralizing the completely oxidized solution with neutralizer, controlling pH = 2.0-2.5, and Sn in the solution 4+ Precipitating, filter-pressing, blowing, washing for many times, drying filter residues, and then performing pyrogenic process for tin recovery;
(8) Copper replacement: and (4) adding iron powder into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper precipitates containing more than 80% of copper, wherein the replacement rate is more than 99%, and the wastewater generated by copper precipitation is directly fed into a sewage center for harmless treatment.
Further, in the step (2), the liquid-solid ratio of the mixed solution of hydrogen peroxide and hydrochloric acid to the material is 2-4: 1, the concentration of hydrochloric acid is 5-7 mol/L, and the mass percentage content of hydrogen peroxide is 0-10%.
Further, in the step (5), the pH value regulator is sodium hydroxide or ammonia water solution, preferably ammonia water, and if the addition amount of the ammonia water is too much, antimony white can be directly generated.
Further, in the step (5), the antimony oxychloride can be dissolved by ammonia water to prepare antimony white or the crude antimony is smelted by a fire method.
Further, in the step (7), the Sn content in the solution after tin precipitation is less than 0.15g/l.
Further, in the step (2), the precipitant is at least one of sodium sulfate, sodium bisulfate, sulfuric acid and sodium sulfite, the addition amount of the precipitant is 0.8 times of the mass of the lead, and when the sodium sulfite is used as the precipitant, the oxidant can oxidize the sodium sulfite into the sodium sulfate and consume the redundant oxidant in the solution, thereby being beneficial to the operation of the subsequent step.
Further, in the step (3), an oxidant is added in the secondary acid leaching process, wherein the oxidant is at least one of sodium chlorate, oxygen, hydrogen peroxide and percarbonateamide.
Furthermore, in the step (8), the adding amount of the iron powder is 0.9 to 1 time of the mass of the copper.
Further, the neutralizing agent in the step (7) is at least one of sodium hydroxide and sodium carbonate, sodium carbonate and sodium bicarbonate, ammonium sulfate and ammonia water. When the latter two neutralizers are adopted, the pH value can be more stably controlled, and particularly when the ammonium sulfate and the ammonia water are adopted for neutralization, no gas is generated, thereby being beneficial to process control.
Furthermore, the content of gold in antimony oxychloride is less than 2g/t, the content of silver is less than 1000g/t, the content of tin is less than 2.0%, the recovery rate of gold and silver is improved by 1-2% compared with the original process, and the direct recovery rate of tin is improved by 4-6%.
Compared with the prior art, the invention has the following advantages:
1. by repeated research and comparative experiments, the method can efficiently treat the materials containing copper, antimony, tin and lead. Through twice acid leaching, the leaching rate of base metals is obviously improved; lead in the solution is added into the slag in the form of lead sulfate, which is beneficial to the subsequent pyrometallurgical recovery of the noble slag. The added solution replacement link greatly reduces the loss of the gold and silver in the leaching link,
2. the method adds secondary acid leaching in the leaching link, selects low acid leaching tin antimony, high acid leaching copper, and returns high acid solution to complex acid for low acid leaching. The low acid liquor is replaced by self-produced fresh anode mud, so that the content of gold and silver in the leaching liquor is reduced, and sb in the solution is also replaced 5+ Reduction to sb 3+ So as to completely hydrolyze the antimony.
3. The neutralization tin precipitation and the recovery of copper are exchanged in process sequence, firstly, hydrolysis and post-oxidation are carried out, tin is precipitated in a tin hydroxide form, and the filtered liquid is replaced to recover copper, so that the loss of tin is avoided.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the disclosure.
Example 1
The existing material comprises the following main components (%): sb 23.31Sn 39.16 Pb 1.45 Cu 3.57Ag 10.69 Au 0.0168
200 g of 80-mesh dried material is slowly added into 600 ml of 6mol/L hydrochloric acid, stirred, heated to 80 ℃ and reacted for 4 hours. 1 hour before filtration, 2.4 g of sodium sulfate was added, filtration was carried out, washing was carried out with 5% diluted hydrochloric acid, and then washing was carried out with clear water to obtain an acid solution, wherein the total volume of the filtrate was 750 ml, and the content (g/l) of Sn was 98.60 Sb 53.61 Cu 9.07 Pb 0.06.Ag 0.17, and the amount of the residue was 64.6 g, which was determined by oven-drying and weighing, and the content was (%) Sn 6.77 Sb 9.92 Cu 0.53 Pb 4.41.Ag 32.99.
