CN111607698A - Method for treating copper anode slime - Google Patents
Method for treating copper anode slime Download PDFInfo
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- CN111607698A CN111607698A CN201910143688.1A CN201910143688A CN111607698A CN 111607698 A CN111607698 A CN 111607698A CN 201910143688 A CN201910143688 A CN 201910143688A CN 111607698 A CN111607698 A CN 111607698A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
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- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention discloses a method for treating copper anode slime, which comprises the following steps: (1) mixing and reacting copper anode slime with first concentrated sulfuric acid, and filtering to obtain copper-removed slime and copper-containing filtrate; (2) mixing the copper-removed mud and second concentrated sulfuric acid for slurrying to obtain slurry; (3) roasting and selenium steaming treatment is carried out on the slurry to obtain selenium steaming slag and selenium steaming flue gas; (4) mixing the selenium steaming slag with a solvent to separate copper, so as to obtain a copper separating liquid and a copper separating slag; (5) sending the copper-separating slag, a reducing agent, a first gold and silver trapping agent and a first slagging agent to a metallurgical furnace for smelting treatment to obtain precious lead, smelting slag and smelting flue gas; (6) under the environment of oxygen-containing compressed gas, blowing the precious lead, a second gold and silver collecting agent and a second slagging agent in a metallurgical furnace to obtain blowing slag, gold and silver-containing alloy and blowing flue gas; (7) and refining the gold-silver-containing alloy and the third slagging constituent in a metallurgical furnace to obtain the gold-silver alloy, refining slag and refining flue gas.
Description
Technical Field
The invention belongs to the field of copper anode slime treatment, and particularly relates to a method for treating copper anode slime.
Background
At present, the traditional domestic method for treating the copper anode slime generally comprises a wet process and a fire process, and in addition, a Kaldo furnace process introduced from abroad is also provided.
The traditional domestic wet process has the problems of long flow, large noble metal overstock amount, large waste water amount, difficult thorough removal of lead element and the like, and meanwhile, the copper anode slime has complex components, different flows adopted by different enterprises and poor flow adaptability. The traditional domestic fire process has stronger adaptability than a wet process, is suitable for large-scale production, but has the problems of large number of furnace bodies, low automation degree, difficult solution of environmental protection problems such as flue gas pollution and the like, long production period, overstocked capital and the like. The Kaldo furnace process introduced from abroad has the advantages of strong adaptability, high automation degree, short production period, environmental friendliness and the like, but also has the defects of high introduction cost, relatively low selenium recovery rate and the like.
Thus, the existing techniques for treating copper anode slime are in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one object of the present invention is to provide a method for treating copper anode slime, which can effectively remove selenium in the copper anode slime, can complete the smelting, blowing and refining of the component copper slag in one device, can significantly reduce the device usage amount of the copper anode slime treatment process, can obtain a gold-silver alloy with gold-silver content not less than 97 wt%, and has significant economic value.
In one aspect of the invention, the invention proposes a method of treating copper anode slime, the method comprising, according to an embodiment of the invention:
(1) mixing and reacting copper anode slime with first concentrated sulfuric acid, and filtering to obtain copper-removed slime and copper-containing filtrate;
(2) mixing the copper-removed mud with second concentrated sulfuric acid for slurrying treatment so as to obtain slurry;
(3) roasting and selenium steaming treatment is carried out on the slurry, so as to obtain selenium steaming slag and selenium steaming flue gas;
(4) mixing the selenium steaming slag with a solvent for copper separation so as to obtain a copper separation liquid and a copper separation slag;
(5) sending the copper-separating slag, a reducing agent, a first gold and silver trapping agent and a first slagging agent to a metallurgical furnace for smelting treatment so as to obtain precious lead, smelting slag and smelting smoke;
(6) under the environment of oxygen-containing compressed gas, converting the precious lead, a second gold and silver collecting agent and a second slagging agent in the metallurgical furnace to obtain converting slag, a gold and silver-containing alloy and converting flue gas;
(7) and refining the gold-silver-containing alloy and a third slagging constituent in the metallurgical furnace so as to obtain a gold-silver alloy, refining slag and refining flue gas.
According to the method for treating the copper anode slime, disclosed by the embodiment of the invention, the copper anode slime is mixed with the first concentrated sulfuric acid for reaction and is filtered, so that part of copper, arsenic, antimony, bismuth and other impurities in the copper anode slime can be removed; in the process of roasting and selenium steaming of the slurry, selenide in the slurry reacts with sulfuric acid in the slurry to generate selenate, the selenate is decomposed into selenium dioxide and is volatilized to enter selenium steaming flue gas, the selenium in the copper anode mud is removed, the redundant sulfur dioxide generated by the decomposition of the sulfuric acid also enters the selenium steaming flue gas, and meanwhile, impurities such as copper, nickel and the like in the slurry react with the sulfuric acid to generate soluble salt which is stored in selenium steaming slag; after mixing with the solvent, evaporating soluble sulfate in the selenium slag to dissolve in the solvent, and after copper separation, obtaining copper separation liquid containing copper and nickel salt and copper separation slag containing lead, gold and silver, thereby further realizing the separation of copper from lead, gold and silver; in the smelting process of the obtained copper-separating slag, most of oxides of arsenic impurities volatilize into smelting smoke, a small amount of oxides of antimony impurities enter into the smoke, part of the oxides enter into smelting slag, part of the oxides enter into precious lead, and the oxides of bismuth impurities are mainly reduced and enter into the precious lead; during the blowing process of the precious lead, most Pb and the rest Cu, Se, Sb, Bi and Te are strongly oxidized into blowing slag, and most impurities in the precious lead are removed after blowing; during the refining process of the gold-silver-containing alloy, part of impurity Te enters refining slag, and the rest of impurities Se and Te are strongly oxidized and volatilized to enter flue gas. Therefore, the method can effectively remove selenium in the copper anode mud, can finish smelting, blowing and refining of the copper slag in one device, obviously reduces the device usage of the copper anode mud treatment process, can obtain the gold-silver alloy with the gold-silver content not less than 97 wt%, and has obvious economic value.
