System for comprehensively recovering lead anode slime

Abstract

The utility model belongs to the technical field of lead anode slime recovery, and particularly relates to a system and a method for comprehensively recovering lead anode slime, the system comprises a copper recovery system and an antimony bismuth recovery system, and the method comprises the steps of preimpregnation, antimony bismuth precipitation, copper replacement, slurrying, neutralization, antimony precipitation and the like. By adopting the system and the method disclosed by the utility model, the content of gold and silver in the lead anode slime leached into the liquid is lower than 20mg / L, the leached slag is smelted by a back fire method, a small amount of lead is leached into the liquid and can be completely recovered, the leaching rate of copper, antimony and bismuth reaches more than 98%, the recovery rate reaches more than 99%, antimony and bismuth can be independently recovered and purified, and the cost is low. The process is combined treatment by a wet process and a pyrogenic process and is controllable and good in effect, wastewater can be supplemented for recycling, and the advanced level is achieved in China.

Description

Technical Field

[0001] The utility model belongs to the technical field of lead anode mud recovery, and in particular relates to a system for comprehensively recovering lead anode mud. Background Art

[0002] Lead anode mud, as a by-product of the lead electrolysis process, contains many valuable metals such as gold, silver, lead, copper, antimony, bismuth, etc., and is an important economic growth point for smelting companies. Traditionally, the main method for processing this material is pyrometallurgy. In this process, lead anode mud is usually added to the reduction smelting furnace together with the material after copper removal treatment, and finally recovers precious metals through a series of steps such as blowing and silver electrolysis. However, the devices used in this traditional method have multiple defects: first, they usually require large-scale material processing capabilities, resulting in large and complex equipment; second, these devices will generate a large amount of waste and emissions during operation, which has a serious impact on the environment; finally, due to the involvement of multiple processing steps, the efficiency of the entire process is low, and the recovery rate of precious metals is not ideal.

[0003] In order to overcome the shortcomings of pyrometallurgy, the hydrometallurgical process began to be widely studied and gradually matured in the late 1980s. The hydrometallurgical process usually involves pre-treating the lead anode mud with an acidic solution to remove base metals, and then extracting precious metals by chemical methods. Although the hydrometallurgical process is superior to the pyrometallurgical process in some aspects, such as the recovery rate of valuable metals, it still faces many challenges in processing lead anode mud. For example, existing hydrometallurgical processing equipment often cannot effectively separate antimony and bismuth, two elements that are very similar in chemical properties, resulting in a complex and inefficient separation process. In addition, existing hydrometallurgical equipment is generally unable to achieve precise control during large-scale production, which affects the quality of the final product. Utility Model Content

[0004] In view of the problems existing in the prior art, the utility model provides a system for comprehensively recovering lead anode mud, and the utility model specifically includes the following contents:

[0005] A comprehensive system for recovering lead anode mud, including a copper recovery system and an antimony and bismuth recovery system.

[0006] The copper recovery system comprises a first receiving hopper and a pre-leaching kettle, a first filter press, an antimony-bismuth kettle, a second filter press, a copper replacement kettle, and a copper replacement filter tank, each of which is provided with a liquid inlet and a liquid outlet. The pre-leaching kettle, the first filter press, the antimony-bismuth kettle, the second filter press, the copper replacement kettle, and the copper replacement filter tank are sequentially connected through pipelines; the first filter press is also provided with a first slag outlet, and the second filter press is also provided with a second slag outlet; the first receiving hopper is connected to the first slag outlet of the first filter press;

[0007] The antimony-bismuth recovery system comprises an antimony-bismuth slurry tank, a neutralization kettle, a neutralization filter tank, an antimony precipitation kettle, and an antimony precipitation filter tank, which are connected in sequence through pipelines, and the antimony-bismuth slurry tank is connected to the second slag outlet of the second filter press;

[0008] The pre-leaching kettle, the antimony-bismuth precipitation kettle, the copper replacement kettle, the neutralization kettle and the antimony precipitation kettle are all provided with stirring devices.

[0009] Preferably, the hopper opening of the first receiving hopper is arranged below the first slag outlet of the first filter press; and the slot opening of the antimony-bismuth slurrying tank is arranged below the second slag outlet of the second filter press.

[0010] Preferably, the liquid outlet of the copper replacement filter tank is externally connected to a first liquid outlet pipe; the antimony precipitation filter tank is externally connected to a second liquid outlet pipe; the copper recovery system also includes a first centrifugal pump arranged on the pipeline between the prepreg kettle and the first filter press, a second centrifugal pump arranged on the pipeline between the antimony bismuth precipitation kettle and the second filter press, and a third centrifugal pump arranged on the first liquid outlet pipe; the antimony bismuth recovery system also includes a fourth centrifugal pump arranged on the pipeline between the antimony bismuth slurry tank and the neutralization kettle, a fifth centrifugal pump arranged between the neutralization filter tank and the antimony precipitation kettle, and a sixth centrifugal pump arranged on the second liquid outlet pipe.