Carrying out secondary acid leaching on filter residues, preparing 195 ml of hydrochloric acid leaching liquid with the concentration of 8mol/L, carefully adding 64.6 g of leaching residues, heating to 80 ℃, stirring for reaction for 4 hours, cooling, filtering and washing. The filtrate (with wash) was 270 ml and left for use. The component (g/l) Sn 13.44 Sb19.96 Cu 0.89 Ag 0.22, and hydrochloric acid is added to prepare the reaction solution when the next leaching is carried out. The filter residue is dried and weighed by 43.2 g, and the components are (percent) Sb 1.89 Sn 1.52 Pb 0.01 Cu 0.17 Ag 49.07 Au 0.0772, the gold leaching rate is 99.26 percent, the silver leaching rate is 99.16 percent, the tin leaching rate is 99.1 percent, the copper-antimony leaching rate is more than 98 percent, the base metal components are lower, and the recovery rate of the gold and the silver by the fire method is effectively guaranteed.
Replacing 750 ml of primary leachate with fresh anode mud or crude antimony powder, and replacing silver ions and silver-chlorine complex ions suspended in the solution into a metal state to be recycled. Simultaneously adding Sb possibly existing in the solution 5+ Reduction to Sb 3+ So that the antimony is hydrolyzed and then is thoroughly separated from the copper and the tin. The addition amount of the antimony powder or the anode mud is 20 times of the mass of the free silver, 2.6 g of the antimony powder or the anode mud is added at this time, the Ag content of the filtrate is only 0.053g/l, and the effect is obvious.
Taking 250 ml of 1/3 of replacement liquid, adding a little sodium hydroxide to adjust the pH value to 0.5, uniformly stirring, adding 750 ml of water to dilute, heating to 40 ℃, clarifying, filtering and washing antimony oxychloride after antimony trichloride is completely dehydrated and converted into antimony oxychloride. 1025 ml of hydrolyzed solution with the components (g/l) of Sb 0.215 Sn 24.06 Cu 2.22 Ag 0.02, and the hydrolysis is complete to obtain 20.86 g of antimony mud with the components (%). Sb 60.17 Sn 0..16 Cu 0.22 Ag 0.06, and the direct yield of antimony is 93%.
1025 ml of hydrolysate is added with 28 ml of hydrogen peroxide for oxidation, 12.5 ml of caustic soda is added to adjust the pH value to 1.0, sodium carbonate solution is continuously added to adjust the pH value of the solution to 2.0, the solution is stirred for 30min with stable acidity, the solution is clarified and filtered after reacting for 1 hour, air is blown, the solution is washed by water until the washing solution has no copper color, the filtrate contains 1080 ml of water, the solution contains 0.097 Sn, the filter residue is dried and weighed to be 39.22g, the Sn content is 61.45 percent, and the direct yield of the Sn is 92.3 percent.
1080 ml of the solution after tin removal is added with 2.2 g of reduced iron powder and stirred for 1 hour, thus obtaining 2.72 g of copper powder with the content of 81.8 percent and the direct yield of copper of 93.49 percent.
Example 2
The material component (percent) is Sb 8.24 Sn 32.06 Pb 3.26 Cu 15.98 Ag 8.22 Au 0.0511.
300g of the second immersion liquid is taken and ball-milled, and is filtered by 80 meshes of raw materials, 200 ml of the second immersion liquid in the embodiment 1 is taken, the component (g/L) Sn 13.44 Sb19.96 Cu 0.89 Ag 0.22 is added, and industrial hydrochloric acid is added to prepare 900 ml of 6mol/L reaction liquid. Slowly adding the mixture, heating to 80 ℃, timing, and carrying out heat preservation leaching for 4 hours. 7.9 g of sodium sulfate is added 1 hour before filter pressing, filter pressing is carried out, 100 ml of 5% diluted hydrochloric acid is used for washing filter cakes, and 200 ml of clean water is used for washing acid liquor. The filtrate washings were combined to a total of 1250 ml. The component (g/l) is Sn 73.59 Sb 19.48 Cu 36.21 Pb 0.08 Ag 0.19, the filter cake is dried and weighed 90.92 g, and the main component (%) is Sn 7.30 Sb 4.51 Cu 2.86 Pb 10.72.