In addition, the method for treating copper anode slime according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the above method of treating copper anode slime further comprises: (8) and (5) returning the blowing slag and the refining slag to the step (5) for smelting. Therefore, the recovery rate of the heavy metal in the copper anode mud is improved.
In some embodiments of the present invention, the above method of treating copper anode slime further comprises: (9) and before the copper separation slag is subjected to the smelting treatment, drying the copper separation slag. Therefore, the energy consumption of smelting treatment is reduced.
In some embodiments of the present invention, the above method of treating copper anode slime further comprises: (10) and carrying out first dynamic wave washing on the selenium steaming flue gas so as to obtain crude selenium, a first washing liquid and first washed flue gas. Thereby, selenium recovery can be achieved.
In some embodiments of the invention, step (10) comprises: (10-1) carrying out first primary dynamic wave washing on the selenium steaming flue gas by adopting first washing water so as to obtain first primary washed flue gas and first primary washed liquid; (10-2) carrying out first secondary dynamic wave washing on the first primary washed flue gas by using second washing water so as to obtain the first washed flue gas and first secondary washed liquid, and returning the first secondary washed liquid to the step (10-1) for use as first washing water; (10-3) settling the first primary washing liquid to obtain a first supernatant and a first underflow; (10-4) sending a part of the first supernatant to a first incident head tank, and extracting the rest part of selenium to obtain a first washing solution and first crude selenium; (10-5) carrying out pressure filtration on the first bottom flow to obtain a first filtrate and second crude selenium, and returning the first filtrate to the step (10-3) for carrying out the sedimentation; wherein the crude selenium comprises the first crude selenium and the second crude selenium.
In some embodiments of the present invention, the above method of treating copper anode slime further comprises: (11) and (3) carrying out second dynamic wave washing on the smelting flue gas, the blowing flue gas and the refining flue gas so as to obtain a filter cake, a second washing liquid and second washed flue gas, and returning the filter cake to the step (5) for smelting. Therefore, the smelting flue gas, the blowing flue gas and the refining flue gas can be efficiently treated, and the treatment cost of the process is reduced.
In some embodiments of the invention, step (11) comprises: (11-1) carrying out second-stage dynamic wave washing on the smelting flue gas, the blowing flue gas and the refining flue gas by using third washing water so as to obtain second-stage washed flue gas and second-stage washed liquid; (11-2) carrying out second-stage dynamic wave washing on the second-stage washed flue gas by adopting fourth washing water so as to obtain second-stage washed flue gas and second-stage washed liquid, and returning the second-stage washed liquid to the step (11-1) to be used as third washing water; (11-3) settling the second primary washing liquid to obtain a second supernatant and a second underflow; (11-4) sending a part of the second supernatant to a second accident head tank, and the rest is the second washing liquid; (11-5) performing pressure filtration on the second underflow to obtain a second filtrate and the filter cake, and returning the second filtrate to the step (11-3) for the sedimentation.
In some embodiments of the present invention, in step (5), the temperature of the melting process is 1100-1200 ℃.
