CN115369252A - Treatment method of copper smelting white smoke dust - Google Patents
Treatment method of copper smelting white smoke dust Download PDFInfo
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- CN115369252A CN115369252A CN202210923687.0A CN202210923687A CN115369252A CN 115369252 A CN115369252 A CN 115369252A CN 202210923687 A CN202210923687 A CN 202210923687A CN 115369252 A CN115369252 A CN 115369252A
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- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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Abstract
The invention discloses a treatment method of copper smelting white smoke dust, which comprises the following steps: low-temperature volatilization, primary oxidation leaching, secondary oxidation leaching, copper removal treatment, purification and impurity removal, concentration and crystallization. The invention volatilizes and enriches more than 95 percent of arsenic by adopting a low-temperature volatilization process, realizes high-efficiency separation of the arsenic and valuable metals in the smoke dust at low temperature, provides possibility for efficiently recovering valuable elements such as copper, lead, zinc, lead, silver, bismuth and the like in the smoke dust with short process and low cost, can efficiently leach and enrich the valuable metals such as copper, zinc and the like after the arsenic-removing smoke dust is subjected to two-stage normal-pressure oxidation leaching treatment, and can realize high-efficiency recovery of the copper and the zinc after the procedures such as decoppering treatment, purification and impurity removal, concentration and crystallization and the like.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a method for treating copper smelting white smoke dust.
Background
The copper smelting white smoke dust is one of main byproducts of the pyrometallurgical copper smelting process and contains valuable metal elements such as copper, zinc, lead, silver, bismuth and the like and harmful element arsenic, wherein the method for separating the arsenic from the valuable metal comprises a high-temperature smelting method and a wet leaching precipitation method. The high-temperature smelting method can realize the high-efficiency volatilization and removal of arsenic, but volatile oxides of lead, zinc and tin in the copper smelting white smoke are volatilized along with the volatile oxides, so that the dispersion and the loss of valuable elements are caused. In the process of leaching the copper smelting white smoke dust, a large amount of arsenic enters a leaching solution along with copper, zinc and the like, and lead, silver, bismuth and the like enter leaching residues. At present, the separation method of arsenic in arsenic-containing solution mainly comprises two types, firstly, the arsenic is prepared into crude arsenic trioxide by adopting a sulfur dioxide reduction cooling method, and then refined arsenic trioxide or simple substance arsenic products are obtained by refining and reducing; secondly, the hazardous waste arsenic slag generated in the process needs to be further treated in a harmless way by adopting a calcium salt-iron salt arsenic precipitation method or a scorodite arsenic precipitation method to convert the hazardous waste arsenic slag into calcium arsenate-ferric arsenate slag or scorodite arsenic precipitation slag. When the existing arsenic removal method is adopted to treat the copper smelting white smoke dust, the arsenic is easily dispersed in the leaching solution and the leaching slag, the arsenic removal process of the leaching solution is complex, the reagent consumption is high, and hazardous waste arsenic slag is easily generated.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for treating copper smelting white smoke, which aims to solve the problems that hazardous waste arsenic slag is easily generated and valuable metal elements are easily lost when the conventional arsenic removal method is used for treating the copper smelting white smoke.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a treatment method of copper smelting white smoke dust comprises the following steps:
reacting copper smelting white smoke dust at a first preset temperature for a first preset time to obtain white arsenic and arsenic-removed smoke dust;
mixing the arsenic-removed smoke dust with low acid liquor, introducing oxidizing gas, reacting at a second predetermined temperature for a second predetermined time, and performing liquid-solid separation after the reaction is finished to obtain a first leaching solution and a first leaching residue;
mixing the first leaching residue with a high-acid solution, introducing oxidizing gas, reacting at a third predetermined temperature for a third predetermined time, and performing liquid-solid separation after the reaction is finished to obtain a second leaching solution and a second leaching residue;
decoppering the first leaching solution to obtain cathode copper and a decoppered solution;
adding zinc oxide smoke dust into the decoppering solution, introducing air or oxidizing gas, reacting at a fourth preset temperature for a fourth preset time, and performing liquid-solid separation after the reaction is finished to obtain purified impurity-removing slag and purified impurity-removing liquid;
concentrating and crystallizing the purified impurity-removed solution to obtain refined zinc sulfate heptahydrate and crystallized solution;
wherein the low acid liquid is a mixed solution of concentrated sulfuric acid and water, and the acidity of the low acid liquid is 5-40 g/L; the high acid liquid is a mixed solution of concentrated sulfuric acid and water, and the acidity of the high acid liquid is 10-70 g/L.
