CN115572832B - Method for treating Gao Jingao silver material containing copper, antimony, tin and lead - Google Patents
Method for treating Gao Jingao silver material containing copper, antimony, tin and lead Download PDFInfo
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Abstract
The invention discloses a method for separating Gao Jingao silver materials containing copper, antimony, tin and lead, which comprises the following steps: ball milling the materials, wherein the granularity is 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 part of precipitant to precipitate lead 1 hour before press filtration after the reaction is finished, so as to prevent cooling crystallization of lead chloride from blocking a pipeline, a valve and a conveying pump; (3) secondary acid leaching; (4) primary acid liquor replacement; (5) hydrolysis; (6) oxidation; (7) neutralizing and depositing tin; (8) replacing copper. The method provided by the invention has the advantages of high recovery rate of gold and silver of the final noble metal, thorough antimony hydrolysis, high copper purity and stable technological process.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal separation and enrichment, and particularly relates to a separation method of Gao Jingao silver materials containing copper, antimony, tin and lead.
Background
In the technical field of separation and enrichment of colored technology, noble metals are expensive, so that the noble metals have important positions for separation and purification. For separation and enrichment of copper, antimony, tin, lead and gold and silver materials, the basic idea is that hydrochloric acid and an oxidant dissolve all base metals, the solution gradually separates antimony, copper and tin, and precious metals enter a pyrometallurgy. The main technical problems existing in the prior art are as follows: the pickle liquor (1) has higher gold and silver content. (2) The hydrolysis is incomplete when the antimony is hydrolyzed, the liquid after the hydrolysis contains 2 to 3g/l of antimony, and 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) substitution produced copper powder mixed with 4% tin. The recovery rate of Jin Yinxi antimony and other metals is not ideal, and the subsequent treatment and recovery are difficult and complicated.
Disclosure of Invention
The invention aims to provide a processing method of Gao Jingao silver materials containing copper, antimony, tin and lead, which has the advantages of high recovery rate of gold and silver of the final noble metal, thorough antimony hydrolysis, high copper purity and stable technological process.
The invention adopts the following technical scheme:
a method for separating Gao Jingao silver materials containing copper, antimony, tin and lead comprises the following steps:
(1) Ball milling the materials, wherein the granularity is 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 part of precipitant to precipitate lead 1 hour before press filtration after the reaction is finished, so as to prevent cooling crystallization of lead chloride from blocking a pipeline, a valve and a conveying pump;
(3) Secondary acid leaching: step (1) after precipitation is finished, filtering and pressing the slurry to obtain primary filter residues and primary filter residues, adding hydrochloric acid into the filter residues for secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out the same acid leaching for the liquid-solid ratio, the temperature and the reaction time, separating to obtain secondary filter residues and secondary filter residues after the secondary acid leaching is finished, cleaning the secondary filter residues, airing the secondary filter residues, entering a pyrogenic process section for recycling gold and silver, and returning the secondary filter residues 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 in the solution 5+ Conversion to Sb 3+ Obtaining a replacement liquid 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, adding water with the volume of 3-4 times of the replacement liquid, controlling the temperature to be between 35 and 55 ℃, controlling the stirring rotation speed to be 105-120 r/mjn, reacting for 20-40 min, filtering and separating to obtain antimony oxychloride and hydrolyzed antimony rear liquid;
(6) Oxidizing: adding an oxidant into the hydrolyzed antimony postsolution obtained in the step (5), and adding Sn into the hydrolyzed antimony postsolution 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin precipitation: neutralizing the completely oxidized solution with a neutralizing agent, controlling pH to be 2.0-2.5, and controlling Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing a pyrogenic process to recover tin;
(8) Replacement of copper: adding iron powder 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 directly introducing wastewater generated by copper precipitation 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 of hydrogen peroxide is 0-10%.
Further, in the step (5), the pH regulator is sodium hydroxide or ammonia water solution, preferably ammonia water, and if the ammonia water is added in an excessive amount, antimony white can be directly produced.
In the step (5), antimony oxychloride can be dissolved by ammonia water to prepare antimony white or fire refining crude antimony.
