CN106086440A - Method for separating and recovering valuable metals in Kaldo furnace smelting slag by wet method - Google Patents

Abstract

The invention discloses a method for separating and recovering valuable metals in Kaldo furnace smelting slag by a wet method, which comprises the steps of leaching ore grinding water of the Kaldo furnace smelting slag to remove soluble salts; then, the copper, selenium and tellurium in the slag is dissolved and leached by utilizing pressure oxidation acid leaching, copper sulfate solution, silver, selenium slag and copper telluride slag can be respectively obtained through treatment, and tellurium, silver and selenium can be respectively recovered from the silver, selenium slag and copper telluride slag; leaching the pressurized decoppered filter residue by hydrochloric acid to remove antimony and bismuth, and finally obtaining lead-silver residue which can be returned to the Kaldo furnace for smelting; the antimony and bismuth are further recovered from the antimony bismuth solution. The method adopts a mode of removing and recovering metals such as copper, antimony, bismuth, selenium, tellurium, silver, lead and the like rich in the Kaldo furnace smelting slag step by step, has good compatibility with a wet-fire method combined process for treating copper anode slime and recovering rare and precious metals in the Kaldo furnace, can return the smelting slag to the Kaldo furnace smelting treatment, avoids adverse effects on copper smelting caused by returning to a copper smelting system, and obtains the lead-silver slag with higher enrichment degree of valuable metals such as lead, silver and the like.

Description

A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag

technical field

The invention belongs to the technical field of hydrometallurgical engineering, and in particular relates to a method for wet separation and recovery of valuable metals in smelting slag of a Kaldor furnace.

Background technique

Kaldor furnace smelting generally produces three types of slag: smelting slag, blowing slag and refining slag. At present, the processing method of Kaldor slag at home and abroad is to return the blowing slag and refining slag to the Kaldor furnace for processing, and return the smelting slag to copper Smelting main system processing. The small amount of blowing slag and refining slag returned to the Kaldor furnace will not bring adverse effects, but the amount of smelting slag is large and contains a large amount of copper, gold, silver, antimony, bismuth, tellurium, selenium, tin and other non-ferrous metals and rare precious metals. This brings two unfavorable factors: the one, a large amount of smelting slag returns copper smelting system and can cause lead to form vicious cycle in large system, influences copper smelting system and copper electrolysis system, and seriously affects the quality of anode copper and cathode copper; The copper smelting system can only recover gold and silver, but cannot recover rare and precious metals rich in smelting slags such as lead, antimony, bismuth, tellurium and selenium. Patent CN102732735A aims at the problems existing in the conventional technology, and proposes to remove base metals such as silicon, lead, and barium step by step to separate gold and silver from base metals, effectively enrich gold and silver, and then further recover gold and silver, but this process It is tedious and complicated, consumes a lot of equipment and raw materials, and does not consider the recovery of antimony, bismuth, selenium, tellurium and other metals in the smelting slag.

Contents of the invention

In order to solve the problems in the prior art, the present invention provides a method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag, and the present invention comprehensively recovers gold, silver, lead, copper and antimony in Kaldor furnace smelting slag , bismuth, tellurium, selenium and other rare and precious metals, and improve the recovery rate of various metals.

The present invention is achieved through the following technical solutions:

A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag, carried out according to the following steps:

(1) Grinding and water leaching desalination: crushing and ball milling the smelting slag of the Kaldor furnace to make a slurry, so that the soluble salt in the smelting slag of the Kaldor furnace is dissolved in water, and after the reaction, the neutral filtrate and desalted filter residue are obtained by pressure filtration;

(2) Decopper removal by pressurized acid leaching: add desalted filter residue, sulfuric acid, and water into the autoclave, heat and introduce oxygen for pressure treatment, react to obtain decopper slag and decopper solution, and filter;

(3) Recovery of antimony and bismuth by hydrochloric acid leaching of decopper slag: add decopper slag, hydrochloric acid, sodium chloride, and water into the hydrochloric acid leaching tank, and obtain lead-silver slag and antimony-bismuth leaching solution after reaction, in which the lead-silver slag is directly returned to the Kaldor furnace for smelting Recover lead and silver; antimony and bismuth leaching solution is hydrolyzed and separated to recover antimony; filtrate after deantimony is replaced by iron powder or alkali neutralized to separate and recover bismuth;

(4) Recycling silver-selenium-tellurium-copper in decopper solution: add copper powder, sulfur dioxide or sodium sulfite to the decopper solution, filter and separate to obtain precipitated silver-selenium slag, which can be returned to the Kaldor furnace for further recovery of silver and selenium; Copper powder is added to the filtered filtrate to obtain copper telluride, which can be further recovered to extract silver, selenium, tellurium, and copper; the copper sulfate solution from which silver, selenium, and tellurium have been removed is returned to copper electrolysis to recover copper.