Then carrying out secondary acid leaching on the leaching residue. 275 ml of 6mol/L hydrochloric acid leaching solution is prepared, 90.92 g of leaching residue is slowly added, stirring is carried out, the temperature is increased to 80 ℃, timing is started, heat preservation leaching is carried out for 4 hours, 10 ml of hydrogen peroxide is added after 2 hours of reaction, cooling, filtering and blowing are carried out, 5% of dilute hydrochloric acid is added to wash filter cakes, and tin and copper ions are washed clean by clean water. The filtrate and washing liquid amounted to 505 ml, and the content (g/l) of the main component of Sn 12.13 Sb 6.97 Cu 4.79 Ag 0.26. The filter cake was dried and weighed 63.4 g, and the main components (%) Sn 1.21 Sb 0.98 Cu 0.75 Pb 15.09 Ag 38.51 Au 0.2416, the rate of gold incorporation was 99.86%, and the rate of silver incorporation was 99.02%. The leaching rate of tin is 98.9, and the leaching rates of copper and antimony are all more than 98%.
625 ml of first immersion liquid is taken and added with lead powder to replace free complex silver ions and Sb 5+ The adding amount of the antimony ions and the lead powder is about 30 to 40 times of the amount of the silver in the solution. Taking 35 times of the raw materials, adding 4.2 g of the raw materials for replacement for 2 hours, filtering, returning filter residues to perform primary acid leaching to recover precious metals, wherein the volume of the filtrate is about 640 ml, and the detected Ag is only 0.037g/l, so that the effect is obvious.
Taking 1/2 of the replacement solution and 320 ml, adding a little alkali liquor to adjust the pH value to 0.5, stirring, adding tap water with 3 times of volume to dilute, heating to about 40 ℃, controlling the rotating speed of a speed reducer to be 105-120 r/min, reacting until antimony trichloride is completely hydrolyzed, clarifying, filtering, and washing antimony oxychloride with water. The total amount of the hydrolyzed solution is 1380 ml, and the main component (g/l) of Sb is 0.25 Sn 17.15 Cu 8.45 Ag 0.03, and antimony oxychloride is dried and weighed for 9.8 g, contains 57.34 percent of antimony and has the direct yield of the antimony of 90.21 percent.
1380 ml of hydrolyzed solution is oxidized, the volume of hydrogen peroxide is 1.1 to 1.5 times of the tin amount, 26 ml of 20 percent industrial hydrogen peroxide is added to oxidize Sn 2+ Oxidized to Sn 4+ Adding alkali solution to adjust pH to 1.0, continuously adding sodium carbonate solution to adjust pH to about 2.5, stabilizing pH value, reacting for 1 hr, clarifying, filtering, and air blowing and washing until the lotion is colorless. The dried tin mud weighed 39.56 grams, the tin content was 53.16%, and the copper was 0.62%. The direct yield of tin was 91.47%. The filtrate washings amounted to 1470 ml and contained Sn 0.102 Cu 7.66.
1470 ml of the solution after tin removal is stirred and added with 10.5 g of reduced iron powder, after 1 hour of reaction, the solution is filtered and dried to obtain 12.9 g of sponge copper powder, 82.3 percent of copper and 93.9 percent of copper direct yield.
Through the above example and production practice, the scheme has strong pertinence to the copper-tin-lead-antimony material containing high precious metals, has high recovery rate, solves the problem that antimony is not hydrolyzed thoroughly, and obviously improves the economic benefit of the difficult problem that the content of tin and precious metals in antimony mud and sponge copper is higher.
Example 3
A method for separating a copper-antimony-tin-lead-containing high-gold high-silver material comprises the following steps:
(1) Ball milling the materials to obtain a particle size of more than 80 meshes;
(2) Primary acid leaching: adding a mixed solution of hydrogen peroxide and hydrochloric acid into the ball-milled material obtained in the step (1), reacting for 2-6 hours at the temperature of 60-80 ℃, adding sodium sulfate to precipitate lead 1 hour before filter pressing after the reaction is finished, so as to prevent the lead chloride from cooling and crystallizing to block pipelines, valves and delivery pumps, wherein the addition amount of a precipitator is 0.8 times of the mass of the lead; wherein the liquid-solid ratio of the mixed solution of hydrogen peroxide and hydrochloric acid to the materials is 2: 1, the concentration of hydrochloric acid is 5mol/L, and the mass percentage content of hydrogen peroxide is 0%.