In some embodiments of the present invention, in step (6), the temperature of the blowing process is 1150-3/h。
In some embodiments of the present invention, in step (7), the temperature of the refining process is 1800-.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of treating copper anode slime according to one embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method of treating copper anode slime according to yet another embodiment of the present invention;
FIG. 3 is a schematic flow diagram of a method of treating copper anode slime according to yet another embodiment of the present invention;
FIG. 4 is a schematic flow diagram of a method of treating copper anode slime in accordance with yet another embodiment of the present invention
FIG. 5 is a schematic flow diagram of a method of treating copper anode slime according to yet another embodiment of the present invention;
FIG. 6 is a schematic flow diagram of a method of treating copper anode slime according to yet another embodiment of the present invention;
fig. 7 is a schematic flow diagram of a method of treating copper anode slime according to yet another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, the invention proposes a method of treating copper anode slime, according to an embodiment of the invention, with reference to fig. 1, the method comprising:
s100: mixing and reacting copper anode mud with first concentrated sulfuric acid, and filtering
In the step, copper anode slime and first concentrated sulfuric acid are mixed and reacted and then filtered, so that copper removal slime and copper-containing filtrate are obtained. Specifically, the copper anode slime and first concentrated sulfuric acid are mixed, stirred and reacted for 4-6 hours, compressed air or oxygen can be introduced to enhance the reaction effect if necessary, copper, arsenic, antimony, bismuth and the like in the copper anode slime form soluble sulfate with sulfuric acid, and after filtration, the copper-removed slime is separated from copper-containing filtrate, so that the removal of impurities such as copper, arsenic, antimony, bismuth and the like in the copper anode slime is realized, the subsequent recovery of selenium and heavy metals is facilitated, and the product quality of the subsequently obtained gold-silver alloy is improved; meanwhile, the content of the copper anode mud is reduced, and the reduction of the specification of subsequent equipment is facilitated. The content of copper in the copper anode slime is not particularly limited, and may be, for example, 10 wt% to 20 wt%. According to an embodiment of the present invention, the mixing mass ratio of the copper anode slime to the first concentrated sulfuric acid may be 1: 0.7 to 1.2. The inventor finds that if the mixing mass ratio of the copper anode slime to the first concentrated sulfuric acid is too high, the first concentrated sulfuric acid is relatively insufficient, and the content of impurities in the obtained decoppered slime is high after the pretreatment of the mixing reaction, so that the product quality of the subsequent gold-silver alloy is adversely affected, the decoppered slime amount is increased, and the treatment burden of subsequent equipment is increased; if the mixing mass ratio of the copper anode slime to the first concentrated sulfuric acid is too low, the first concentrated sulfuric acid is relatively excessive, which not only causes the waste of sulfuric acid, but also aggravates the corrosion of subsequent equipment and pipelines.
S200: mixing the decoppered mud with second concentrated sulfuric acid for slurrying
In the step, the decoppered mud and second concentrated sulfuric acid are mixed and pulped so as to obtain slurry. Adding the pretreated decoppered mud into a slurrying tank, adding a certain amount of sulfuric acid in proportion, and uniformly stirring and reacting the decoppered mud and the sulfuric acid in the slurrying tank for 4-6 hours to form slurry. According to an embodiment of the invention, the mass ratio of the decoppered mud to the second concentrated sulfuric acid may be 1: 0.7 to 0.8. The inventor finds that if the mixing mass ratio of the decoppered mud to the second concentrated sulfuric acid is too high, the second concentrated sulfuric acid is relatively insufficient, and the content of impurities in the obtained slurry is high after the mixing and slurrying treatment, so that the quality of the subsequent gold-silver alloy product is adversely affected, and the treatment burden of subsequent equipment is increased; if the mixing mass ratio of the decoppered mud to the second concentrated sulfuric acid is too low, the second concentrated sulfuric acid is relatively excessive, which not only causes the waste of sulfuric acid, but also aggravates the corrosion of subsequent equipment and pipelines.
S300: roasting and selenium steaming treatment is carried out on the slurry
In the step, the slurry is roasted and selenium-evaporated so as to obtain selenium-evaporated slag and selenium-evaporated flue gas. Specifically, the equipment for roasting and selenium steaming treatment is usually a rotary kiln and a muffle furnace. After the slurry is heated at a high temperature in a roasting selenium steaming device, selenide in the slurry reacts with sulfuric acid in the slurry to generate selenate, then the selenate is decomposed into selenium dioxide at a higher temperature and is volatilized to enter selenium steaming smoke, so that selenium in the copper anode slime is removed, and redundant sulfur dioxide generated by the decomposition of the sulfuric acid also enters the selenium steaming smoke; meanwhile, impurities such as copper, nickel and the like in the slurry react with sulfuric acid to generate soluble salt, and the soluble salt is stored in the selenium steaming slag. The selenium content in the obtained selenium steaming slag is less than 0.5 wt%. Therefore, the sulfated slurry is adopted for roasting and selenium steaming, so that selenium element can be separated out independently, the recovery rate of subsequent selenium is improved, and the corrosion of selenious acid to subsequent equipment can be reduced. According to one embodiment of the invention, the conditions of the roasting and selenium steaming treatment can be as follows: roasting at 250-350 deg.c for 1-4 hr, and steaming at 550-650 deg.c for 2-4 hr. The inventor finds that the low temperature or the short time of roasting and selenium steaming can affect the reaction degree of copper, nickel and other elements with sulfuric acid and the volatilization of selenium element; too high temperature or too long time not only wastes energy, and the material is easy to harden simultaneously.
S400: mixing the selenium-steaming slag with a solvent to separate copper
In the step, the selenium steaming slag and a solvent are mixed for copper separation, so that a copper separation liquid and a copper separation slag are obtained. Specifically, the solvent can be water, and in order to improve the leaching rate of soluble salts in the selenium steaming residue, the solvent can also comprise a small amount of sulfuric acid. The inventor finds that elements such as copper, nickel and the like in the selenium steaming slag exist as soluble salts, the soluble salts can be taken out after the elements are mixed with the solvent, copper is separated to obtain copper-nickel salt-containing copper separating liquid and lead, gold and silver-containing copper separating slag, and further separation of copper from lead, gold and silver is realized. The copper content in the obtained copper-separating slag is less than 0.5 wt%. Therefore, when dilute acid or water is used for copper separation, the residual sulfuric acid in the selenium steaming slag can be fully utilized, so that sulfates and oxides of base metals such as copper, nickel and the like in the selenium steaming slag are dissolved in a liquid phase, and precious metals such as gold, silver and the like are left in the slag, thereby realizing the separation of the precious metals such as gold, silver and the like and the base metals such as copper, nickel and the like.