The smelting slag of the Kaldor furnace is slag obtained by smelting copper anode slime, lead anode slime, replaced silver powder, Venturi slime, secondary selenium precipitation and other materials, and its composition content is: Pb 10-35%; S 2-15% %; Na 0.5-15%; Ba 5-10%; Cu 0.5-15%; Sb 3-20%; Bi 1-15%; Ag 0.2-10%; As 0.2-8%; Si 0.5-5%; Ca 0.5-5%; Mg 0.2-3%; Sn0.5-2%; K 0.1-1%; Fe 0.5-5%; Cl 0.1-1%; Al 0.1-1%; Te 0.1-2%; Se 0.1-2%; Ni 0.01-1%.

In the step (1), after crushing the smelting slag from the Kaldor furnace, a wet ball mill is used to grind the slag to make a slurry, and the fineness of the slurry is over 95% at -200 mesh.

The mass parts of the materials added in the step (2) are 1 part of desalted filter residue, 2-4 parts of water, 0.05-0.5 parts of concentrated sulfuric acid with a mass fraction of 98%, the heating temperature is 120-180 ° C, and the oxygen passing time is 4-4 parts. 7h, the oxygen pressure is 8-15MPa.

The mass parts of the hydrochloric acid leaching operation materials added in the step (3) are 1 part of copper removal slag, 3-5 parts of water, 0.5-1.5 parts of concentrated hydrochloric acid with a mass fraction of 30%, 0.05-0.5 parts of sodium chloride, and the reaction temperature The temperature is 80-90°C, and the stirring and leaching time is 2-5h.

In the step (3), the mass parts of the hydrolyzed antimony precipitation operation materials are 1 part of antimony bismuth leaching solution and 2-4 parts of water, and the antimony oxychloride is obtained by precipitation, and antimony oxychloride is further processed to obtain antimony white or metal antimony.

The filtrate after deantimony in the step (3) can be replaced with iron powder to obtain bismuth sponge, or neutralized with sodium carbonate or sodium hydroxide to obtain bismuth hydroxide precipitate.

When the step (4) is used to recover silver selenium, it is necessary to cool the decopper solution to 30-45°C, use SO ₂ or copper powder to deposit Ag, Se and Te; then heat it to 90-100°C, add copper powder and Excessive 2-5% to deposit copper-tellurium slag, the filtrate is analyzed for Ag, Se and Te content, and if it is qualified, it will be sent to electrolytic copper or copper sulfate.

The invention provides a method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag. The Kaldor furnace smelting slag is ground and water-leached to remove soluble salts; Tellurium is dissolved and leached, and the solution is further processed to obtain copper sulfate solution, silver selenium slag and copper telluride slag respectively, and tellurium, silver and selenium can be recovered from silver selenium slag and copper telluride slag respectively; decopper filter residue after pressurization Antimony and bismuth are removed by hydrochloric acid leaching to obtain lead and silver slag that can be returned to the Kaldor furnace for smelting; further processing of the antimony and bismuth solution can recover antimony and bismuth. Compared with the prior art, the present invention adopts step-by-step removal and recovery of copper, antimony, bismuth, selenium, tellurium, silver, lead and other metals rich in the smelting slag of the Kaldor furnace, and is similar to the introduction and construction of the Kaldor comprehensive workshop. Furnace treatment of copper anode slime to recover rare and precious metals combined wet-fire process has good compatibility, which can return the smelting slag to the Kaldor furnace for smelting treatment, avoiding the adverse effects of returning to the copper smelting system on copper smelting. In addition, various valuable metals in the smelting slag have a high degree of enrichment. Experiments show that the method provided by the invention has a slag rate of more than 85% for lead, silver, and gold, and a copper recovery rate of more than 95%. Antimony, bismuth, The recoveries of selenium and tellurium both reached more than 80%.