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 adding amount of the precipitant is 0.8 times of the mass of lead, and when sodium sulfite is adopted as the precipitant, the oxidant can oxidize sodium sulfite into sodium sulfate and consume redundant oxidant in the solution, thereby being beneficial to the operation of the subsequent steps.
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 percarbonic acid amide.
Further, in the step (8), the addition 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, amine sulfate and ammonia water. When the latter two neutralizing agents are adopted, the pH value can be controlled more stably, and particularly when the neutralizing agents are adopted, no gas is generated when the neutralizing agents are adopted for neutralization by using the amine sulfate and the ammonia water, so that the process control is facilitated.
Further, the gold content in the antimony oxychloride is less than 2g/t, the silver content is less than 1000g/t, the tin content 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 yield of tin is improved by 4-6%.
Compared with the prior art, the invention has the following advantages:
1. the method can be used for efficiently treating the materials containing copper, antimony, tin and lead through repeated research and comparison experiments. The leaching rate of base metals is obviously improved through twice acid leaching; lead in the solution enters the slag in the form of lead sulfate, which is of great benefit to the subsequent pyrogenic recovery of noble slag. The added solution replacement link greatly reduces the loss of gold and silver in the leaching link,
2. the method adds secondary acid leaching in the leaching step, and adopts low acid leaching of tin antimony, high acid leaching of copper and high acid leaching of return acid of the acid mixture. Low acid liquor is replaced by self-produced fresh anode mud, so that the gold and silver content in the leaching solution is reduced, and sb in the solution is also removed 5+ Reduction to sb 3+ Antimony was thoroughly allowed to hydrolyze.
3. The process sequence of neutralizing and depositing tin and recovering copper is exchanged, hydrolysis and post-oxidation are carried out, tin is precipitated in the form of tin hydroxide, and the filtered liquid is replaced to recover copper, so that tin loss is avoided.
Detailed Description
The present invention is further described below with reference to examples, but the present invention is not limited to the examples, and it should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for 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 scope of disclosure.
Example 1
Main components (%) of the existing materials: sb 23.31Sn 39.16 Pb 1.45 Cu 3.57Ag 10.69 Au 0.0168
200 g of 80 mesh drying material is taken, slowly added into 600 ml of 6mol/L hydrochloric acid, stirred, heated to 80 ℃ and reacted for 4 hours. 1 hour before filtering, 2.4 g of sodium sulfate is added, filtering is carried out, washing is carried out by 5% of dilute hydrochloric acid, and then the acid liquor is washed by clean water, the total amount of the filtrate is 750 ml, the component (g/l) of Sn 98.60 Sb 53.61 Cu 9.07 Pb 0.06.Ag 0.17 is contained, the filter residue is dried and weighed for 64.6 g, and the component is (%) Sn 6.77 Sb 9.92 Cu 0.53 Pb 4.41.Ag 32.99.
Performing secondary acid leaching on filter residues, preparing 195 ml of 8mol/L hydrochloric acid leaching solution, carefully adding 64.6 g of leaching residues, heating to 80 ℃, stirring for reacting for 4 hours, cooling, filtering and washing. 270 ml of filtrate (containing washing liquid) was left for use. The component (g/l) Sn 13.44 Sb19.96 Cu 0.89 Ag 0.22 is added with hydrochloric acid to prepare a reaction solution in the next leaching. The filter residue is dried and weighed 43.2 g, and the components are (in percent) Sb 1.89 Sn 1.52 Pb 0.01 Cu 0.17 Ag 49.07 Au 0.0772, 99.26 percent of gold, 99.16 percent of silver, 99.1 percent of tin leaching rate, more than 98 percent of copper and antimony leaching rate, and lower base metal components, so that powerful guarantee is provided for the recovery rate of the fire gold and silver.
And (3) replacing 750 ml of primary leaching liquid with fresh anode mud or crude antimony powder, replacing silver ions and silver-chlorine complex ions suspended in the solution with metallic state, and recycling the metallic state slag. At the same time to remove Sb possibly present in the solution 5+ Reduction to Sb 3+ Antimony is thoroughly separated from copper tin after hydrolysis. The adding amount of the antimony powder or the anode slime is 20 times of the mass of free silver, 2.6 g is added at this time, and the Ag detected by filtrate is only 0.053g/l, so that the effect is obvious.