According to one embodiment of the invention, the solid-to-liquid ratio of the selenium steaming slag to the solvent can be 1: 4-6. The inventor finds that if the mixing mass ratio of the selenium steaming slag to the solvent is too high, namely the solvent is insufficient, impurities such as copper, nickel and the like in the selenium steaming slag can not be removed, the energy consumption of a subsequent metallurgical furnace is increased, and the product quality of the finally obtained gold-silver alloy is influenced; if the mixing mass ratio of the selenium steaming slag and the solvent is too low, namely the solvent is excessive, the solvent is wasted, and the cost of copper separation treatment is increased.
According to another embodiment of the present invention, the temperature of the copper separation treatment can be 80-90 degrees centigrade, and the time can be 4-6 h. The inventor finds that the evaporation amount of the acid mist greatly influences the environment when the temperature of the copper separation treatment is too high, and the reaction degree is influenced when the temperature of the copper separation treatment is too low; too long copper separation treatment time causes energy waste, and too short copper separation treatment time affects reaction degree.
S500: delivering the copper-separating slag, a reducing agent, a first gold and silver trapping agent and a first slagging agent to a metallurgical furnace for smelting treatment
In the step, the copper-separating slag, a reducing agent, a first gold and silver trapping agent and a first slagging agent are sent to a metallurgical furnace for smelting treatment, so that precious lead, smelting slag and smelting smoke are obtained. Specifically, in the smelting process, fuel is blown into the smelting furnace through a burner or a spray gun so that the smelting furnace maintains the temperature required by smelting. Impurities in the copper-separating slag mainly exist in the form of oxides or salts containing oxides, and the oxides or the salts react with the added flux to generate smelting slag which floats on the surface of the melt and is removed; and other metal oxides volatilize into smelting flue gas due to low boiling points. The lead-containing compound in the copper separating slag can be directly reduced into metallic lead by the added reducing agent, and the lead melt is a good collecting agent for gold and silver. Because the specific gravity of the lead, the gold and the silver is higher, the lead, the gold and the silver particles form Pb (Au + Ag) alloy (namely noble lead) to deposit at the bottom of the smelting furnace in the process of precipitation, thereby achieving the purpose of separating the gold, the silver and the furnace slag. After the copper-separating slag is smelted, the content of gold in the smelting slag is not more than 0.01 wt%, and the content of silver in the smelting slag is less than 0.6 wt%. After smelting is finished, a furnace mouth of the metallurgical furnace is slowly tilted downwards, a thin slag layer with good fluidity on the surface of the metal melt in the furnace is poured into a slag ladle, and separation of precious lead and smelting slag is realized. The smelting aims to enrich gold and silver in the copper-separating slag to form noble lead, so that impurities enter the smelting slag or volatilize the impurities into smelting smoke, primary separation of the gold and the silver from the impurities is achieved, and preparation is provided for further separation of the gold and the silver from the impurities. The inventor finds that during the smelting process of the copper-separating slag, most of oxides of arsenic as impurities volatilize into smelting smoke, a small amount of oxides of antimony as impurities enter into the smoke, part of the oxides enter into the smelting slag, part of the oxides enter into the precious lead, and the oxides of bismuth as impurities are mainly reduced and enter into the precious lead. The reducing agent can reduce PbO in the copper-separating slag into metallic lead. The Pb content in the copper separating slag is generally insufficient, and the first gold and silver trapping agent needs to be additionally supplemented to completely trap the precious metals such as Au, Ag and the like in the copper separating slag. The first slag former can comprise an alkaline slag former and an acidic slag former, wherein the alkaline slag former can form salt slag with high-valence oxides such As As, Sb and the like, the melting point of the slag can be reduced, the fluidity of the slag is improved, and the slag is convenient to separate from a melt; the acid slag former can form slag with alkaline oxides (such as PbO and the like) in the furnace charge.
According to one embodiment of the invention, the temperature of the melting process may be 1100-1200 degrees Celsius. To maintain the melting temperature, 700-1000 Nm can be used3Blowing natural gas into the smelting furnace at the flow rate of/h. The inventors have found that the temperature must be controlled within the range of 1100 to 1200 ℃ during melting in order to completely dissolve gold and silver in the molten lead.
According to another embodiment of the invention, the mass ratio of the copper-separating slag to the reducing agent, the first gold and silver trapping agent and the first slag former is not particularly limited, and a person skilled in the art can select the copper-separating slag according to actual needs, for example, the copper-separating slag can be determined according to components after testing, and too high or too low affects the slag form, thereby affecting the production index.
According to another embodiment of the present invention, the specific types of the reducing agent, the first gold and silver trapping agent and the first slagging agent required in the smelting process are not particularly limited, and can be selected by those skilled in the art according to the actual needs, for example, the reducing agent can be coke powder, the first gold and silver trapping agent can be refined lead or lead oxide, and the first slagging agent can be soda (NaCO)3) Silica (SiO)2). The inventor finds that the materials can meet the process requirements, are low in cost and are easy to obtain.