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

detailed description

The technical solutions in the embodiments of the present invention are further described below. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag, carried out according to the following steps:

(1) Sampling and crushing

A total of 8 kg of Kaldor furnace smelting slag was used in the comprehensive workshop of Baiyin Nonferrous Group Company to carry out a small test. All the Kaldor furnace smelting slag samples were crushed into small particles with a particle size of 0-5 mm for use. The raw material composition and content of Kaldor furnace smelting slag are: Pb 28.89%; S 3.58%; Na 10.48%; Ba 7.20%; Cu 12.39%; Sb 10.18%; Bi 6.47%; Ag4.82%; As 1.71%; Si 1.57%; Ca 0.72%; Mg 0.78%; Sn 1.14%; K 0.57%; Fe 1.55%; Cl 0.45%; Al 0.26%; Te 0.20%; Se 0.32%; Ni 0.29%.

(2) Grinding and water leaching desalination

Weigh 500g of the crushed sample and put it into a ball mill, add 500g of water, and grind for 10 minutes. At this time, the mineral fineness is -200 mesh and 95%, then rinse with 500g of water and transfer to a beaker, filter, wash, dry, Weighed to obtain 402g of desalted material after grinding, and filtered water was discarded.

(3) Decopper removal by pressure acid leaching

Weigh 200g of the ground desalted material and put it into a 1L small autoclave, add 400g of water and 10g of concentrated sulfuric acid with a mass fraction of 98%. Heating was discontinued and nitrogen was removed by releasing partial pressure in the autoclave. Then close the valve and feed oxygen into the autoclave for 7 hours. After the pressure in the autoclave reaches 8MPa and the temperature in the autoclave reaches 160°C, cool down. After the pressurized leaching operation is completed, the temperature of the feed liquid is reduced to 80°C , filtered, and washed with water to obtain copper-removing slag and copper-removing solution.

(4) Recovery of antimony and bismuth by hydrochloric acid leaching

Weigh 100g of copper removal slag and put it into a three-necked flask, add 300g of water, 50g of concentrated hydrochloric acid with a mass fraction of 30%, and 50g of sodium chloride, install a stirring, water bath and condenser, heat to 90°C, and stir for 2 hours. Filter, wash with 15% hydrochloric acid first, and then wash with water. The obtained filter residue is lead and silver slag, which can be collected and stored and returned to the Kaldor furnace for smelting and recycling lead and silver. The combined filtrate is the antimony bismuth leaching solution, the antimony bismuth leaching solution is added with twice the amount of water, and after hydrolysis, the antimony oxychloride precipitate is obtained. After the antimony oxychloride is separated, the antimony oxychloride is decomposed with ammonia water to obtain the antimony trioxide product. The filtrate after deantimony removal is replaced with iron powder to obtain bismuth sponge, which is separated by filtration, and the filtrate is discarded.

(5) Recycling silver selenium tellurium copper by decopper solution treatment

Put the decopper solution obtained in step (3) into a beaker, cool to 40°C and filter, analyze the filtrate, use SO ₂ or copper powder to deposit Ag, Se and Te when the content of Ag and Se in the solution is lower than 0.005g/ L stop deposition, filter and separate to obtain silver-selenium slag, this silver-selenium slag can return to the Kaldor furnace system to smelt and reclaim silver and selenium. Then heat the solution to 90°C and analyze the tellurium content, carefully add copper powder with an excess of 5%, when the tellurium content of the solution is less than 0.005g/L, then cool to 80°C and filter to obtain copper tellurium slag, the filtrate is analyzed for Ag, Se and Te content If it is qualified, it will be sent to electrolytic copper or copper sulfate.

(6) Test results

The analysis results show that the slag entry rate is 86% lead, 88% silver, and 95% gold, and the recovery rate is 95% copper, 80% antimony, 82% bismuth, 85% selenium, and 84% tellurium.

Example 2

(1) The smelting slag from Kaldor furnace in the comprehensive workshop of Baiyin Nonferrous Metals Group Co., Ltd. was used to carry out a small test.

(2) Weigh 150g of the crushed sample and put it into a ball mill, add 150g of water, and grind for 10 minutes. At this time, the mineral fineness is 98% at -200 mesh.

(3) Decopper removal by pressure acid leaching

Weigh 100g of the ground desalted material and put it into a 1L small autoclave, add 400g of water and 20g of concentrated sulfuric acid with a mass fraction of 98%. Heating was stopped, and a certain pressure was controlled at this time, and nitrogen was removed by releasing partial pressure in the kettle. Then close the valve and feed oxygen into the autoclave for 5 hours. After the pressure in the autoclave reaches 12MPa and the temperature in the autoclave reaches 180°C, cool it down. , filtered, and washed with water to obtain copper-removing slag and copper-removing solution.