Taking 250 ml of 1/3 replacement liquid, adding a little sodium hydroxide to adjust the pH value to 0.5, stirring uniformly, adding 750 ml of water for dilution, heating to 40 ℃, after the antimony trichloride is completely dehydrated, converting into antimony oxychloride, clarifying, filtering, and washing the antimony oxychloride. The hydrolyzed solution contains 1025 ml of Sb 0.215 Sn 24.06 Cu 2.22 Ag 0.02 (g/l) and is thoroughly hydrolyzed to obtain 20.86 g of antimony paste, wherein the content of Sb 60.17 Sn 0. 16 Cu 0.22 Ag 0.06 and the direct yield of antimony are 93%.
1025 ml of hydrolysis liquid is supplemented with 28 ml of hydrogen peroxide for oxidation, 12.5 ml of liquid caustic soda is added for regulating the PH value to 1.0, sodium carbonate liquid is continuously added for regulating the PH value of the solution to 2.0, the stable acidity is stirred for 30min, the solution is clarified and filtered after the reaction is carried out for 1 hour, air blowing and water washing are carried out until the washing liquid has no copper color, the total amount of filtrate water is 1080 ml, sn is 0.097, the filter residue is dried and weighed 39.22g, sn content is 61.45%, and the direct yield of tin is 92.3%.
1080 ml of the tin-removed liquid is added with 2.2 g of reduced iron powder and stirred for 1 hour to obtain 2.72 g of copper powder, the content of which is 81.8 percent and the direct yield of the copper is 93.49 percent.
Example 2
The material composition (%) is Sb 8.24 Sn 32.06 Pb 3.26 Cu 15.98 Ag 8.22 Au 0.0511.
300g of the mixture is ball-milled, 80-mesh raw materials are adopted, 200 ml of the second immersion liquid in the example 1 is additionally taken, the component (g/L) Sn 13.44 Sb19.96 Cu 0.89 Ag 0.22 is added, and 900 ml of 6mol/L reaction solution is prepared by adding industrial hydrochloric acid. Slowly adding, heating to 80 ℃, starting timing, and preserving heat and leaching for 4 hours. 7.9 g of sodium sulfate is added 1 hour before the filter pressing, the filter cake is washed by 100 ml of 5% dilute hydrochloric acid, and then 200 ml of clear water is used for washing the acid liquor. The filtrate washes were combined together to total 1250 ml. The component (g/l) of 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 (%) of Sn 7.30 Sb 4.51 Cu 2.86 Pb 10.72.
And then carrying out secondary acid leaching on the leached residues. Preparing 275 ml of 6mol/L hydrochloric acid leaching solution, slowly adding 90.92 g of primary leaching slag, stirring, heating to 80 ℃, starting timing, preserving heat and leaching for 4 hours, adding 10 ml of hydrogen peroxide after 2 hours of reaction, cooling, filtering, blowing, adding 5% of dilute hydrochloric acid to wash a filter cake, and then washing tin and copper ions with clean water. The filtrate and washings amounted to 505 ml, with a major content (g/l) of Sn 12.13 Sb 6.97 Cu 4.79 Ag 0.26. The filter cake was dried and weighed to 63.4 g, and the main component (%) Sn 1.21 Sb 0.98 Cu 0.75 Pb 15.09 Ag 38.51 Au 0.2416, the slag inclusion rate of gold was 99.86%, and the slag inclusion rate of silver was 99.02%. The leaching rate of tin is 98.9, and the leaching rate of copper and antimony is more than 98%.
Taking 625 ml of an immersion liquid, adding lead powder to replace free complex silver ions and Sb 5+ The adding amount of the lead powder is about 30-40 times of the silver amount in the solution. The method is 35 times of that of the method, 4.2 g is added for replacement for 2 hours, the mixture is filtered, the filter residue is returned to be subjected to primary acid leaching to recover noble metal, the filtrate is about 640 ml, and the detection Ag is only 0.037g/l, so that the effect is remarkable.