S600: under the environment of oxygen-containing compressed gas, blowing the noble lead, a second gold and silver trapping agent and a second slagging agent in a metallurgical furnace
In the step, under the environment of oxygen-containing compressed gas, blowing treatment is carried out on the precious lead, a second gold and silver collecting agent and a second slag forming agent in a metallurgical furnace so as to obtain blowing slag, gold and silver-containing alloy and blowing flue gas. During the blowing process of the precious lead, most Pb and the rest Cu, Se, Sb, Bi and Te are strongly oxidized into the blowing slag, and most impurities in the precious lead are removed after the blowing. The content of impurities such as Pb, Sb, Bi and the like in the obtained gold-silver-containing alloy is not more than 0.01 wt%. After the converting is finished, the furnace mouth of the metallurgical furnace is slowly tilted downwards, and a thin slag layer with good fluidity on the surface of the metal melt in the furnace is poured into a slag ladle, so that the separation of the gold-silver-containing alloy and the converting slag is realized. The blowing process is that under the temperature higher than the melting point of the main metal (Pb) oxide of the noble lead, oxygen-containing compressed gas is blown to the surface of the melt, and most impurities are oxidized into the oxide which is insoluble in gold and silver melts through strong oxidation. Some oxides are removed by the blowing slag, some oxides are gaseous volatile matters and enter the blowing flue gas, and noble metals such as gold, silver and the like are deposited at the bottom of the furnace, so that the aim of separating the noble metals from impurities is fulfilled. The inventors have found that, in the blowing operation, since the melt in the furnace contains high content of Pb and is also easily oxidized, Pb is oxidized first. In fact, PbO is mainly used As a transfer agent of oxygen to oxidize As and Sb, and then part of As, Sb and Bi oxides are reacted with PbO to form slag for removal. The second slag former removes excess PbO-forming slag.
According to one embodiment of the present invention, the temperature of the converting process may be 1150-2000 degrees celsius. The inventor finds that if the temperature of the converting treatment is too high, the impurities which have penetrated into the brick lining can overflow into the melt again, and the quality of the gold-silver-containing alloy is adversely affected; if the temperature of the converting treatment is too low, partial impurities are not easy to volatilize into the flue gas.
According to yet another embodiment of the present invention, the flow rate of the oxygen-containing compressed gas may be 500-750Nm3H is used as the reference value. The inventor finds that because the oxygen-containing compressed gas is blown to the melt at high speed, the melt in the furnace can be violently stirred and splashed, if the flow is too large, the melt splashing is too violent, the production control is not facilitated, if the flow is too small, the blowing time is too long, and the production efficiency is influenced.
According to another embodiment of the invention, the oxygen-containing compressed gas can be compressed air, the second gold and silver trapping agent can be lead blocks, and the second slagging agent can be quartz sand. The inventor finds that the materials can meet the process requirements, are low in cost and are easy to obtain.
According to another embodiment of the present invention, the mass ratio of the precious lead to the second gold and silver collector and the second slagging agent is not particularly limited, and those skilled in the art can select the mass ratio according to actual needs, for example, the mass ratio can be determined according to the components of the precious lead after test, if the mass ratio of the precious lead to the second gold and silver collector and the second slagging agent is too high, the blowing slag amount is too large, which affects the production index, and if the mass ratio of the precious lead to the second gold and silver collector and the second slagging agent is too low, the impurities in the precious lead cannot be completely removed.
S700: the alloy containing the gold and the silver and the third slagging constituent are refined in a metallurgical furnace
In the step, the gold-silver alloy and the third slagging agent are refined in a metallurgical furnace so as to obtain the gold-silver alloy, the refining slag and the refining flue gas. Specifically, the addition amount of the third slag former is determined according to the amount of Te in the gold-silver-containing alloy. The gold and silver-containing alloy can be further purified after refining, the total content of gold and silver in the finally obtained gold and silver alloy is not less than 97 wt%, the content of impurity copper is less than 2.5 wt%, and the content of Pb, Se, Te, Bi and Sb is not more than 0.01 wt%. After refining is finished, the refining slag on the surface of the melt is removed by adopting a manual slag skimming mode, and the separation of the gold-silver alloy and the refining slag is realized. The inventor finds that the third slagging agent is generally soda, part of impurities Te reacts with the soda to generate sodium tellurate to enter refining slag in the refining process, and the rest impurities Se and Te are strongly oxidized and volatilized to enter flue gas.
According to one embodiment of the present invention, the temperature of the refining process may be 1800-. The inventor finds that if the temperature of the refining treatment is too high, impurities which penetrate into the brick lining can overflow into the melt again, and the quality of the gold-silver alloy is adversely affected; if the temperature of the refining treatment is too low, partial impurities are not easy to volatilize into the flue gas.