The treatment method of the copper smelting white smoke dust comprises the following steps that the first preset temperature is 280-450 ℃, the first preset time is 60-150 min, the second preset temperature is room temperature-95 ℃, the second preset time is 60-120 min, the third preset temperature is room temperature-95 ℃, the third preset time is 60-120 min, the fourth preset temperature is room temperature-95 ℃, and the fourth preset time is 60-180 min.
The treatment method of the copper smelting white smoke dust is characterized in that the oxidizing gas is oxygen or oxygen-enriched air.
The treatment method of the copper smelting white smoke dust is characterized in that the second leaching solution and the crystallized solution are mixed to be used as a low acid solution for returning.
The treatment method of the copper smelting white smoke dust comprises the following steps:
and washing the second leaching residue to obtain washing water and lead, silver and bismuth residues.
The treatment method of the copper smelting white smoke dust is characterized in that the washing water and the concentrated sulfuric acid are mixed to be used as high-acid liquid to be returned for use.
The treatment method of the copper smelting white smoke dust is characterized in that lead, silver and bismuth slag are treated by adopting a pyrometallurgical method to recover lead, silver and bismuth respectively.
The treatment method of the copper smelting white smoke dust is characterized in that the first leaching solution is a solution containing 10-30 g/L of acid and 19-65 g/L of copper.
The treatment method of the copper smelting white smoke dust is characterized in that the second leaching solution contains 20-60 g/L of acid.
The treatment method of the copper smelting white smoke dust, wherein the step of decoppering the first leaching solution to obtain cathode copper and a decoppering solution specifically comprises the following steps:
and (3) carrying out copper removal on the first leaching solution by adopting a traditional electrodeposition process or a rotational flow electrodeposition process, and controlling the concentration of residual copper ions in the solution after electrodeposition copper removal to be 300-800 mg/L to obtain cathode copper and a copper removal solution.
Has the advantages that: the invention discloses a treatment method of copper smelting white smoke dust, which volatilizes and enriches over 95 percent of arsenic by adopting a low-temperature volatilization process, realizes high-efficiency separation of the arsenic and valuable metals in the smoke dust at low temperature, and provides possibility for recovering the valuable elements such as copper, lead, zinc, lead, silver, bismuth and the like in the smoke dust with short flow, low cost and high efficiency. The arsenic-removing smoke dust is treated by two stages of normal pressure oxidation leaching, so that valuable metals such as copper, zinc and the like can be efficiently leached and enriched, and the copper and the zinc can be efficiently recovered after the procedures of decoppering, purifying, impurity removing, concentrating, crystallizing and the like are carried out.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of the method for treating copper smelting white flue dust according to the present invention.
FIG. 2 is a flow chart of the actual production process of the treatment method of copper smelting white smoke dust of the present invention.
Detailed Description
The invention provides a method for treating copper smelting white smoke dust, which is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a treatment method of copper smelting white smoke dust, which comprises the following steps of:
s10, low-temperature volatilization: reacting copper smelting white smoke dust at a first preset temperature for a first preset time to obtain white arsenic and arsenic-removed smoke dust;
s20, primary oxidation leaching: mixing the arsenic-removing smoke dust with low acid liquor, introducing oxidizing gas, reacting at a second preset temperature for a second preset time, and performing liquid-solid separation after the reaction is finished to obtain a first leaching solution and first leaching residues;
s30, secondary oxidation leaching: mixing the first leaching residue with a high acid solution, introducing an oxidizing gas, reacting at a third predetermined temperature for a third predetermined time, and performing liquid-solid separation after the reaction is finished to obtain a second leaching solution and a second leaching residue;
s40, decoppering treatment: decoppering the first leaching solution to obtain cathode copper and a decoppered solution;
s50, purifying and removing impurities: adding zinc oxide smoke dust into the decoppering solution, introducing air or oxidizing gas, reacting at a fourth preset temperature for a fourth preset time, and performing liquid-solid separation after the reaction is finished to obtain purified impurity-removing slag and purified impurity-removing liquid;
s60, concentrating and crystallizing: and concentrating and crystallizing the purified impurity-removed solution to obtain refined zinc sulfate heptahydrate and crystallized solution.