(3) Secondary acid leaching: filter-pressing the slurry after the precipitation is finished in the step (1) to obtain primary filter residue and primary filtrate, adding hydrochloric acid into the filter residue to carry out secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out primary acid leaching at the same liquid-solid ratio, temperature and reaction time, separating to obtain secondary filtrate and secondary filter residue after the secondary acid leaching is finished, cleaning the secondary filter residue, airing the secondary filter residue, entering a pyrogenic process section to recover gold and silver, and returning the secondary filtrate to the primary acid leaching; adding percarbonate amide for oxidation in the secondary acid leaching process.
(4) Primary acid liquor replacement: adding fresh anode mud into the primary filtrate obtained in the step (2) to reduce free gold and silver in the solution into a simple substance state, and reducing Sb in the solution 5+ Conversion to Sb 3+ Replacing to obtain replacement liquid;
(5) Hydrolysis: adjusting the pH value of the replacement liquid obtained in the step (4) to 0.4-0.6 by using a sodium hydroxide solution, supplementing water with the volume 3-4 times that of the replacement liquid, controlling the temperature to be 35-55 ℃, controlling the stirring speed to be 105-120 r/mjn, reacting for 20-40 min, and filtering and separating to obtain antimony oxychloride and antimony hydrolysate liquid; the antimony oxychloride can be dissolved by ammonia water to prepare antimony;
(6) And (3) oxidation: adding oxidant into the antimony hydrolyzed liquid obtained in the step (5) to obtain Sn 2+ Is oxidized to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) And (3) neutralizing and tin depositing: neutralizing the completely oxidized solution with sodium hydroxide and sodium carbonate, controlling the pH to be between 2.0 and 2.5, and Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing pyrogenic process for tin recovery; sn content in solution after tin precipitation<0.14g/l。
(8) Copper replacement: and (4) adding iron powder which is 0.9 time of the mass of copper into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper precipitate containing more than 80% of copper, wherein the replacement rate is more than 99%, and the wastewater generated by copper precipitation is directly treated in a sewage center in a harmless manner.
In the process of the treatment process, the gold content in the antimony oxychloride is 1.92g/t, the silver content is 980g/t, the tin content is 1.8 percent, the recovery rate of gold and silver is improved by 1 percent compared with the original process, and the direct recovery rate of tin is improved by 4 percent.
Example 4
A method for separating a copper-antimony-tin-lead-containing high-gold high-silver material comprises the following steps:
(1) Ball milling the materials to obtain the granularity of more than 80 meshes;
(2) Primary acid leaching: adding a mixed solution of hydrogen peroxide and hydrochloric acid into the ball-milled material obtained in the step (1), reacting for 2-6 hours at the temperature of 60-80 ℃, adding sodium sulfite to precipitate lead 1 hour before filter pressing after the reaction is finished, preventing the lead chloride from cooling and crystallizing to block pipelines, valves and delivery pumps, wherein the addition amount of a precipitator is 0.8 times of the mass of the lead; wherein the liquid-solid ratio of the mixed solution of hydrogen peroxide and hydrochloric acid to the material is 4: 1, the concentration of hydrochloric acid is 7mol/L, and the mass percentage of hydrogen peroxide is 10%.
(3) Secondary acid leaching: after the precipitation is finished, filter-pressing the slurry to obtain primary filter residue and primary filtrate, adding hydrochloric acid into the filter residue to carry out secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out primary acid leaching at the same liquid-solid ratio, temperature and reaction time, after the secondary acid leaching is finished, separating to obtain secondary filtrate and secondary filter residue, cleaning the secondary filter residue, airing the secondary filter residue, entering a pyrogenic process section to recover gold and silver, and returning the secondary filtrate to the primary acid leaching; adding hydrogen peroxide and oxygen to oxidize in the secondary acid leaching process.