According to the method for treating the copper anode slime, disclosed by the embodiment of the invention, the copper anode slime is mixed with the first concentrated sulfuric acid for reaction and is filtered, so that part of copper, arsenic, antimony, bismuth and other impurities in the copper anode slime can be removed; in the process of roasting and selenium steaming of the slurry, selenide in the slurry reacts with sulfuric acid in the slurry to generate selenate, the selenate is decomposed into selenium dioxide and is volatilized to enter selenium steaming flue gas, the selenium in the copper anode mud is removed, the redundant sulfur dioxide generated by the decomposition of the sulfuric acid also enters the selenium steaming flue gas, and meanwhile, impurities such as copper, nickel and the like in the slurry react with the sulfuric acid to generate soluble salt which is stored in selenium steaming slag; after mixing with the solvent, evaporating soluble sulfate in the selenium slag to dissolve in the solvent, and after copper separation, obtaining copper separation liquid containing copper and nickel salt and copper separation slag containing lead, gold and silver, thereby further realizing the separation of copper from lead, gold and silver; in the smelting process of the obtained copper-separating slag, most of oxides of arsenic impurities volatilize into smelting smoke, a small amount of oxides of antimony impurities enter into the smoke, part of the oxides enter into smelting slag, part of the oxides enter into precious lead, and the oxides of bismuth impurities are mainly reduced and enter into the precious lead; during the blowing process of the precious lead, most Pb and the rest Cu, Se, Sb, Bi and Te are strongly oxidized into blowing slag, and most impurities in the precious lead are removed after blowing; during the refining process of the gold-silver-containing alloy, part of impurity Te enters refining slag, and the rest of impurities Se and Te are strongly oxidized and volatilized to enter flue gas. Therefore, the method can effectively remove selenium in the copper anode mud, can finish smelting, blowing and refining of the copper slag in one device, obviously reduces the device usage of the copper anode mud treatment process, can obtain the gold-silver alloy with the gold-silver content not less than 97 wt%, and has obvious economic value.
According to an embodiment of the present invention, referring to fig. 2, the above method of treating copper anode slime further comprises:
s800: returning the blowing slag and the refining slag to S500 for smelting
In this step, the blowing slag and the refining slag are returned to S500 to be smelted. Therefore, the recycling of the blowing slag and the refining slag can be realized, and the recovery rate of the noble metal in the blowing slag and the refining slag is improved.
According to an embodiment of the present invention, referring to fig. 3, the above method of treating copper anode slime further includes:
s900: before the copper separating slag is smelted, the copper separating slag is dried
In the step, before the copper separation slag is smelted, the copper separation slag is dried. Specifically, the water content of the copper separation slag is 20-25%, and after drying treatment, the water content of the copper separation slag is less than 3%. Therefore, the energy consumption of the subsequent smelting treatment can be obviously reduced, and the cost of the process for treating the copper anode slime can be reduced.
According to an embodiment of the present invention, referring to fig. 4, the method of treating copper anode slime described above further includes:
s1000: washing the selenium-steaming flue gas by a first dynamic wave
In the step, the selenium steaming flue gas is subjected to first dynamic wave washing so as to obtain crude selenium, a first washing liquid and first washed flue gas. Specifically, the selenium dioxide smoke contains selenium dioxide and sulfur dioxide, in the washing process, the selenium dioxide reacts with water to generate selenious acid, the selenious acid is reduced by the sulfur dioxide to generate crude selenium to be settled, meanwhile, the temperature of the selenium steaming smoke is reduced, namely, the selenium steaming smoke is washed through the first power wave, the purification and cooling of the selenium steaming smoke are realized, the recovery rate of the selenium is 90-95%. Compared with the foreign technology, the method improves the recovery rate of selenium by 5-10%, and the technology is simpler, more mature, more reliable and more efficient. Evaporate the selenium flue gas and adopt dynamic wave washing, compare traditional washing equipment, dynamic wave scrubber has following advantage: the efficiency is high, the operation elasticity is large, the efficiency change of air flow is small when fluctuation occurs, a large-aperture nozzle is not blocked, circulating liquid is allowed to have higher solid content, and corresponding sedimentation equipment can be smaller. The selenium steaming flue gas is treated by adopting a dynamic wave washing and purifying technology, so that accidents such as lead poisoning and the like can be avoided, and the dust removal effect is better.
According to an embodiment of the present invention, referring to fig. 5, S1000 includes:
s1001: first washing water is adopted to carry out first primary dynamic wave washing on selenium steaming flue gas
In the step, first washing water is adopted to carry out first primary dynamic wave washing on the selenium steaming flue gas so as to obtain first primary washed flue gas and first primary washed liquid. Specifically, the selenium steaming flue gas firstly enters a reverse injection cylinder of a first primary dynamic wave scrubber and collides with first washing water reversely injected from a large-caliber nozzle, so that the first washing water is forced to radially emit from inside to outside to the cylinder wall, and a foam area with a certain height is established at a gas-liquid interface. According to the relative momentum of gas and liquid, the foam column moves up and down along the cylinder. As the selenium steaming flue gas is contacted with the surface of the first washing water which is large in area and is continuously updated, the particles are trapped and the gas is absorbed in the foam area, and the heat is correspondingly transferred, thereby achieving the purposes of purifying and cooling the selenium steaming flue gas. During the washing process, selenium dioxide reacts with water to generate selenious acid, and the selenious acid is reduced by sulfur dioxide to generate crude selenium which is settled. And gas-liquid separation is carried out in the gas-liquid separation tank to obtain first primary washed flue gas and first primary washed liquid.