Wherein the low acid liquid is a mixed solution of concentrated sulfuric acid and water, and the acidity of the low acid liquid is 5-40 g/L; the high acid liquid is a mixed solution of concentrated sulfuric acid and water, and the acidity of the high acid liquid is 10-70 g/L.
Specifically, the invention adopts a low-temperature volatilization process to volatilize and enrich more than 95 percent of arsenic, realizes the high-efficiency separation of the arsenic and valuable metals in smoke dust at low temperature, provides possibility for the short-flow, low-cost and high-efficiency recovery of the valuable elements such as copper, lead, zinc, lead, silver, bismuth and the like in the smoke dust, can realize the high-efficiency leaching and enrichment of the valuable metals such as copper, zinc and the like after the arsenic-removed smoke dust is subjected to two-stage normal-pressure oxidation leaching treatment, and can realize the high-efficiency recovery of the copper and zinc after the procedures such as electrodeposition copper removal, hydrolysis impurity removal, concentration crystallization and the like.
In some embodiments, the first predetermined temperature is 280-450 ℃, the first predetermined time is 60-150 min, more than 95% of arsenic in the copper smelting white smoke can be removed after the treatment by adopting a low-temperature volatilization process, meanwhile, the volatilization loss of volatile elements such as zinc, lead and the like in the smoke is inhibited, the arsenic-removed smoke with low arsenic content is obtained, and white arsenic with 70-90% of arsenic trioxide content and arsenic-removed smoke with 0.5-1% of arsenic are obtained after the treatment by adopting the low-temperature volatilization process.
In some embodiments, in step S20, the second predetermined temperature is 25 to 95 ℃, the second predetermined time is 60 to 120min, and the liquid-solid ratio involved in the reaction is controlled to be 2 to 5m 3 1t, the leachate with low acid and high copper and zinc contents which is beneficial to the subsequent treatment can be obtained.
In some embodiments, in step S30, the third predetermined temperature is room temperature to 95 ℃, the third predetermined time is 60 to 120min, and the liquid-solid ratio involved in the reaction is controlled to be 2 to 5m 3 1t, obtaining a second leaching solution and second leaching residues, returning the second leaching solution to the primary oxidation leaching step, mixing the second leaching solution with the crystallized solution to be used as a low-acid solution, and recovering valuable metal elements such as lead, silver, bismuth and the like contained in the second leaching residues after subsequent treatment.
In some embodiments, in the step S50, the fourth predetermined temperature is room temperature to 95 ℃, the fourth predetermined time is 60 to 180min, and the end point pH of the reaction ore pulp of the purification impurity removal reaction is controlled to be 5.0 to 5.2, so as to finally obtain the purification impurity removal slag and the purification impurity removal liquid containing 110 to 140g/L of zinc, 10 to 40mg/L of iron, and 0.5 to 1mg/L of arsenic.
In some embodiments, the oxidizing gas is oxygen or oxygen-enriched air.
Specifically, in the step S20, oxygen or oxygen-enriched air is continuously introduced during the leaching process, so that the copper ions in the low-acid liquor can be prevented from undergoing secondary sulfidation precipitation during a first-stage leaching process; in the step S30, oxygen or oxygen-enriched air is continuously introduced during the leaching process to promote efficient dissolution of the insoluble phase of the low-valent sulfide in the first leaching residue, thereby comprehensively improving the leaching rates of copper and zinc.
In some embodiments, the second leach solution and the post-crystallization solution are combined for use as a low acid solution.
In some embodiments, further comprising the step of:
and washing the second leaching residue to obtain washing water and lead-silver-bismuth residue.
Alternatively, the washing mode can be selected from rinsing or stirring washing.