[0011] Preferably, the pre-preg kettle, the antimony-bismuth precipitation reactor, the copper displacement kettle, and / or the antimony-bismuth slurry tank are all made of bisphenol A glass fiber reinforced plastics; and / or,

[0012] The prepreg slag hopper, copper replacement filter tank, neutralization filter tank, and antimony precipitation filter tank are all made of steel-lined PO material; and / or,

[0013] The first filter press and the second filter press are both water-washed membrane filter presses; and / or,

[0014] The neutralization kettle and antimony precipitation kettle are both glass-lined jacketed reactors; and / or,

[0015] The first centrifugal pump, the second centrifugal pump, the third centrifugal pump, the fourth centrifugal pump, the fifth centrifugal pump and the sixth centrifugal pump are all engineering plastic pumps; and / or,

[0016] All the pipes described are bisphenol A fiberglass pipes.

[0017] The utility model also relates to a method for comprehensively recovering lead anode mud using the system of the utility model, comprising the following steps:

[0018] (1) Pre-immersion: Add hydrochloric acid solution, oxidant and sodium salt solution to lead anode mud, stir and react at 65-85°C for 50-120 minutes, and then separate the solid and liquid to obtain a pre-immersion solution;

[0019] (2) Precipitating antimony and bismuth: adjusting the pre-immersion solution to a pH value of less than 2.5, stirring the solution at a temperature of 40-60° C. for 30-60 min, and then separating the solid from the liquid to obtain a post-precipitation solution and an antimony-bismuth slag;

[0020] (3) Copper replacement: Adjust the temperature of the solution after precipitation of antimony and bismuth to 30-50°C, add alkali to adjust the acid concentration (referring to H + concentration, the same below) to 10-18g / L, add the replacement agent, stir and react for 30-60min, then separate the solid and liquid to obtain copper replacement liquid and copper slag;

[0021] (4) slurrying: adding water to the antimony-bismuth slag and stirring to obtain a slurry;

[0022] (5) Neutralization: adding an alkaline solution to the slurry, stirring the reaction for 40-80 min, and then separating the solid and liquid to obtain bismuth slag and antimony-containing liquid;

[0023] (6) Antimony precipitation: add an acid solution to the antimony-containing liquid, adjust the pH to 2.0-2.5, stir and react at 30-60°C for 30-60 minutes, and then separate the solid and liquid to obtain an antimony precipitated liquid and antimony slag.

[0024] Preferably, in step (1):

[0025] The concentration of the hydrochloric acid is 2.5-4 mol / L; and / or,

[0026] The oxidant is a sodium chlorate solution with a mass concentration of 45-55%; and / or,

[0027] The sodium salt solution is a saturated sodium chloride solution (herein, a saturated solution at room temperature); and / or,

[0028] The mass ratio of the hydrochloric acid solution, the oxidant and the sodium salt solution is 1:(0.13-0.3):(0.15-0.25); and / or,

[0029] Controlling the liquid-to-solid mass ratio of the prepreg reaction system to be (3-5):1; and / or,

[0030] The stirring speed is 180-220 rpm.

[0031] Preferably, in step (2):

[0032] The method for adjusting the pH of the pre-soak is to add water thereto; and / or,

[0033] The stirring speed is 140-180 rpm.

[0034] Preferably, in step (3):

[0035] The alkali is sodium hydroxide, potassium hydroxide, and / or sodium carbonate; and / or,

[0036] The displacing agent is iron powder with a particle size of 50-200 mesh; and / or,

[0037] The amount of the replacement agent added is 1.2-1.5 times the mass content of copper in the solution after antimony and bismuth precipitation; and / or,

[0038] The stirring speed is 140-180 rpm.

[0039] Preferably, in step (4):

[0040] The mass ratio of water to antimony-bismuth slag is (1-1.5):1; and / or,

[0041] The stirring speed is 80-120 rpm; and / or

[0042] The stirring time is 20-40 min.

[0043] Preferably, in step (5):

[0044] The alkaline solution is a sodium hydroxide solution with a concentration of 5-7 mol / L, and the amount of sodium hydroxide added is 0.8-1.4 times the mass content of antimony in the slurry; and / or,

[0045] The stirring speed is 180-220 rpm.

[0046] Preferably, in step (6):

[0047] The acid solution is a hydrochloric acid solution with a concentration of 2-4 mol / L; and / or,

[0048] The stirring speed is 140-180 rpm.

[0049] Beneficial effects of the utility model:

[0050] By adopting the system and method disclosed in the utility model, suitable reagents are selected for separation and purification according to the characteristics of each metal element, so as to achieve the separation of silver and lead from antimony, bismuth and copper in lead anode mud. The leaching slag, i.e., the main components are silver chloride and lead sulfate precipitation annealing method smelting, the leaching liquid mainly contains copper, antimony and bismuth, and the leaching rate of copper, antimony and bismuth reaches more than 98%. After copper is impurity-removed, antimony and bismuth can be recovered and purified separately, and high-purity products such as antimony trisulfide and bismuth oxychloride can be produced, wherein the purity of bismuth oxychloride reaches more than 98%. This process is a combined treatment of wet and pyrometallurgy, the recovery rate of antimony and bismuth can reach more than 99%, the whole process is controllable and has good effect, and the wastewater can be replenished and recycled, which has reached the leading level in China. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a process flow diagram of the method disclosed in the utility model;

[0052] Figure 2 The figure is a schematic diagram of the connection relationship of each device in the system disclosed in the utility model. DETAILED DESCRIPTION

[0053] The utility model is described in detail below in conjunction with the accompanying drawings and specific implementation methods. The embodiments shown below do not limit the contents of the utility model described in the claims. In addition, the entire contents of the structures represented by the following embodiments are not limited to those necessary as solutions to the utility model described in the claims.