S1002: second washing water is adopted to carry out first and second-stage dynamic wave washing on the flue gas subjected to first primary washing
In the step, the first-stage washed flue gas is subjected to first-stage second-stage dynamic wave washing by using second washing water so as to obtain first-stage washed flue gas and first-stage second-stage washed liquid, and the first-stage second-stage washed liquid is returned to S1001 to be used as the first washing water. Therefore, secondary washing of the selenium steaming flue gas can be realized, the flue gas after first primary washing is further purified, and meanwhile, the first secondary washing liquid obtained after washing can be returned to the primary washing to be used as first washing water, so that the yield of wastewater in the process is reduced. The flue gas after the first washing can be discharged into the atmosphere after being subjected to desulfurization treatment.
S1003: settling the first primary washing liquid
In the step, the first primary washing liquid is settled to obtain a first supernatant and a first underflow. In the first primary washing liquid, after sedimentation, most of selenium is stored in the first bottom flow in a crude selenium mode, and a small amount of selenium is stored in the first supernatant in a selenious acid mode.
S1004: sending a portion of the first supernatant to a first trouble shooting tank, and extracting the remaining portion with selenium
In the step, a part of the first supernatant is sent to a first incident head tank, and the rest part is extracted with selenium to obtain a first washing liquid and first crude selenium. And the supernatant liquid is sent to the first accident head tank, so that the normal operation of the equipment is ensured, and the accident is avoided. In the first supernatant, selenium exists in the form of selenious acid, and first crude selenium can be obtained after selenium extraction, so that selenium recovery is realized.
S1005: filter-pressing the first bottom flow
In the step, the first underflow is subjected to pressure filtration to obtain a first filtrate and second crude selenium, and the first filtrate is returned to S1003 for sedimentation. The crude selenium comprises the first crude selenium and the second crude selenium. In the first bottom flow, selenium exists in a solid state form of crude selenium, and second crude selenium can be obtained after filter pressing, so that the selenium can be further recovered.
According to an embodiment of the present invention, referring to fig. 6, the method of treating copper anode slime described above further includes:
s1100: the smelting flue gas, the blowing flue gas and the refining flue gas are subjected to second dynamic wave washing
In the step, the smelting flue gas, the blowing flue gas and the refining flue gas are subjected to second dynamic wave washingSo as to obtain a filter cake, a second washing liquid and second washed flue gas, and returning the filter cake to S500 for smelting. The inventors found that oxides containing Pb, Bi, As, Sb, Te and the like As main components in the smelting flue gas, oxides containing Pb, Bi, Sb, Te and the like As main components in the blowing flue gas, oxides containing Pb, Bi, Te and the like As main components in the refining flue gas, and the oxides were washed with the second power wave to obtain oxides containing PbO, Bi, and the like As main components2O3、Sb2O3Filter cake of iso-oxides, the main component being H2TeO3、HAsO2And clean second scrubbed flue gas. The dynamic wave washing and purifying technology can adapt to the characteristic that the smoke components generated in the smelting, blowing and refining processes of the copper anode slime are complex and variable.
According to an embodiment of the present invention, referring to fig. 7, S1100 includes:
s1101: performing second-stage dynamic wave washing on the smelting flue gas, the blowing flue gas and the refining flue gas by adopting third washing water
In the step, the smelting flue gas, the blowing flue gas and the refining flue gas are subjected to second-stage dynamic wave washing by using third washing water so as to obtain second-stage washed flue gas and second-stage washed liquid. Smelting flue gas, blowing flue gas and refining flue gas firstly enter a reverse injection cylinder of a second-stage dynamic wave washer and collide with third washing water reversely injected from a large-caliber nozzle, so that the third washing water is forced to radially inject from inside to outside to the cylinder wall, and a foam area with a certain height is established at a gas-liquid interface. According to the relative momentum of gas and liquid, the foam column moves up and down along the cylinder. As the flue gas is contacted with the surface of the liquid which is large in area and is continuously renewed, the particles are trapped and the gas is absorbed in the foam area, and the heat is correspondingly transferred, thereby achieving the purposes of purifying and cooling the flue gas. And gas-liquid separation is carried out to obtain the second-stage washed flue gas and the second-stage washed liquid.
S1102: second-stage dynamic wave washing is carried out on the flue gas subjected to second-stage washing by adopting fourth washing water
In the step, second-stage dynamic wave washing is carried out on the second-stage washed flue gas by adopting fourth washing water so as to obtain second-stage washed flue gas and second-stage washed liquid, and the second-stage washed liquid is returned to S1101 to be used as third washing water. Therefore, secondary washing of smelting flue gas, blowing flue gas and refining flue gas can be realized, flue gas after second-stage washing is further purified, and meanwhile second-stage washing liquid obtained after washing can be returned to primary washing to be used as third washing water, so that the yield of wastewater in the process is reduced. The flue gas after the second washing can be discharged to the atmosphere after desulfurization treatment.