In some embodiments, the washing water and the concentrated sulfuric acid are mixed to be used as a high-acid solution for return, and the higher acidity can promote the efficient dissolution of the low-valent sulfide insoluble phase in the first leaching residue, so that the leaching rates of copper and zinc are comprehensively improved.
In some embodiments, the lead-silver-bismuth slag is treated by pyrometallurgical lead smelting to recover lead, silver, and bismuth separately.
Specifically, the valuable metals in the lead, silver and bismuth slag can be removed in a segmented manner by adopting a pyrogenic process for smelting lead, wherein the silver is removed by adopting a zinc-adding and silver-removing method, the zinc is added in batches by adopting a counter-current operation method, so that the silver floats on the surface of the liquid lead in a solid silver-zinc shell form and is classified with the lead, and then the bismuth is removed by adopting a calcium-magnesium adding manner, the calcium, the magnesium and the bismuth in the liquid lead can form a compound with a high melting point and a density smaller than that of the lead, and the compound floats on the surface of the liquid lead in a hard shell form to be separated from the lead, thereby realizing the respective recovery of the lead, the silver and the bismuth.
In some embodiments, the first leaching solution is a solution containing 10 to 30g/L of acid and 19 to 65g/L of copper.
In some embodiments, the second leachate comprises 20 to 60g/L of acid.
In some embodiments, the step of decoppering the first leach solution to obtain cathode copper and a decoppering solution includes:
and (3) carrying out copper removal on the first leaching solution by adopting a traditional electrodeposition process or a rotational flow electrodeposition process, and controlling the concentration of residual copper ions in the solution after electrodeposition copper removal to be 300-800 mg/L to obtain cathode copper and a copper removal solution.
The specific process flow chart in the actual production can be seen in fig. 2.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for treating copper smelting white smoke dust comprises the following specific steps:
(1) And (3) low-temperature volatilization: putting copper smelting white smoke dust containing 13.23% of copper, 8.42% of arsenic, 15.74% of zinc, 15.73% of lead, 0.015% of silver and 2.87% of bismuth, which is provided by a pyrometallurgical copper smelting enterprise, into a reaction furnace, reacting for 150min at 280 ℃ to obtain white arsenic with the arsenic trioxide content of 85.94% and arsenic-removing smoke dust with the arsenic content of 1.0%, and enabling the arsenic-removing smoke dust to enter a primary oxidation leaching process;
(2) Primary oxidation leaching: continuously adding the low acid liquid formed by mixing the arsenic-removed smoke dust obtained in the step (1) with the second leaching solution and the crystallized solution into a reaction tank with a stirring device, continuously introducing oxygen into the reaction tank, and controlling the solid-to-solid ratio of the reaction ore pulp to be 2 1m 3 T, the reaction temperature is 95 ℃, the reaction time is 90min, after the reaction is finished, the leached ore pulp is subjected to liquid-solid separation to obtain a first leaching solution containing 30g/L of acid and 64.83g/L of copper and first leaching slag, and the first leaching solution entersPerforming an electrodeposition copper removal process, and performing secondary oxidation leaching on the first leaching residue;
(3) Secondary oxidation leaching: continuously adding high-acid liquor formed by mixing the first leaching slag in the step (2) with washing water and concentrated sulfuric acid into a reaction tank with a stirring device, continuously introducing oxygen into the reaction tank, and controlling the solid-to-solid ratio of the reaction ore pulp to be 2 3 T, the reaction temperature is 50 ℃, the reaction time is 90min, and after the reaction is finished, the leached ore pulp is subjected to liquid-solid separation to obtain a second leaching solution containing 60g/L of acid and second leaching residues; and stirring and washing the second leaching residue to obtain washing water and lead-silver-bismuth residues containing 41.37% of lead, 0.039% of silver and 7.55% of bismuth, wherein after the lead-silver-bismuth residues enter a pyrogenic lead smelting system or are treated independently, valuable metals such as lead, silver, bismuth and the like are respectively recovered, and the washing water is returned to a secondary oxidation leaching process.
(4) And (3) electrodeposition copper removal: and (3) continuously pumping the first leaching solution produced in the step (2) into a copper electrolytic tank, and adopting a three-section traditional electrodeposition process to remove copper to obtain a copper-removed solution with the concentration of cathode copper and residual copper ions of 800mg/L, wherein the copper-removed solution enters a purification and impurity removal process.