[0054] Reference Figure 2 On the other hand, the utility model also discloses a comprehensive recovery system for lead anode mud, including a copper recovery system and an antimony-bismuth recovery system, wherein the copper recovery system includes a first receiving hopper 4 and a pre-soaking kettle 1, a first filter press 3, an antimony-bismuth precipitation kettle 5, a second filter press 7, a copper replacement kettle 9, and a copper replacement filter tank 10, each of which is provided with a liquid inlet and a liquid outlet, wherein the pre-soaking kettle 1, the first filter press 3, the antimony-bismuth precipitation kettle 5, the second filter press 7, the copper replacement kettle 9, and the copper replacement filter tank 10 are connected in sequence through pipelines; the first filter press 3 is also provided with A first slag outlet is provided, and the second filter press 7 is also provided with a second slag outlet; the first receiving hopper 4 is connected to the first slag outlet of the first filter press 3; the antimony-bismuth recovery system includes an antimony-bismuth slurry tank 8, a neutralization kettle 11, a neutralization filter tank 12, an antimony precipitation kettle 13, and an antimony precipitation filter tank 14 connected in sequence by pipelines, and the antimony-bismuth slurry tank 8 is connected to the second slag outlet of the second filter press 7; the pre-impregnation kettle 1, the antimony-bismuth precipitation kettle 5, the copper replacement kettle 9, the neutralization kettle 11, and the antimony precipitation kettle 13 are all provided with a stirring device.

[0055] In one embodiment of the present invention, the hopper 4 mouth of the first receiving hopper 4 is arranged below the first slag outlet of the first filter press 3; the slot of the antimony-bismuth slurrying tank 8 is arranged below the second slag outlet of the second filter press 7.

[0056] In one embodiment of the utility model, the liquid outlet of the copper replacement filter tank 10 is externally connected to a first liquid outlet pipe; the antimony precipitation filter tank 14 is externally connected to a second liquid outlet pipe; the copper recovery system also includes a first centrifugal pump 2 arranged on the pipeline between the prepreg kettle 1 and the first filter press 3, a second centrifugal pump 6 arranged on the pipeline between the antimony precipitation kettle 5 and the second filter press 7, and a third centrifugal pump 16 arranged on the first liquid outlet pipe; the antimony bismuth recovery system also includes a fourth centrifugal pump 17 arranged on the pipeline between the antimony bismuth slurry tank 8 and the neutralization kettle 11, a fifth centrifugal pump 18 arranged between the neutralization filter tank 12 and the antimony precipitation kettle 13, and a sixth centrifugal pump 15 arranged on the second liquid outlet pipe.

[0057] In one embodiment of the utility model, the prepreg kettle 1, the antimony-bismuth precipitation reactor, the copper replacement kettle 9, and / or the antimony-bismuth slurry tank 8 are all made of bisphenol A glass fiber reinforced plastics; the prepreg slag bucket, the copper replacement filter tank 10, the neutralization filter tank 12, and the antimony precipitation filter tank 14 are all made of steel-lined PO material; the first filter press 3 and the second filter press 7 are both water-washed diaphragm filter presses; the neutralization kettle 11 and the antimony precipitation kettle 13 are both glass-lined jacketed reactors; the first centrifugal pump 2, the second centrifugal pump 6, the third centrifugal pump 16, the fourth centrifugal pump 17, the fifth centrifugal pump 18, and the sixth centrifugal pump 15 are all engineering plastic pumps; all the pipelines are bisphenol A glass fiber reinforced plastic pipelines.

[0058] Reference Figure 1 The utility model also provides a method for comprehensively recovering lead anode mud, comprising the following steps:

[0059] (1) Pre-immersion: add hydrochloric acid solution, oxidant and sodium salt solution to lead anode mud, stir and react at 65-85°C (e.g. 68°C, 70°C, 75°C, 78°C, 80°C, 82°C, etc.) for 50-120 min (e.g. 60 min, 80 min, 90 min, 100 min, 110 min, etc.), then separate the solid and liquid to obtain a pre-immersion solution; the concentration of the hydrochloric acid is 2.5-4 mol / L (e.g. 2.8 mol / L, 3 mol / L, 3.2 mol / L, 3.5 mol / L, 3.8 mol / L, etc.); the mass concentration of the oxidant is 45-55% (e.g. 48%, 50%, 52%, 54%). % etc.); the sodium salt solution is a saturated sodium chloride solution (saturated solution at room temperature); the mass ratio of the hydrochloric acid solution, the oxidant and the sodium salt solution is 1:(0.13-0.3):(0.15-0.25) (for example, 1:0.15:0.15, 1:0.18:0.17, 1:0.25:0.2, 1:0.28:0.24, etc.); the liquid-solid mass ratio of the pre-impregnation reaction system is controlled to be (3-5):1 (for example, 3.5:1, 3.8:1, 4:1, 4.5:1, etc.); the stirring speed is 180-220rpm (for example, 190rpm, 200rpm, 210rpm, 215rpm, etc.).