S1103: settling the second-stage washed liquid
In this step, the second first-stage washed liquid is settled to obtain a second supernatant and a second underflow. In the second stage post-washing liquor, PbSO is contained4、H2SO4、H2SeO3、Bi2(SO4)3、HAsO2、H2TeO3After settling, the substances are obtained to include H2SO4、H2SeO3、Bi2(SO4)3、HAsO2、H2TeO3And a second supernatant with PbSO4To the second underflow stream.
S1104: sending a portion of the second supernatant to a second accident head tank
In this step, a portion of the second supernatant is sent to the second accident head tank, and the remainder is the second cleaning solution. And the supernatant liquid is sent to the second accident head tank, so that the normal operation of the equipment is ensured, and the accident is avoided.
S1105: filter pressing the second bottom flow
In this step, the second underflow is subjected to pressure filtration to obtain a second filtrate and a filter cake, and the second filtrate is returned to S1103 for settling. The second bottom flow is filtered and pressed to obtain PbSO4The substances enter the filter cake, and the obtained second filtrate can be settled again to reduce the amount of wastewater-second washing liquid.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of treating copper anode slime, comprising:
(1) mixing and reacting copper anode slime with first concentrated sulfuric acid, and filtering to obtain copper-removed slime and copper-containing filtrate;
(2) mixing the copper-removed mud with second concentrated sulfuric acid for slurrying treatment so as to obtain slurry;
(3) roasting and selenium steaming treatment is carried out on the slurry, so as to obtain selenium steaming slag and selenium steaming flue gas;
(4) mixing the selenium steaming slag with a solvent for copper separation so as to obtain a copper separation liquid and a copper separation slag;
(5) sending the copper-separating slag, a reducing agent, a first gold and silver trapping agent and a first slagging agent to a metallurgical furnace for smelting treatment so as to obtain precious lead, smelting slag and smelting smoke;
(6) under the environment of oxygen-containing compressed gas, converting the precious lead, a second gold and silver collecting agent and a second slagging agent in the metallurgical furnace to obtain converting slag, a gold and silver-containing alloy and converting flue gas;
(7) and refining the gold-silver-containing alloy and a third slagging constituent in the metallurgical furnace so as to obtain a gold-silver alloy, refining slag and refining flue gas.
2. The method of claim 1, further comprising:
(8) and (5) returning the blowing slag and the refining slag to the step (5) for smelting.
3. The method of claim 1 or 2, further comprising:
(9) and before the copper separation slag is subjected to the smelting treatment, drying the copper separation slag.
4. The method of claim 1, further comprising:
(10) and carrying out first dynamic wave washing on the selenium steaming flue gas so as to obtain crude selenium, a first washing liquid and first washed flue gas.
5. The method of claim 4, wherein step (10) comprises:
(10-1) carrying out first primary dynamic wave washing on the selenium steaming flue gas by adopting first washing water so as to obtain first primary washed flue gas and first primary washed liquid;
(10-2) carrying out first secondary dynamic wave washing on the first primary washed flue gas by using second washing water so as to obtain the first washed flue gas and first secondary washed liquid, and returning the first secondary washed liquid to the step (10-1) for use as first washing water;
(10-3) settling the first primary washing liquid to obtain a first supernatant and a first underflow;
(10-4) sending a part of the first supernatant to a first incident head tank, and extracting the rest part of selenium to obtain a first washing solution and first crude selenium;
(10-5) carrying out pressure filtration on the first bottom flow to obtain a first filtrate and second crude selenium, and returning the first filtrate to the step (10-3) for carrying out the sedimentation;
wherein the crude selenium comprises the first crude selenium and the second crude selenium.
6. The method of claim 1, further comprising:
(11) and (3) carrying out second dynamic wave washing on the smelting flue gas, the blowing flue gas and the refining flue gas so as to obtain a filter cake, a second washing liquid and second washed flue gas, and returning the filter cake to the step (5) for smelting.
7. The method of claim 6, wherein step (11) comprises:
(11-1) carrying out second-stage dynamic wave washing on the smelting flue gas, the blowing flue gas and the refining flue gas by using third washing water so as to obtain second-stage washed flue gas and second-stage washed liquid;
(11-2) carrying out second-stage dynamic wave washing on the second-stage washed flue gas by adopting fourth washing water so as to obtain second-stage washed flue gas and second-stage washed liquid, and returning the second-stage washed liquid to the step (11-1) to be used as third washing water;
(11-3) settling the second primary washing liquid to obtain a second supernatant and a second underflow;
(11-4) sending a part of the second supernatant to a second accident head tank, and the rest is the second washing liquid;
(11-5) performing pressure filtration on the second underflow to obtain a second filtrate and the filter cake, and returning the second filtrate to the step (11-3) for the sedimentation.
8. The method as claimed in claim 1, wherein in step (5), the temperature of the smelting process is 1100-1200 ℃.
9. The method of claim 1, wherein the step of removing the metal oxide layer comprises removing the metal oxide layer from the metal oxide layerIn the step (6), the temperature of the blowing treatment is 1150-3/h。
10. The method as claimed in claim 1, wherein, in the step (7), the temperature of the refining treatment is 1800-2000 ℃.
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