(5) Purifying and removing impurities: pumping the decoppered solution obtained in the step (4) into a reaction tank with a stirring device, continuously adding zinc oxide smoke dust into the reaction tank, introducing air, controlling the reaction temperature to be 70 ℃, the reaction time to be 2 hours and the pH value of the reaction ore pulp to be 5.2, carrying out liquid-solid separation after the reaction is finished to obtain purified impurity-removed slag and purified impurity-removed liquid containing 100g/L zinc, 40mg/L iron and 1mg/L arsenic, and enabling the purified impurity-removed liquid to enter a concentration and crystallization process.
(6) Concentration and crystallization: and (4) concentrating and crystallizing the purified impurity-removed solution produced in the step (5) to obtain a refined zinc sulfate heptahydrate product and a crystallized solution, and returning the concentrated crystallized solution to the first-stage oxidation leaching process.
After the copper smelting white smoke dust is treated by the method, the low-temperature volatilization dearsenification rate is 93.33%, the copper leaching rate is 98.33% after the two-stage oxidation leaching, and the zinc leaching rate is 98.95%.
Example 2
A method for treating copper smelting white smoke dust comprises the following specific steps:
(1) And (3) low-temperature volatilization: putting copper smelting white smoke containing 10.64% of copper, 10.02% of arsenic, 19.35% of zinc, 21.23% of lead, 0.05% of silver and 1.28% of bismuth, which are provided by a pyrometallurgical copper smelting enterprise, into a reaction furnace, reacting for 60min at 450 ℃ to obtain white arsenic with the arsenic trioxide content of 90.45% and arsenic-removed smoke containing 0.5% of arsenic, and allowing the arsenic-removed smoke to enter a primary oxidation leaching process;
(2) Primary oxidation leaching: continuously adding low acid liquid formed by mixing the arsenic-removed smoke dust obtained in the step (1) with the second leaching solution and the crystallized solution into a reaction tank with a stirring device, continuously introducing oxygen-enriched air into the reaction tank, and controlling the solid-to-solid ratio of reaction ore pulp to be 5m 3 T, reacting at room temperature for 120min, carrying out liquid-solid separation on leached ore pulp after the reaction is finished to obtain a first leaching solution containing 10g/L of acid and 21.08g/L of copper and first leaching residues, carrying out an electrodeposition copper removal process on the first leaching solution, and carrying out a secondary oxidation leaching process on the first leaching residues;
(3) Secondary oxidation leaching: continuously adding high-acid liquid formed by mixing the first leaching slag in the step (2) with washing water and concentrated sulfuric acid into a reaction tank with a stirring device, continuously introducing oxygen-enriched air into the reaction tank, and controlling the solid-to-solid ratio of the reaction ore pulp to be 5m 3 T, the reaction temperature is 95 ℃, the reaction time is 60min, and after the reaction is finished, liquid-solid separation is carried out on leached ore pulp to obtain a second leaching solution containing 20g/L of acid and second leached residues; leaching the second leaching residue to obtain washing water and lead-silver-bismuth residue containing 70.06% of lead, 0.165% of silver and 4.22% of bismuth, wherein after the lead-silver-bismuth residue enters a pyrogenic process lead smelting system or is treated independently, valuable metals such as lead, silver, bismuth and the like are respectively recovered, and the washing water is returned to a second-stage oxidation leaching process.
(4) And (3) electrodeposition copper removal: continuously pumping the first leaching solution produced in the step (2) into a copper electrolytic tank, and adopting a two-stage cyclone electrodeposition process to remove copper to obtain a copper removal solution with the concentration of cathode copper and residual copper ions of 300mg/L, and introducing the copper removal solution into a purification and impurity removal process.
(5) Purifying and removing impurities: pumping the decoppered solution obtained in the step (4) into a reaction tank with a stirring device, continuously adding zinc oxide smoke dust into the reaction tank, introducing oxygen, controlling the reaction temperature to be 95 ℃, the reaction time to be 1h and the end point pH of reaction ore pulp to be 5.2, carrying out liquid-solid separation after the reaction is finished to obtain purified impurity-removed slag and purified impurity-removed liquid containing 110g/L zinc, 10mg/L iron and 0.5mg/L arsenic, and enabling the purified impurity-removed liquid to enter a concentration and crystallization process.