[0060] (2) Precipitating antimony and bismuth: adjusting the pre-dip solution to a pH value of less than 2.5 (e.g., 1, 1.5, 2, 2.2, etc.), stirring the reaction at a temperature of 40-60°C (e.g., 42°C, 45°C, 48°C, 50°C, 52°C, 55°C, 58°C, etc.) for 30-60 min (e.g., 35 min, 40 min, 45 min, 50 min, 55 min, etc.), and then performing solid-liquid separation to obtain a post-precipitation antimony and bismuth solution and an antimony and bismuth slag; the method for adjusting the pH value of the pre-dip solution is to add water thereto; the stirring speed is 140-180 rpm (e.g., 145 rpm, 150 rpm, 155 rpm, 160 rpm, 170 rpm, 175 rpm, etc.).

[0061] (3) Copper replacement: adjusting the temperature of the solution after precipitation of antimony and bismuth to 30-50°C (e.g., 32°C, 35°C, 40°C, 45°C, 48°C, etc.), adding alkali to adjust the acid concentration to 10-18 g / L (e.g., 12 g / L, 14 g / L, 16 g / L, 17 g / L, etc.), adding the replacement agent, stirring the reaction for 30-60 min (e.g., 35 min, 40 min, 45 min, 50 min, 55 min, etc.), and then separating the solid and the liquid to obtain a copper replacement solution and copper slag; the alkali is sodium hydroxide, Potassium hydroxide, and / or sodium carbonate; the displacing agent is iron powder with a particle size of 50-200 mesh (for example, 50 mesh, 100 mesh, 150 mesh, 200 mesh, etc.); the amount of the displacing agent added is 1.2-1.5 times (for example, 1.25 times, 1.3 times, 1.35 times, 1.4 times, 1.45 times, etc.) the mass content of copper in the solution after antimony and bismuth precipitation; the stirring speed is 140-180rpm (for example, 145rpm, 150rpm, 155rpm, 160rpm, 170rpm, etc.).

[0062] (4) Slurrying: adding water to the antimony-bismuth slag and stirring to obtain a slurry; the mass ratio of water to the antimony-bismuth slag is (1-1.5):1 (for example, 1.2:1, 1.3:1, 1.4:1, etc.); the stirring speed is 80-120rpm (for example, 85rpm, 90rpm, 95rpm, 100rpm, 105rpm, 110rpm, etc.); the stirring time is 20-40min (for example, 25min, 30min, 35min, 38min, etc.).

[0063] (5) Neutralization: adding an alkaline solution to the slurry, stirring the reaction for 40-80 min (e.g., 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, etc.), and then separating the solid and liquid to obtain bismuth slag and antimony-containing liquid; the alkaline solution is a sodium hydroxide solution with a concentration of 5-7 mol / L (e.g., 5.2 mol / L, 5.5 mol / L, 6 mol / L, 6.2 mol / L, 6.5 mol / L, 6.8 mol / L, etc.), and the amount of sodium hydroxide added is 0.8-1.4 times (e.g., 0.9 times, 1 times, 1.1 times, 1.2 times, 1.3 times, etc.) the mass content of antimony in the slurry; the stirring speed is 180-220 rpm (e.g., 185 rpm, 190 rpm, 195 rpm, 200 rpm, 205 rpm, 210 rpm, etc.).

[0064] (6) Antimony precipitation: add an acid solution to the antimony-containing liquid, adjust the pH to 2.0-2.5 (e.g., 2.1, 2.2, 2.3, 2.4, etc.), stir and react at 30-60°C (e.g., 35°C, 40°C, 45°C, 50°C, 55°C, etc.) for 30-60min (e.g., 35min, 40min, 45min, 50min, 55min, etc.), and then perform solid-liquid separation to obtain an antimony precipitation liquid and antimony slag. The acid solution is a hydrochloric acid solution with a concentration of 2-4mol / L (e.g., 2.2mol / L, 2.5mol / L, 2.8mol / L, 3mol / L, 3.2mol / L, 3.5mol / L, 3.8mol / L, etc.); the stirring speed is 140-180rpm (e.g., 145rpm, 150rpm, 160rpm, 165rpm, 170rpm, 175rpm, etc.).

[0065] The method of the present invention is further explained below through specific examples. Examples 1-3 of the present invention are carried out in a laboratory, and Examples 4-7 are completed using the system disclosed in the present invention.

[0066] Example 1

[0067] A method for comprehensively recovering lead anode mud comprises the following steps:

[0068] (1) 100 g of lead anode mud was placed in a 1000 ml three-necked flask, and 310 ml of 3 mol / L hydrochloric acid solution, 55 ml of 50% sodium chlorate solution, and 47 ml of sodium chloride solution were added to the three-necked flask in sequence. The temperature was raised to 70° C. and stirring was started. The stirring speed was 180 rpm and the stirring time was 50 min. After the reaction was completed, the solid and liquid were separated. The prepreg residue was washed with water once to produce a washing liquid, and the prepreg residue was further treated.