Taking 1/2 of displacement liquid 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 for dilution, 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. 1380 ml of hydrolyzed solution is prepared from main component (g/l) of Sb 0.25 Sn 17.15 Cu 8.45 Ag 0.03, dried antimony oxychloride, weighing 9.8 g, and containing 57.34% of antimony with a direct yield of 90.21%.
1380 ml of hydrolyzed solution is oxidized, the volume of hydrogen peroxide is 1.1-1.5 times of the tin amount, and 26 ml of 20% industrial hydrogen peroxide is added to carry out Sn treatment 2+ Oxidation to Sn 4+ Adding alkali solution to adjust the pH value to 1.0, continuously adding sodium carbonate solution to adjust the pH value to about 2.5, stabilizing the pH value without returning, clarifying and filtering after reacting for 1 hour, and washing with air blowing water until the washing liquid has no color. The tin mud is dried and weighed 39.56 g, and the tin content is 53.16 percent and the copper content is 0.62 percent. The direct yield of tin was 91.47%. The total of 1470 ml of filtrate and washing liquid contains Sn 0.102 Cu 7.66.
1470 ml of the tin-removed liquid is stirred and added with 10.5 g of reduced iron powder, after reacting for 1 hour, the mixture is filtered and dried to obtain 12.9 g of sponge copper powder, the copper content is 82.3%, and the direct yield of copper is 93.9%.
Through the above examples and production practices, the scheme has strong pertinence to the copper-tin-lead-antimony material with high noble metal content and high recovery rate, solves the problems of incomplete antimony hydrolysis and high tin and noble metal content in antimony mud and sponge copper, and has remarkably improved economic benefit.
Example 3
A method for separating Gao Jingao silver materials containing copper, antimony, tin and lead comprises the following steps:
(1) Ball milling the materials, wherein the granularity is 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 sodium sulfate to precipitate lead 1 hour before press filtration after the reaction is finished, so as to prevent cooling crystallization of lead chloride from blocking a pipeline, a valve and a conveying pump, wherein the adding amount of a precipitant 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 2:1, the concentration of hydrochloric acid is 5mol/L, and the mass percentage of hydrogen peroxide is 0%.
(3) Secondary acid leaching: step (1) after precipitation is finished, filtering and pressing the slurry to obtain primary filter residues and primary filter residues, adding hydrochloric acid into the filter residues for secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out the same acid leaching for the liquid-solid ratio, the temperature and the reaction time, separating to obtain secondary filter residues and secondary filter residues after the secondary acid leaching is finished, cleaning the secondary filter residues, airing the secondary filter residues, entering a pyrogenic process section for recycling gold and silver, and returning the secondary filter residues to the primary acid leaching; and 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+ Obtaining a replacement liquid after replacement;
(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, adding water with the volume of 3-4 times of the replacement liquid, controlling the temperature to be between 35 and 55 ℃, controlling the stirring rotation speed to be 105-120 r/mjn, reacting for 20-40 min, filtering and separating to obtain antimony oxychloride and hydrolyzed antimony rear liquid; the antimony oxychloride can be dissolved by ammonia water to prepare antimony;
(6) Oxidizing: adding an oxidant into the hydrolyzed antimony postsolution obtained in the step (5), and adding Sn into the hydrolyzed antimony postsolution 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin precipitation: neutralizing the completely oxidized solution with sodium hydroxide and sodium carbonate, controlling pH value to be 2.0-2.5, and controlling Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing a pyrogenic process to recover tin; sn content in solution after tin precipitation<0.14g/l。
(8) Replacement of copper: adding iron powder with the mass 0.9 times of copper into the filtrate obtained in the step (7) to replace a solution containing copper ions with sponge copper sediment with copper content more than 80%, wherein the replacement rate is more than 99%, and directly introducing wastewater generated by copper sedimentation into a sewage center for harmless treatment.
In 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%, the recovery rate of gold and silver is improved by 1% compared with the original process, and the direct recovery rate of tin is improved by 4%.