(6) Concentration and crystallization: and (4) concentrating and crystallizing the purified impurity-removed solution produced in the step (5) to obtain a refined zinc sulfate heptahydrate product and a crystallized solution, and returning the concentrated crystallized solution to the first-stage oxidation leaching process.
After the copper smelting white smoke dust is treated by the method, the low-temperature volatilization arsenic removal rate is 98.36%, the copper leaching rate is 98.57% after the two-stage oxidation leaching, and the zinc leaching rate is 98.36%.
Comparative example 2 (first-stage and second-stage oxidation leaching, respectively)
A method for treating copper smelting white smoke dust comprises the following specific steps:
(1) And (3) low-temperature volatilization: putting copper smelting white smoke containing 10.64% of copper, 10.02% of arsenic, 19.35% of zinc, 21.23% of lead, 0.05% of silver and 1.28% of bismuth, which are provided by a pyrometallurgical copper smelting enterprise, into a reaction furnace, reacting for 60min at 450 ℃ to obtain white arsenic with the arsenic trioxide content of 90.45% and arsenic-removed smoke containing 0.5% of arsenic, and allowing the arsenic-removed smoke to enter a primary oxidation leaching process;
(2) Primary leaching: continuously adding low acid liquid formed by mixing the arsenic-removing smoke dust obtained in the step (1) with the second leaching solution and the crystallized solution into a reaction tank with a stirring device, and controlling the solid-to-liquid ratio of reaction ore pulp to be 5m 3 T, reacting at room temperature for 120min, carrying out liquid-solid separation on leached ore pulp after the reaction is finished to obtain a first leaching solution containing 15g/L of acid and 14.89g/L of copper and first leaching residues, carrying out an electrodeposition copper removal process on the first leaching solution, and carrying out a secondary oxidation leaching process on the first leaching residues;
(3) Secondary leaching: continuously adding high-acid liquor formed by mixing the first leaching slag in the step (2) with washing water and concentrated sulfuric acid into a reaction tank with a stirring device, and controlling the solid-to-solid ratio of reaction ore pulp to be 5m 3 T, the reaction temperature is 95 ℃, the reaction time is 60min, and after the reaction is finished, liquid-solid separation is carried out on leached ore pulp to obtain a second leaching solution containing 28g/L acid and second leached residues; leaching the second leaching residue to obtain washing water and lead-silver-bismuth residue containing 58.81% of lead, 0.139% of silver and 3.55% of bismuth, and introducing the lead-silver-bismuth residue into a pyrogenic processAfter the lead smelting system or the single treatment, valuable metals such as lead, silver, bismuth and the like are respectively recovered, and washing water is returned to the secondary oxidation leaching process.
(4) And (3) electrodeposition copper removal: and (3) continuously pumping the first leaching solution produced in the step (2) into a copper electrolytic tank, and removing copper by adopting a two-stage cyclone electrodeposition process to obtain cathode copper and a copper-removing solution with the residual copper ion concentration of 300mg/L, wherein the copper-removing solution enters a purification and impurity removal process.
(5) Purifying and removing impurities: pumping the decoppered solution obtained in the step (4) into a reaction tank with a stirring device, continuously adding zinc oxide smoke dust into the reaction tank, introducing oxygen, controlling the reaction temperature to be 95 ℃, the reaction time to be 1h and the end point pH of reaction ore pulp to be 5.2, carrying out liquid-solid separation after the reaction is finished to obtain purified impurity-removed slag and purified impurity-removed liquid containing 100g/L zinc, 10mg/L iron and 0.5mg/L arsenic, and enabling the purified impurity-removed liquid to enter a concentration and crystallization process.
(6) Concentration and crystallization: and (4) concentrating and crystallizing the purified impurity-removed solution produced in the step (5) to obtain a refined zinc sulfate heptahydrate product and a crystallized solution, and returning the concentrated crystallized solution to the first-stage oxidation leaching process.