[0069] (2) The primary washing liquid and the pre-soaking liquid are added to a new three-necked flask, and production water is added to control the pH value to 2.3. Stirring is started, the stirring speed is 150 rpm, the stirring time is 30 min, and the temperature is 40°C. After the reaction is completed, the solid and liquid are separated, and the antimony-bismuth precipitated slag is washed twice with water to produce a secondary washing liquid, and the antimony-bismuth precipitated slag is further treated.

[0070] (3) The second washing liquid and the solution after precipitation of antimony and bismuth were added to a new three-necked flask, the temperature was raised to 30°C, stirring was started, the stirring speed was 140 rpm, the stirring time was 30 min, sodium hydroxide was added, the acid concentration of the solution was adjusted to 12 g / L, iron powder was added, the amount of iron powder was 1.2 times the amount of copper in the solution, the reaction was completed, the solid and liquid were separated, the copper slag was further processed, and the liquid after replacement was poured into the wastewater discharge system.

[0071] (4) The antimony-precipitated bismuth slag in step (2) is added to a new three-necked flask, and the mass ratio of produced water to the antimony-precipitated bismuth slag is 1:1. Stirring is started, the stirring speed is 80 rpm, the stirring time is 20 min, and then a 6 mol / L sodium hydroxide solution is added, the amount of sodium hydroxide added is 0.8 times the amount of antimony in the solution, the stirring speed is increased to 180 rpm, the stirring time is 40 min, the reaction is completed, the solid-liquid separation is performed, and the bismuth slag is further processed.

[0072] (5) The neutralized liquid in step (4) is added to a new three-necked flask, the temperature is raised to 30° C., stirring is started, the stirring speed is 140 rpm, 3 mol / L hydrochloric acid solution is added, the pH value is adjusted to 2.1, and the stirring time is 30 min. After the reaction is completed, the solid-liquid separation is performed, the antimony precipitate slag is further processed, and the antimony precipitate liquid is poured into the wastewater treatment system.

[0073] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is 98.2% and the recovery rate is 99.1%.

[0074] Example 2

[0075] (1) 100 g of lead anode mud was placed in a 1000 ml three-necked flask, and 410 ml of 3 mol / L hydrochloric acid solution, 61 ml of 50% sodium chlorate solution, and 66 ml of sodium chloride solution were added to the three-necked flask in sequence. The temperature was raised to 75° C. and stirring was started. The stirring speed was 200 rpm and the stirring time was 50 min. After the reaction was completed, the solid and liquid were separated. The prepreg residue was washed with water once to produce a washing liquid, and the prepreg residue was further treated.

[0076] (2) The primary washing liquid and the pre-soaking liquid are added to a new three-necked flask, and production water is added. The pH value is controlled at 2.3, and stirring is started. The stirring speed is 150 rpm, the stirring time is 45 min, and the temperature is 48° C. After the reaction is completed, the solid and liquid are separated. The antimony-bismuth precipitate slag is washed twice with water to produce a secondary washing liquid, and the antimony-bismuth precipitate slag is further treated.

[0077] (3) The second washing liquid and the solution after precipitation of antimony and bismuth were added to a new three-necked flask, the temperature was raised to 39° C., stirring was started, the stirring speed was 160 rpm, the stirring time was 45 min, sodium hydroxide was added, the acid concentration of the solution was adjusted to 15 g / L, iron powder was added, and the amount of iron powder was 1.32 times the amount of copper in the solution. After the reaction was completed, the solid and liquid were separated, the copper slag was further processed, and the liquid after replacement was poured into the wastewater discharge system.

[0078] (4) The antimony-precipitated bismuth slag in step (2) is added to a new three-necked flask, and the mass ratio of produced water to the antimony-precipitated bismuth slag is 1:1. Stirring is started, the stirring speed is 90 rpm, the stirring time is 30 min, and then a 6 mol / L sodium hydroxide solution is added, the amount of sodium hydroxide added is 1.34 times the amount of antimony in the solution, the stirring speed is increased to 195 rpm, the stirring time is 56 min, the reaction is completed, the solid-liquid separation is performed, and the bismuth slag is further processed.

[0079] (5) The neutralized liquid in step (4) was added to a new three-necked flask, the temperature was raised to 46° C., stirring was started, the stirring speed was 167 rpm, 3 mol / L hydrochloric acid solution was added, the pH value was adjusted to 2.2, the stirring time was 47 min, the reaction was completed, the solid-liquid separation was performed, the antimony precipitate slag was further processed, and the antimony precipitate liquid was poured into the wastewater treatment system.

[0080] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is 98.5%, and the recovery rate is 99.3%.

[0081] Example 3

[0082] (1) 100 g of lead anode mud was placed in a 1000 ml three-necked flask, and 435 ml of 3 mol / L hydrochloric acid solution, 82 ml of 50% sodium chlorate solution, and 85 ml of sodium chloride solution were added to the three-necked flask in sequence. The temperature was raised to 85° C. and stirring was started. The stirring speed was 220 rpm and the stirring time was 120 min. After the reaction was completed, the solid and liquid were separated. The prepreg residue was washed with water once to produce a washing liquid, and the prepreg residue was further treated.