Example 4
A method for separating Gao Jingao silver materials containing copper, antimony, tin and lead comprises the following steps:
(1) Ball milling the materials, wherein the granularity is 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 sodium sulfite to precipitate lead 1 hour before press filtration after the reaction is finished, so as to prevent cooling crystallization of lead chloride from blocking a pipeline, a valve and a conveying pump, wherein the adding amount of a precipitant 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: step (1) after precipitation is finished, filtering and pressing the slurry to obtain primary filter residues and primary filter residues, adding hydrochloric acid into the filter residues for secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out the same acid leaching for the liquid-solid ratio, the temperature and the reaction time, separating to obtain secondary filter residues and secondary filter residues after the secondary acid leaching is finished, cleaning the secondary filter residues, airing the secondary filter residues, entering a pyrogenic process section for recycling gold and silver, and returning the secondary filter residues to the primary acid leaching; hydrogen peroxide and oxygen are added for oxidation 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 liquid after replacement;
(5) Hydrolysis: adjusting the pH value of the replacement liquid obtained in the step (4) to 0.4-0.6 by using an ammonia water solution, adding water with the volume of 3-4 times of the replacement liquid, controlling the temperature to be between 35 and 55 ℃, controlling the stirring rotation speed to be 105-120 r/mjn, reacting for 20-40 min, filtering and separating to obtain antimony oxychloride and hydrolyzed antimony rear liquid; the antimony oxychloride can be used for pyrometallurgy of crude antimony;
(6) Oxidizing: adding an oxidant into the hydrolyzed antimony postsolution obtained in the step (5), and adding Sn into the hydrolyzed antimony postsolution 2+ Oxidation to Sn 4+ The oxygen isThe chemical agent is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin precipitation: neutralizing the completely oxidized solution with ammonium sulfate and ammonia water, controlling pH value to be 2.0-2.5, and controlling Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing a pyrogenic process to recover tin; sn content in solution after tin precipitation<0.06g/l。
(8) Replacement of copper: adding iron powder with the mass 1 time of copper into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper sediment with copper content more than 80%, wherein the replacement rate is more than 99.2%, and directly introducing wastewater generated by copper sedimentation into a sewage center for harmless treatment.
In the treatment process, the gold content in the antimony oxychloride is 0.9g/t, the silver content is 540g/t, the tin content is 0.9%, the recovery rate of gold and silver is improved by 2% compared with the original process, and the direct yield of tin is improved by 6%.
Example 5
A method for separating Gao Jingao silver materials containing copper, antimony, tin and lead comprises the following steps:
(1) Ball milling the materials, wherein the granularity is 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 sulfuric acid to precipitate lead 1 hour before press filtration after the reaction is finished, so as to prevent cooling crystallization of lead chloride from blocking a pipeline, a valve and a conveying pump, wherein the adding amount of a precipitant is 0.8 times of the mass of 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: step (1) after precipitation is finished, filtering and pressing the slurry to obtain primary filter residues and primary filter residues, adding hydrochloric acid into the filter residues for secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, carrying out the same acid leaching for the liquid-solid ratio, the temperature and the reaction time, separating to obtain secondary filter residues and secondary filter residues after the secondary acid leaching is finished, cleaning the secondary filter residues, airing the secondary filter residues, entering a pyrogenic process section for recycling gold and silver, and returning the secondary filter residues to the primary acid leaching; sodium chlorate is added 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+ Obtaining a replacement liquid after replacement;
(5) Hydrolysis: adjusting the pH value of the replacement liquid obtained in the step (4) to 0.4-0.6 by using an ammonia water solution, adding water with the volume of 3-4 times of the replacement liquid, controlling the temperature to be between 35 and 55 ℃, controlling the stirring rotation speed to be 105-120 r/mjn, reacting for 20-40 min, filtering and separating to obtain antimony oxychloride and hydrolyzed antimony rear liquid; the antimony oxychloride can be used for pyrometallurgy of crude antimony;
(6) Oxidizing: adding an oxidant into the hydrolyzed antimony postsolution obtained in the step (5), and adding Sn into the hydrolyzed antimony postsolution 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin precipitation: neutralizing the completely oxidized solution with sodium carbonate and sodium bicarbonate, controlling pH to be 2.0-2.5, and controlling Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing a pyrogenic process to recover tin; sn content in solution after tin precipitation<0.09g/l。
(8) Replacement of copper: adding iron powder with the mass 1 time of copper into the filtrate obtained in the step (7) to replace the solution containing copper ions with sponge copper sediment with copper content more than 80%, wherein the replacement rate is more than 99.1%, and directly introducing wastewater generated by copper sedimentation into a sewage center for harmless treatment.