After the copper smelting white smoke dust is treated by the method, the low-temperature volatilization arsenic removal rate is 98.36%, the copper leaching rate is 70.34% after two-stage leaching, and the zinc leaching rate is 85.01%.
Therefore, the leaching rates of copper and zinc are respectively reduced by 28.23 percent and 13.25 percent after the two-stage oxidation leaching of the arsenic-removing smoke dust is replaced by the two-stage leaching, which is not beneficial to the comprehensive and efficient recovery of copper and zinc.
Example 3
A method for treating copper smelting white smoke dust comprises the following specific steps:
(1) And (3) low-temperature volatilization: putting copper smelting white smoke containing 6.07% of copper, 6.43% of arsenic, 10.94% of zinc, 25.79% of lead, 0.08% of silver and 5.02% of bismuth, which are provided by a pyrometallurgical copper smelting enterprise, into a reaction furnace, reacting for 90min at 350 ℃ to obtain white arsenic with 74% of arsenic trioxide content and arsenic-removing smoke dust with 0.8% of arsenic, and enabling the arsenic-removing smoke dust to enter a first-stage oxidation leaching process;
(2) Primary oxidation leaching: continuously adding the low acid liquid formed by mixing the arsenic-removing smoke dust in the step (1) with the second leaching solution and the crystallized solution into a stirrerIn the reaction tank of the stirring device, continuously introducing oxygen into the reaction tank, and controlling the liquid-solid ratio of the reaction ore pulp to be 3 3 T, the reaction temperature is 70 ℃, the reaction time is 60min, after the reaction is finished, liquid-solid separation is carried out on leached ore pulp to obtain a first leaching solution containing 18g/L of acid and 19.62g/L of copper and first leaching slag, the first leaching solution enters an electrodeposition copper removal process, and the first leaching slag enters a secondary oxidation leaching process;
(3) Secondary oxidation leaching: continuously adding high-acid liquor formed by mixing the first leaching slag in the step (2) with washing water and concentrated sulfuric acid into a reaction tank with a stirring device, continuously introducing oxygen-enriched air into the reaction tank, and controlling the solid-to-solid ratio of the reaction ore pulp to be 3 3 T, the reaction temperature is 70 ℃, the reaction time is 120min, and after the reaction is finished, liquid-solid separation is carried out on leached ore pulp to obtain a second leaching solution containing 46g/L acid and second leached residues; and stirring and washing the second leaching residue to obtain washing water and lead-silver-bismuth residue containing 67.83% of lead, 0.039% of silver and 13.20% of bismuth, wherein after the lead-silver-bismuth residue enters a pyrogenic lead smelting system or is treated independently, valuable metals such as lead, silver, bismuth and the like are respectively recovered, and the washing water is returned to a secondary oxidation leaching process.
(4) And (3) electrodeposition copper removal: continuously pumping the first leaching solution produced in the step (2) into a copper electrolytic tank, and adopting a two-stage cyclone electrodeposition process to remove copper to obtain a copper removal solution with cathode copper and residual copper ion concentration of 500mg/L, and introducing the copper removal solution into a purification and impurity removal process.
(5) Purifying and removing impurities: pumping the decoppered solution obtained in the step (4) into a reaction tank with a stirring device, continuously adding zinc oxide smoke dust into the reaction tank, introducing oxygen-enriched air, controlling the reaction time to be 3 hours at room temperature and the end point pH of the reaction ore pulp to be 5.0, carrying out liquid-solid separation after the reaction is finished to obtain purified impurity-removed slag and purified impurity-removed liquid containing 125g/L zinc, 25mg/L iron and 0.7mg/L arsenic, and enabling the purified impurity-removed liquid to enter a concentration and crystallization process.
(6) Concentration and crystallization: and (4) concentrating and crystallizing the purified impurity-removed solution produced in the step (5) to obtain a refined zinc sulfate heptahydrate product and a crystallized solution, and returning the concentrated crystallized solution to the first-stage oxidation leaching process.
After the copper smelting white smoke dust is treated by the method, the low-temperature volatilization arsenic removal rate is 91.29%, the copper leaching rate is 98.03% after the two-stage oxidation leaching, and the zinc leaching rate is 98.63%.