(4) Recovery of antimony and bismuth by hydrochloric acid leaching

Weigh 50g of copper removal slag and put it into a three-necked flask, add 250g of water, 50g of concentrated hydrochloric acid with a mass fraction of 30%, and 5g of sodium chloride, install agitator, water bath and condenser, heat to 90°C, and stir and leaching for 5h. Filter, wash with 15% hydrochloric acid first, and then wash with water. The obtained filter residue is lead and silver slag, which can be collected and stored and returned to the Kaldor furnace for smelting and recycling lead and silver. The combined filtrate is the antimony bismuth leaching solution, the antimony bismuth leaching solution is added with 4 times of water, after hydrolysis, the antimony oxychloride precipitate is obtained, after the antimony oxychloride is separated, the antimony oxychloride is decomposed with ammonia water, and the antimony trioxide product is obtained. The filtrate after deantimony removal was neutralized with sodium carbonate to a pH value of 4.0 to obtain a bismuth carbonate precipitate, which was filtered to separate the bismuth precipitate, and the filtrate was discarded.

(5) Recycling silver selenium tellurium copper by decopper solution treatment

Put the decopper solution obtained in step (3) into a beaker, cool to 40°C and filter, analyze the filtrate, use SO ₂ or copper powder to deposit Ag, Se and Te when the content of Ag and Se in the solution is lower than 0.005g/ L stop deposition, filter and separate to obtain silver-selenium slag, this silver-selenium slag can return to the Kaldor furnace system to smelt and reclaim silver and selenium. Then heat the solution to 100°C and analyze the tellurium content, carefully add copper powder and over 2%, when the tellurium content of the solution is less than 0.005g/L, then cool to 80°C and filter to obtain copper tellurium slag, the filtrate is analyzed for Ag, Se and Te content If it is qualified, it will be sent to electrolytic copper or copper sulfate.

(6) Test results

The analysis results show that the slag entering rate is 86% for lead, 88% for silver, and 90% for gold, and the recovery rate is 95% for copper, 87% for antimony, 88% for bismuth, 85% for selenium, and 82% for tellurium.

Example 3

(1) The smelting slag from Kaldor furnace in the comprehensive workshop of Baiyin Nonferrous Metals Group Co., Ltd. was used to carry out a small test.

(2) Weigh 150g of the crushed sample and put it into a ball mill, add 150g of water, and grind for 10 minutes. At this time, the mineral fineness is 98% at -200 mesh.

(3) Decopper removal by pressure acid leaching

Weigh 100g of the ground desalted material and put it into a 1L small autoclave, add 400g of water, and 50g of concentrated sulfuric acid with a mass fraction of 98%. Heating was stopped, and a certain pressure was controlled at this time, and nitrogen was removed by releasing partial pressure in the kettle. Then close the valve and feed oxygen into the autoclave for 6 hours. After the pressure in the autoclave reaches 10MPa and the temperature in the autoclave reaches 180°C, cool down. After the pressure leaching operation is completed, the temperature of the feed liquid is reduced to 80°C , filtered, and washed with water to obtain copper-removing slag and copper-removing solution.

(4) Recovery of antimony and bismuth by hydrochloric acid leaching

Weigh 50g of decopper slag and put it into a three-necked flask, add 250g of water, 75g of concentrated hydrochloric acid with a mass fraction of 30%, and 2.5g of sodium chloride, install the stirring, water bath and condenser, heat to 80°C, and stir for leaching time of 5h . Filter, first wash with 15% hydrochloric acid by mass fraction, and then wash with water. The obtained filter residue is lead and silver slag, which can be collected and stored and returned to the Kaldor furnace for smelting and recycling lead and silver. The combined filtrate is the antimony bismuth leaching solution, the antimony bismuth leaching solution is added with 4 times of water, after hydrolysis, the antimony oxychloride precipitate is obtained, after the antimony oxychloride is separated, the antimony oxychloride is decomposed with ammonia water, and the antimony trioxide product is obtained. The filtrate after deantimony was neutralized with sodium hydroxide to a pH value of 4.0 to obtain bismuth hydroxide precipitate, which was separated by filtration, and the filtrate was discarded.