In 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%, the recovery rate of gold and silver is improved by 1.2% compared with the original process, and the direct yield of tin is improved by 4.5%.
Comparative example 1
The difference between comparative example 1 and example 2 is: the second acid leaching is not performed, and the rest is the same as in example 2, and is not repeated. The gold content in the final antimony oxychloride is 8g/t, the silver content is 4300g/t, the tin content is 6.2%, and the recovery rate of gold and silver is equivalent to that of the prior art without improvement.
Claims (4)
1.A method for separating Gao Jingao silver materials containing copper, antimony, tin and lead comprises the following steps:
(1) Ball milling the materials, wherein the granularity is 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 part of precipitant to precipitate lead 1 hour before press filtration after the reaction is finished, preventing cooling crystallization of lead chloride from blocking a pipeline, a valve and a conveying pump, wherein the precipitant is sodium sulfite, the adding amount of the precipitant is 0.8 times of the mass of the lead, 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 of the hydrogen peroxide is 0-10%;
(3) Secondary acid leaching: step (1) after precipitation is finished, filter-pressing slurry to obtain primary filter residue and primary filtrate, adding hydrochloric acid into the filter residue, adding an oxidant, performing secondary acid leaching, continuously dissolving unremoved tin and copper, controlling the concentration of the hydrochloric acid to be 8mol/L, performing acid leaching for the same time at the liquid-solid ratio, the temperature and the 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, recycling gold and silver in a pyrogenic process section, and returning the secondary filtrate to the primary acid leaching, wherein the oxidant is at least one of sodium chlorate, oxygen, hydrogen peroxide and percarbonic acid amide;
(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 in the solution 5+ Conversion to Sb 3+ Obtaining a replacement liquid after replacement;
(5) Hydrolysis: adjusting the pH value of the replacement liquid obtained in the step (4) to 0.4-0.6 by using a pH value regulator, adding water with the volume which is 3-4 times that of the replacement liquid, controlling the temperature to be 35-55 ℃, controlling the stirring rotation speed to be 105-120 r/min, reacting for 20-40 min, filtering and separating to obtain antimony oxychloride and hydrolyzed antimony rear liquid, wherein the gold content in the antimony oxychloride is less than 2g/t, the silver content is less than 1000g/t, the tin content is less than 2.0%, and the pH value regulator is sodium hydroxide or ammonia water solution;
(6) Oxidizing: adding an oxidant into the hydrolyzed antimony solution obtained in the step (5),sn is mixed with 2+ Oxidation to Sn 4+ The oxidant is hydrogen peroxide, oxygen or air;
(7) Neutralizing and tin precipitation: neutralizing the completely oxidized solution with a neutralizing agent, controlling pH to be 2.0-2.5, and controlling Sn in the solution 4+ Precipitating, filter pressing, blowing, washing for multiple times, drying filter residues, and then performing a pyrogenic process to recover tin, wherein the neutralizer is ammonium sulfate and ammonia water;
(8) Replacement of copper: adding iron powder 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 directly introducing wastewater generated by copper precipitation into a sewage center for harmless treatment.
2. The method according to claim 1, wherein in the step (5), antimony oxychloride is dissolved in aqueous ammonia to produce antimony white or to produce crude antimony by pyrometallurgy.
3. The method according to claim 1, wherein in step (7), the Sn content of the solution after tin precipitation is <0.15g/l.
4. The method according to claim 1, wherein in the step (8), the iron powder is added in an amount of 0.9 to 1 time by mass of copper.
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