[0083] (2) The primary washing liquid and the pre-soaking liquid are added to a new three-necked flask, and production water is added to control the pH value to 2.4. Stirring is started, the stirring speed is 180 rpm, the stirring time is 58 min, and the temperature is 56° C. After the reaction is completed, the solid and liquid are separated, and the antimony-bismuth precipitated slag is washed twice with water to produce a secondary washing liquid, and the antimony-bismuth precipitated slag is further treated.

[0084] (3) The second washing liquid and the solution after precipitation of antimony and bismuth were added to a new three-necked flask, the temperature was raised to 49° C., stirring was started, the stirring speed was 178 rpm, the stirring time was 58 min, sodium hydroxide was added, the acid concentration of the solution was adjusted to 18 g / L, iron powder was added, and the amount of iron powder was 1.47 times the amount of copper in the solution. After the reaction was completed, the solid and liquid were separated, the copper slag was further processed, and the liquid after replacement was poured into the wastewater discharge system.

[0085] (4) The antimony-precipitated bismuth slag in step (2) is added to a new three-necked flask, and the mass ratio of produced water to the antimony-precipitated bismuth slag is 1:1. Stirring is started, the stirring speed is 137 rpm, the stirring time is 39 min, and then a 6 mol / L sodium hydroxide solution is added, the amount of sodium hydroxide added is 1.35 times the amount of antimony in the solution, the stirring speed is increased to 220 rpm, the stirring time is 75 min, the reaction is completed, the solid-liquid separation is performed, and the bismuth slag is further processed.

[0086] (5) The neutralized liquid in step (4) was added to a new three-necked flask, the temperature was raised to 58° C., stirring was started, the stirring speed was 175 rpm, 3 mol / L hydrochloric acid solution was added, the pH value was adjusted to 2.4, the stirring time was 55 min, the reaction was completed, the solid-liquid separation was performed, the antimony precipitate slag was further processed, and the antimony precipitate liquid was poured into the wastewater treatment system.

[0087] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is 99%, and the recovery rate is 99.6%.

[0088] Example 4

[0089] A method for comprehensively recovering lead anode mud comprises the following steps:

[0090] (1) Lead anode mud is placed in a pre-impregnation kettle 1, and hydrochloric acid solution, oxidant and sodium salt are added to the pre-impregnation kettle 1. The pre-impregnation kettle 1 is heated to 65-85°C and stirred. The stirring speed is 180-220rpm and the stirring time is 50-120min. After the reaction is completed, the solid-liquid separation is carried out. The material in the pre-impregnation kettle 1 is pumped into the first filter press 3 through the first centrifugal pump 2 for filter pressing to obtain pre-impregnation residue and pre-impregnation liquid. The pre-impregnation residue enters the pre-impregnation residue receiving hopper 4, and the pre-impregnation liquid enters the antimony-bismuth precipitation reactor 5. The hydrochloric acid concentration is 3 mol / L, the sodium salt is a saturated sodium chloride solution, the oxidant is a 50% sodium chlorate solution, the liquid-solid ratio is 3-5:1, and the mass ratio of hydrochloric acid: sodium chlorate: sodium chloride solution is 1:0.13-0.3:0.15-0.25.

[0091] (2) After the pre-impregnation liquid is pumped into the antimony-bismuth precipitation reactor 5, production water is added, the pH value is controlled, stirring is started, the stirring speed is 140-180 rpm, the stirring time is 30-60 min, and the temperature is 40-60° C. After the reaction is completed, the slurry is pumped into the second filter press 7 through the second centrifugal pump 6 for pressure filtration and water washing, the liquid after antimony-bismuth precipitation and the first washing liquid are pumped into the copper replacement reactor 9, and the antimony-bismuth slag enters the antimony-bismuth slurry tank 8, wherein the reaction pH value is controlled to be less than 2.5.

[0092] (3) The liquid after precipitation of antimony and bismuth and the first washing liquid are pumped into the copper replacement kettle 9, the temperature is raised to 30-50°C, alkali is added to adjust the acid concentration, stirring is started at 140-180rpm, the stirring time is 30-60min, and the replacement agent is added. After the reaction is completed, the solid-liquid separation is carried out through the copper replacement filter tank 10, the filter residue is further processed, and the filtrate is sent to the wastewater treatment system through the third centrifugal pump 16. The alkali is sodium hydroxide or potassium hydroxide or sodium carbonate. This process uses sodium hydroxide, the acid concentration is adjusted to 10g / L-18g / L, the replacement agent is iron powder, the iron powder is sieved with a mesh number of 100, and the amount of iron powder added is 1.2-1.5 times the amount of copper in the solution.

[0093] (4) The antimony-bismuth slag is added to the slurry tank 8, and the production water is added. The stirring is started at a stirring speed of 80-120 rpm and a stirring time of 20-40 min. Then the material is pumped into the neutralization kettle 11 through the fourth centrifugal pump 17, and the strong alkali solution is added to the neutralization kettle 11. The stirring is started at a stirring speed of 180-220 rpm and a stirring time of 40-80 min. After the reaction is completed, the bismuth slag is separated from the solid and liquid through the neutralization filter tank 12. The bismuth slag is further processed, and the filtrate is pumped into the antimony precipitation kettle 13 through the fifth centrifugal pump 18. The mass ratio of the production water to the antimony-bismuth slag is 1:1, the strong alkali is a 6 mol / L sodium hydroxide solution, and the amount of sodium hydroxide added is 0.8-1.4 times the amount of antimony.