(5) Recycling silver selenium tellurium copper by decopper solution treatment

Put the decopper solution obtained in step (3) into a beaker, cool to 40°C and filter, analyze the filtrate, use SO ₂ or copper powder to deposit Ag, Se and Te when the content of Ag and Se in the solution is lower than 0.005g/ L stop deposition, filter and separate to obtain silver-selenium slag, this silver-selenium slag can return to the Kaldor furnace system to smelt and reclaim silver and selenium. Then heat the solution to 100°C and analyze the tellurium content, carefully add copper powder and over 4%, when the tellurium content of the solution is less than 0.005g/L, then cool to 80°C and filter to obtain copper tellurium slag, the filtrate is analyzed for Ag, Se and Te content If it is qualified, it will be sent to electrolytic copper or copper sulfate.

(6) Test results

The analysis results show that the slag entry rate is 80% lead, 86% silver, and 90% gold, and the recovery rate is 95% copper, 85% antimony, 85% bismuth, 82% selenium, and 82% tellurium.

Example 4

(1) The smelting slag of Kaldor furnace in the comprehensive workshop of Baiyin Nonferrous Metals Group Co., Ltd. was used to carry out the pilot scale test. The composition and content of the raw materials were Pb 16.82%; S 11.06%; Na 10.48%; Ba 7.51%; Cu 6.78%; Sb 18.59%; Bi 1.86%; Ag2.37%; As 1.14%; Si 1.0%; Ca0.93%; Mg 0.71%; Sn 0.65%; K 0.06%; Fe 0.57%; Cl 0.24%; Al0.23%; Te 0.41% ; Se 0.33%; Ni 0.13%.

(2) Grinding water leaching desalination

Break the 800.0kg sample of Kaldor furnace smelting slag into small particles with a particle size of 0-5mm. The laboratory weighs 500kg of the sample and puts it into a ball mill, adds 50.0kg of water, and grinds the ore for 10 minutes. At this time, the mineral fineness is 95 %-200 mesh, then rinse with 50.0kg of water and transfer to a beaker, filter, wash, dry and weigh to obtain 40.0kg of ground solids, filter the water and discard.

(3) Decopper removal by pressure acid leaching

Take 50.0kg of ground solids and put them into a 250.0L small autoclave, add 150kg of water and 25kg of sulfuric acid. After the addition is completed, close the autoclave, start stirring, and heat to 130°C with high-pressure steam for 2 hours. Stop heating when the predetermined temperature is reached, control a certain pressure at this time, and remove the _N2 gas by releasing the partial pressure in the kettle. Then close the valve to ventilate oxygen, add about 60m ³ /h of oxygen in the standard state for the first hour, and then reduce it to 30m ³ /h, when the pressure in the kettle reaches the specified pressure, the time of oxygen ventilation is 4h, and the pressure in the kettle reaches 15MPa , when the temperature in the reactor reaches 160°C, stop oxygen and heating, then pass in circulating water to cool to 80°C, open the discharge valve and put it in a buffer tank to cool to 40°C, filter, wash with water, and obtain decopper slag and decopper solution.

(4) Recovery of antimony and bismuth by hydrochloric acid leaching

Add copper removal slag, hydrochloric acid, sodium chloride, and water into the acid leaching tank according to the amount, and the material weight ratio is 1 part of copper removal slag, 4 parts of water, 1 part of concentrated hydrochloric acid with a mass fraction of 30%, and 0.1 part of sodium chloride. Heating to 90°C, stirring and leaching for 3h. Filter, wash with hydrochloric acid with a concentration of 15% mass fraction first, and then wash with water. The obtained filter residue is lead and silver slag, which can be collected and stored and returned to the Kaldor furnace for smelting and recycling lead and silver. The combined filtrates are the hydrochloric acid solution containing antimony and bismuth. The antimony and bismuth leaching solution is added with 4 times of water, and after hydrolysis, the antimony oxychloride precipitate is obtained. After the antimony oxychloride is separated, the antimony oxychloride is decomposed with ammonia water to obtain the antimony trioxide product. The filtrate after deantimony removal is replaced by iron powder to obtain bismuth sponge. The bismuth sponge is filtered and separated, and the filtrate is sent to the waste water treatment pool after recovering hydrochloric acid.