In summary, the invention discloses a method for treating copper smelting white smoke dust, which comprises the following steps: low-temperature volatilization, primary oxidation leaching, secondary oxidation leaching, electrodeposition copper removal, purification and impurity removal, concentration and crystallization. The invention volatilizes and enriches more than 95% of arsenic by adopting a low-temperature volatilization process, realizes the high-efficiency separation of the arsenic and valuable metals in the smoke dust at low temperature, provides possibility for the short-flow, low-cost and high-efficiency recovery of valuable elements such as copper, lead, zinc, lead, silver, bismuth and the like in the smoke dust, can efficiently leach and enrich the valuable metals such as copper, zinc and the like after the arsenic-removed smoke dust is subjected to two-stage normal-pressure oxidation leaching treatment, and can realize the high-efficiency recovery of the copper and the zinc after the working procedures such as electrodeposition copper removal, hydrolysis impurity removal, concentration crystallization and the like.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A treatment method of copper smelting white smoke dust is characterized by comprising the following steps:
reacting copper smelting white smoke dust at a first preset temperature for a first preset time to obtain white arsenic and arsenic-removed smoke dust;
mixing the arsenic-removing smoke dust with low acid liquor, introducing oxidizing gas, reacting at a second preset temperature for a second preset time, and performing liquid-solid separation after the reaction is finished to obtain a first leaching solution and first leaching residues;
mixing the first leaching residue with a high acid solution, introducing an oxidizing gas, reacting at a third predetermined temperature for a third predetermined time, and performing liquid-solid separation after the reaction is finished to obtain a second leaching solution and a second leaching residue;
decoppering the first leaching solution to obtain cathode copper and a decoppered solution;
adding zinc oxide smoke dust into the decoppering solution, introducing oxidizing gas, reacting at a fourth preset temperature for a fourth preset time, and performing liquid-solid separation after the reaction is finished to obtain purified impurity-removed slag and purified impurity-removed liquid;
concentrating and crystallizing the purified impurity-removed solution to obtain refined zinc sulfate heptahydrate and a crystallized solution;
wherein the low acid liquid is a mixed solution of concentrated sulfuric acid and water, and the acidity of the low acid liquid is 5-40 g/L; the high acid liquid is a mixed solution of concentrated sulfuric acid and water, and the acidity of the high acid liquid is 10-70 g/L.
2. The method of treating copper smelting white dust according to claim 1, wherein the first predetermined temperature is 280-450 ℃, the first predetermined time is 60-150 min, the second predetermined temperature is room temperature-95 ℃, the second predetermined time is 60-120 min, the third predetermined temperature is room temperature-95 ℃, the third predetermined time is 60-120 min, the fourth predetermined temperature is room temperature-95 ℃, and the fourth predetermined time is 60-180 min.
3. The method of treating copper smelting white flue dust according to claim 1, characterized in that the oxidizing gas is oxygen or oxygen-enriched air.
4. The method of claim 1, wherein the second leach solution and the post-crystallization solution are combined for return use as a low acid solution.
5. The method of treating copper smelting white flue dust according to claim 1, further comprising the steps of:
and washing the second leaching residue to obtain washing water and lead-silver-bismuth residue.
6. The method of claim 5, wherein the wash water is mixed with concentrated sulfuric acid and returned to use as a high acid liquor.
7. The method for treating the copper smelting white smoke dust according to claim 5, wherein the lead-silver-bismuth slag is treated by adopting a pyrogenic process for lead smelting, and lead, silver and bismuth are respectively recovered.
8. The method according to claim 1, wherein the first leaching solution is a solution containing 10-30 g/L acid and 19-65 g/L copper.
9. The method according to claim 1, wherein the second leach solution contains 20-60 g/L acid.
10. The method according to claim 1, wherein the step of decoppering the first leach solution to obtain cathode copper and a decoppered solution comprises:
and (3) decoppering the first leaching solution by adopting an electrodeposition process, and controlling the concentration of residual copper ions in the decoppered solution after electrodeposition decoppering to be 300-800 mg/L to obtain cathode copper and a decoppered solution.
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