[0094] (5) After the filtrate is pumped into the antimony precipitation kettle 13, the temperature is raised to 30-60°C, stirring is started, the stirring speed is 140-180rpm, strong acid is added, the pH value is controlled, and the stirring time is 30-60min. After the reaction is completed, solid-liquid separation is performed through the antimony precipitation filter tank 14, the filter residue is further processed, and the filtrate is sent to the waste liquid treatment system through the sixth centrifugal pump 15. The strong acid is 3mol / L hydrochloric acid solution, and the pH value is controlled at 2.0-2.5.

[0095] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is above 98%, and the recovery rate is above 99%.

[0096] Example 5

[0097] A method for comprehensively recovering lead anode mud comprises the following steps:

[0098] (1) Pre-impregnation: add hydrochloric acid solution, oxidant and sodium salt solution to lead anode mud, stir and react at 68°C for 60 minutes, then separate the solid and liquid to obtain a pre-impregnation solution; the concentration of the hydrochloric acid is 2.8 mol / L; the oxidant is a sodium chlorate solution with a mass concentration of 48%; the sodium salt solution is a saturated sodium chloride solution; the mass ratio of the hydrochloric acid solution, the oxidant and the sodium salt solution is 1:0.13:0.18; the liquid-solid ratio of the pre-impregnation reaction system is controlled to be 3.5:1; the stirring speed is 190 rpm.

[0099] (2) Precipitation of antimony and bismuth: the pre-immersion solution was adjusted to a pH of 1-2, and the reaction was stirred at 45°C for 35 minutes, and then the solid and liquid were separated to obtain a post-precipitation liquid of antimony and bismuth and an antimony and bismuth slag; the method for adjusting the pH of the pre-immersion solution was to add water thereto; and the stirring speed was 150 rpm.

[0100] (3) Copper replacement: adjusting the temperature of the solution after the precipitation of antimony and bismuth to 35°C, adding alkali to adjust the acid concentration to 12 g / L, adding a replacement agent, stirring the reaction for 35 minutes, and then separating the solid and liquid to obtain a copper replacement solution and copper slag; the alkali is sodium hydroxide; the replacement agent is iron powder with a particle size of 50 mesh; the amount of the replacement agent added is 1.2 times the copper content in the solution after the precipitation of antimony and bismuth; the stirring speed is 145 rpm.

[0101] (4) Slurrying: adding water to the antimony-bismuth slag and stirring to obtain a slurry; the mass ratio of the water to the antimony-bismuth slag is 1:1; the stirring speed is 80 rpm; and the stirring time is 20 min.

[0102] (5) Neutralization: adding an alkaline solution to the slurry, stirring the reaction for 40 minutes, and then separating the solid and liquid to obtain bismuth slag and antimony-containing liquid; the alkaline solution is a sodium hydroxide solution with a concentration of 5 mol / L, and the amount of sodium hydroxide added is 0.8 times the amount of antimony in the slurry; the stirring speed is 180 rpm.

[0103] (6) Antimony precipitation: add an acid solution to the antimony-containing liquid, adjust the pH to 2.0, stir and react at 30°C for 30 minutes, and then perform solid-liquid separation to obtain an antimony precipitation liquid and antimony slag. The acid solution is a hydrochloric acid solution with a concentration of 2 mol / L; the stirring speed is 140 rpm.

[0104] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is 99.3%, and the recovery rate is 99.6%.

[0105] Example 6

[0106] A method for comprehensively recovering lead anode mud comprises the following steps:

[0107] (1) Pre-impregnation: add hydrochloric acid solution, oxidant and sodium salt solution to lead anode mud, stir and react at 72°C for 85 minutes, then separate the solid and liquid to obtain a pre-impregnation solution; the concentration of the hydrochloric acid is 3.2 mol / L; the oxidant is a sodium chlorate solution with a mass concentration of 50%; the sodium salt solution is a saturated sodium chloride solution; the mass ratio of the hydrochloric acid solution, the oxidant and the sodium salt solution is 1:0.25:0.2; the liquid-solid ratio of the pre-impregnation reaction system is controlled to be 4:1; the stirring speed is 200 rpm.

[0108] (2) Precipitation of antimony and bismuth: adjusting the pre-immersion solution to a pH value of < (1.5-2.2), stirring the reaction at 50°C for 45 minutes, and then separating the solid and liquid to obtain a post-precipitation liquid of antimony and bismuth and an antimony and bismuth slag; the method for adjusting the pH value of the pre-immersion solution is to add water thereto; the stirring speed is 160 rpm.

[0109] (3) Copper replacement: adjusting the temperature of the solution after the precipitation of antimony and bismuth to 40°C, adding alkali to adjust the acid concentration to 15 g / L, adding a replacement agent, stirring the reaction for 45 minutes, and then separating the solid and liquid to obtain a copper replacement solution and copper slag; the alkali is potassium hydroxide; the replacement agent is iron powder with a particle size of 150 mesh; the amount of the replacement agent added is 1.3 times the copper content in the solution after the precipitation of antimony and bismuth; the stirring speed is 160 rpm.