(5) Recycling silver selenium tellurium copper by decopper solution treatment

Put the decopper solution obtained in step (3) into a beaker, heat it to about 95°C, start stirring, slowly add copper powder and sodium sulfite in batches, take a liquid sample and add hydrochloric acid, when there is no longer white precipitation. When the end point of the operation is reached, the silver selenium slag can be obtained through filtration and separation. The silver-selenium slag can be returned to the Kaldor furnace system to smelt and recover silver and selenium. Continue to put the above filtrate into the beaker and heat to 95°C, start stirring, carefully add copper powder with an excess of 2%, when the test shows that the solution contains silver, selenium and tellurium <5mg/L, it means that the end of the operation has been reached, filter and separate That is, coarse copper telluride slag is obtained.

(6) Test results

The analysis results show that the slag rate of lead, silver and gold is over 85%, the recovery rate of copper is over 95%; the recovery rate of antimony, bismuth, selenium and tellurium is over 80%.

Claims (7)

1. a method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag, characterized in that it is carried out according to the following steps: (1) Grinding and water leaching desalination: crushing and ball milling the smelting slag of the Kaldor furnace to make a slurry, so that the soluble salt in the smelting slag of the Kaldor furnace is dissolved in water, and after the reaction, the neutral filtrate and desalted filter residue are obtained by pressure filtration; (2) Decopper removal by pressurized acid leaching: add desalted filter residue, sulfuric acid, and water into the autoclave, heat and introduce oxygen for pressure treatment, react to obtain decopper slag and decopper solution, and filter; (3) Recovery of antimony and bismuth by hydrochloric acid leaching of decopper slag: add decopper slag, hydrochloric acid, sodium chloride, and water into the hydrochloric acid leaching tank, and obtain lead-silver slag and antimony-bismuth leaching solution after reaction, in which the lead-silver slag is directly returned to the Kaldor furnace for smelting Recover lead and silver; antimony and bismuth leaching solution is hydrolyzed and separated to recover antimony; filtrate after deantimony is replaced by iron powder or alkali neutralized to separate and recover bismuth; (4) Recycling silver-selenium-tellurium-copper in decopper solution: add copper powder, sulfur dioxide or sodium sulfite to the decopper solution, filter and separate to obtain precipitated silver-selenium slag, which can be returned to the Kaldor furnace for further recovery of silver and selenium; Copper powder is added to the filtered filtrate to obtain copper telluride, which can be further recovered to extract silver, selenium, tellurium, and copper; the copper sulfate solution from which silver, selenium, and tellurium have been removed is returned to copper electrolysis to recover copper. 2. A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag according to claim 1, characterized in that: in the step (1), after the Kaldor furnace smelting slag is broken, it is ground by a wet ball mill Made into slurry, the slurry fineness is -200 mesh above 95%. 3. A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag according to claim 1 or 2, characterized in that: the mass fraction of the material added in the step (2) is desalted filter residue 1 parts, 2-4 parts of water, 0.05-0.2 parts of concentrated sulfuric acid with a mass fraction of 98%, the heating temperature is 120-180°C, the time of oxygen flow is 4-7h, and the pressure of oxygen flow is 8-15MPa. 4. A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag according to claim 1 or 2, characterized in that: the mass fraction of the hydrochloric acid leaching operation material added in the step (3) is 1 part of copper removal slag, 3-5 parts of water, 0.5-1.5 parts of concentrated hydrochloric acid with a mass fraction of 30%, 0.05-0.5 parts of sodium chloride, the reaction temperature is 80-90 ° C, and the stirring and leaching time is 2-5 hours. 5. A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag according to claim 4, characterized in that: in the step (3), the antimony and bismuth leachate is hydrolyzed and deposited in antimony through hydrolysis, separation and recovery of antimony The mass parts of the materials added are 1 part of antimony bismuth leaching solution and 2-4 parts of water, the precipitation is to obtain antimony oxychloride, and the antimony oxychloride is further processed to obtain antimony white or metallic antimony. 6. A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag according to claim 1 or 5, characterized in that: the filtrate after deantimony in the step (3) uses sodium carbonate or hydrogen Sodium oxide neutralizes to give bismuth hydroxide precipitate. 7. A method for wet separation and recovery of valuable metals in Kaldor furnace smelting slag according to claim 1 or 5, characterized in that: when the silver-selenium recovery is carried out in the step (4), the decopper solution needs to be Cool to 30-45°C, use SO ₂ or copper powder to deposit Ag, Se and Te; then heat to 90-100°C, add copper powder with an excess of 2-5% to deposit copper tellurium slag, and analyze the filtrate for Ag, Se and Te If the Te content is qualified, it will be sent to electrolytic copper or copper sulfate.