(4) Primary acid liquor replacement: adding crude antimony powder into the primary filtrate obtained in the step (2) to reduce free gold and silver in the solution into a simple substance state, and reducing Sb in the solution 5+ Conversion to Sb 3+ Obtaining a replacement solution after replacement;
(5) Hydrolysis: adjusting the pH of the replacement liquid obtained in the step (4) to 0.4-0.6 by using an ammonia water solution, supplementing water with the volume of 3-4 times that of the replacement liquid, controlling the temperature to be 35-55 ℃, controlling the stirring speed to be 105-120 r/mjn, reacting for 20-40 min, and filtering and separating to obtain antimony oxychloride and hydrolyzed antimony liquid; antimony oxychloride can be used for smelting crude antimony by a pyrogenic process;
(6) And (3) oxidation: adding oxidant into the antimony hydrolyzed liquid obtained in the step (5) to obtain Sn 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) And (3) neutralizing and tin depositing: neutralizing the completely oxidized solution with ammonium sulfate and ammonia water, controlling the pH = 2.0-2.5, and keeping Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing pyrogenic process for tin recovery; sn content in solution after tin precipitation<0.06g/l。
(8) Copper replacement: and (3) adding iron powder with the mass 1 time that of copper into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper precipitates containing more than 80% of copper, wherein the replacement rate is more than 99.2%, and the wastewater generated by copper precipitation is directly sent to a sewage center for harmless treatment.
In the treatment process, the gold content, the silver content and the tin content in the antimony oxychloride are 0.9g/t, 540g/t and 0.9 percent respectively, the recovery rate of gold and silver is improved by 2 percent and the direct recovery rate of tin is improved by 6 percent compared with the original process.
Example 5
A method for separating a copper-antimony-tin-lead-containing high-gold high-silver material comprises the following steps:
(1) Ball milling the materials to obtain a particle size of more than 80 meshes;
(2) Primary acid leaching: adding a mixed solution of hydrogen peroxide and hydrochloric acid into the ball-milled material obtained in the step (1), reacting for 2-6 hours at the temperature of 60-80 ℃, adding sulfuric acid to precipitate lead 1 hour before filter pressing after the reaction is finished, so as to prevent the lead chloride from cooling and crystallizing to block pipelines, valves and delivery pumps, wherein the addition amount of a precipitator is 0.8 times of the mass of the lead; wherein the liquid-solid ratio of the mixed solution of hydrogen peroxide and hydrochloric acid to the material is 3: 1, the concentration of hydrochloric acid is 7mol/L, and the mass percentage of hydrogen peroxide is 5%.
(3) Secondary acid leaching: filter-pressing the slurry after the precipitation is finished in the step (1) to obtain primary filter residue and primary filtrate, adding hydrochloric acid into the filter residue to carry out secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out primary acid leaching at the same liquid-solid ratio, temperature and reaction time, separating to obtain secondary filtrate and secondary filter residue after the secondary acid leaching is finished, cleaning the secondary filter residue, airing the secondary filter residue, entering a pyrogenic process section to recover gold and silver, and returning the secondary filtrate to the primary acid leaching; sodium chlorate is added in the secondary acid leaching process for oxidation.
(4) Primary acid liquor replacement: adding fresh anode mud into the primary filtrate obtained in the step (2) to reduce free gold and silver in the solution into a simple substance state, and reducing Sb in the solution 5+ Conversion to Sb 3+ Obtaining a replacement solution after replacement;
(5) Hydrolysis: adjusting the pH of the replacement liquid obtained in the step (4) to 0.4-0.6 by using an ammonia water solution, supplementing water with the volume of 3-4 times that of the replacement liquid, controlling the temperature to be 35-55 ℃, controlling the stirring speed to be 105-120 r/mjn, reacting for 20-40 min, and filtering and separating to obtain antimony oxychloride and hydrolyzed antimony liquid; antimony oxychloride can be used for smelting crude antimony by a pyrogenic process;
(6) And (3) oxidation: adding oxidant into the antimony hydrolyzed liquid obtained in the step (5) to obtain Sn 2+ Is oxidized to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin deposition: neutralizing the completely oxidized solution with sodium carbonate and sodium bicarbonate, controlling pH = 2.0-2.5, and Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing pyrogenic process for tin recovery; sn content in solution after tin precipitation<0.09g/l。
(8) Copper replacement: and (3) adding iron powder with the mass 1 time that of copper into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper precipitates containing more than 80% of copper, wherein the replacement rate is more than 99.1%, and the wastewater generated by copper precipitation is directly sent to a sewage center for harmless treatment.
In the process of the treatment process, the gold content in the antimony oxychloride is 1.2g/t, the silver content is 760g/t, the tin content is 1.1 percent, the recovery rate of gold and silver is improved by 1.2 percent compared with the original process, and the direct recovery rate of tin is improved by 4.5 percent.
Comparative example 1
The difference between comparative example 1 and example 2 is: the rest of the process is the same as example 2 without secondary acid leaching, and the details are not repeated. Finally, the gold content in the antimony oxychloride is 8g/t, the silver content is 4300g/t, the tin content is 6.2 percent, the recovery rate of gold and silver is equivalent to the direct recovery rate of tin in the prior art, and the recovery rate of gold and silver is not improved.
Claims (10)
1.A separation method of a copper, antimony, tin and lead-containing high-gold and high-silver material comprises the following steps:
(1) Ball milling the materials to obtain the granularity of more than 80 meshes;
(2) Primary acid leaching: adding a mixed solution of hydrogen peroxide and hydrochloric acid into the ball-milled material obtained in the step (1), reacting for 2-6 hours at the temperature of 60-80 ℃, and adding a part of precipitator to precipitate lead 1 hour before filter pressing after the reaction is finished, so as to prevent the lead chloride from cooling, crystallizing and blocking pipelines, valves and delivery pumps;
(3) Secondary acid leaching: filter-pressing the slurry after the precipitation is finished in the step (1) to obtain primary filter residue and primary filtrate, adding hydrochloric acid into the filter residue to carry out secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out primary acid leaching at the same liquid-solid ratio, temperature and reaction time, separating to obtain secondary filtrate and secondary filter residue after the secondary acid leaching is finished, cleaning the secondary filter residue, airing the secondary filter residue, entering a pyrogenic process section to recover gold and silver, and returning the secondary filtrate to the primary acid leaching;
(4) Primary acid liquor replacement: adding fresh anode mud or crude antimony powder into the primary filtrate obtained in the step (2) to reduce free gold and silver in the solution to a simple substance state, and reducing Sb in the solution 5+ Conversion to Sb 3+ Obtaining a replacement solution after replacement;
(5) Hydrolysis: regulating the pH value of the replacement liquid obtained in the step (4) to 0.4-0.6 by using a pH value regulator, supplementing water with the volume of 3-4 times that of the replacement liquid, controlling the temperature to be 35-55 ℃, controlling the stirring speed to be 105-120 r/mjn, reacting for 20-40 min, and filtering and separating to obtain antimony oxychloride and hydrolyzed antimony liquid;
(6) And (3) oxidation: adding an oxidant into the antimony hydrolyzed liquid obtained in the step (5) to obtain Sn 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) And (3) neutralizing and tin depositing: neutralizing the completely oxidized solution with neutralizer, controlling pH = 2.0-2.5, and Sn in the solution 4+ Precipitating, filter-pressing, blowing, washing for many times, drying filter residues, and then performing pyrogenic process for tin recovery;
(8) Copper replacement: and (4) adding iron powder into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper precipitates containing more than 80% of copper, wherein the replacement rate is more than 99%, and the wastewater generated by copper precipitation is directly fed into a sewage center for harmless treatment.
2. The method according to claim 1, wherein the liquid-solid ratio of the mixed solution of hydrogen peroxide and hydrochloric acid to the material in step (2) is 2-4: 1, the concentration of hydrochloric acid is 5-7 mol/L, and the mass percentage of hydrogen peroxide is 0-10%.
3. The method of claim 1, wherein in the step (5), the pH regulator is sodium hydroxide or an aqueous ammonia solution.
4. The method of claim 1, wherein in step (5), the antimony oxychloride can be dissolved in ammonia water to produce antimony white or pyrogenic crude antimony.
5. The method according to claim 1, wherein in step (7), the Sn content in the solution after tin deposition is less than 0.15g/l.
6. The method of claim 1, wherein in step (2), the precipitant is at least one of sodium sulfate, sodium bisulfate, sulfuric acid, and sodium sulfite, and is added in an amount of 0.8 times the mass of the lead.
7. The method according to claim 1, wherein in the step (3), an oxidant is added in the secondary acid leaching process, and the oxidant is at least one of sodium chlorate, oxygen, hydrogen peroxide and percarbonateamide.
8. The method of claim 1, wherein in step (8), the amount of iron powder added is 0.9 to 1 times the mass of copper.
9. The method according to claim 1, wherein the neutralizing agent in the step (7) is at least one of sodium hydroxide and sodium carbonate, sodium carbonate and sodium bicarbonate, ammonium sulfate and ammonia water.
10. The method as claimed in claim 1, wherein the antimony oxychloride has a gold content of less than 2g/t, a silver content of less than 1000g/t, and a tin content of less than 2.0%, and the recovery rate of gold and silver is increased by 1-2% and the direct recovery rate of tin is increased by 4-6% compared with the original process.
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