[0110] (4) Slurrying: adding water to the antimony-bismuth slag and stirring to obtain a slurry; the mass ratio of the water to the antimony-bismuth slag is 1.3:1; the stirring speed is 100 rpm; and the stirring time is 30 min.

[0111] (5) Neutralization: adding an alkaline solution to the slurry, stirring the reaction for 60 minutes, and then separating the solid and liquid to obtain bismuth slag and antimony-containing liquid; the alkaline solution is a sodium hydroxide solution with a concentration of 6 mol / L, and the amount of sodium hydroxide added is 1.2 times the amount of antimony in the slurry; the stirring speed is 200 rpm.

[0112] (6) Antimony precipitation: add an acid solution to the antimony-containing liquid, adjust the pH to 2.1-2.3, stir and react at 45°C for 45 minutes, and then perform solid-liquid separation to obtain an antimony precipitation liquid and antimony slag. The acid solution is a hydrochloric acid solution with a concentration of 3 mol / L; the stirring speed is 160 rpm.

[0113] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is 98.7%, and the recovery rate is 99.4%.

[0114] Example 7

[0115] A method for comprehensively recovering lead anode mud comprises the following steps:

[0116] (1) Pre-impregnation: add hydrochloric acid solution, oxidant and sodium salt solution to lead anode mud, stir and react at 85°C for 120 minutes, then separate the solid and liquid to obtain a pre-impregnation solution; the concentration of the hydrochloric acid is 4 mol / L; the oxidant is a sodium chlorate solution with a mass concentration of 55%; the sodium salt solution is a saturated sodium chloride solution; the mass ratio of the hydrochloric acid solution, the oxidant and the sodium salt solution is 1:-0.3:0.25; the liquid-solid ratio of the pre-impregnation reaction system is controlled to be 5:1; the stirring speed is 220 rpm.

[0117] (2) Precipitation of antimony and bismuth: adjusting the pre-immersion solution to a pH value of < (2.4-2.5), stirring the reaction at 60°C for 60 minutes, and then separating the solid and liquid to obtain a post-precipitation liquid of antimony and bismuth and an antimony and bismuth slag; the method for adjusting the pH value of the pre-immersion solution is to add water thereto; the stirring speed is 180 rpm.

[0118] (3) Copper replacement: adjusting the temperature of the solution after the precipitation of antimony and bismuth to 50°C, adding alkali to adjust the acid concentration to 18 g / L, adding a replacement agent, stirring the reaction for 60 minutes, and then separating the solid and liquid to obtain a copper replacement solution and copper slag; the alkali is sodium hydroxide, potassium hydroxide and sodium carbonate; the replacement agent is iron powder with a particle size of 200 mesh; the amount of the replacement agent added is 1.5 times the copper content in the solution after the precipitation of antimony and bismuth; the stirring speed is 180 rpm.

[0119] (4) Slurrying: adding water to the antimony-bismuth slag and stirring to obtain a slurry; the mass ratio of the water to the antimony-bismuth slag is 1.5:1; the stirring speed is 120 rpm; and the stirring time is 40 min.

[0120] (5) Neutralization: adding an alkaline solution to the slurry, stirring the reaction for 80 minutes, and then separating the solid and liquid to obtain bismuth slag and antimony-containing liquid; the alkaline solution is a sodium hydroxide solution with a concentration of 7 mol / L, and the amount of sodium hydroxide added is 1.4 times the amount of antimony in the slurry; the stirring speed is 220 rpm.

[0121] (6) Antimony precipitation: add an acid solution to the antimony-containing liquid, adjust the pH to 2.5, stir and react at 60°C for 60 minutes, and then perform solid-liquid separation to obtain an antimony precipitation liquid and antimony slag. The acid solution is a hydrochloric acid solution with a concentration of 4 mol / L; the stirring speed is 180 rpm.

[0122] According to experimental detection, the leaching rate of copper, antimony and bismuth in this embodiment is 98.8%, and the recovery rate is 99.3%.

[0123] The method for comprehensively recovering lead anode mud disclosed by the utility model is preferably completed by using the system disclosed by the utility model.

[0124] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A system for comprehensive recovery of lead anode mud, characterized in that: Including copper recovery system and antimony and bismuth recovery system, The copper recovery system comprises a first receiving hopper and a pre-leaching kettle, a first filter press, an antimony-bismuth kettle, a second filter press, a copper replacement kettle, and a copper replacement filter tank, each of which is provided with a liquid inlet and a liquid outlet. The pre-leaching kettle, the first filter press, the antimony-bismuth kettle, the second filter press, the copper replacement kettle, and the copper replacement filter tank are sequentially connected through pipelines; the first filter press is also provided with a first slag outlet, and the second filter press is also provided with a second slag outlet; the first receiving hopper is connected to the first slag outlet of the first filter press; The antimony-bismuth recovery system comprises an antimony-bismuth slurry tank, a neutralization kettle, a neutralization filter tank, an antimony precipitation kettle, and an antimony precipitation filter tank, which are connected in sequence through pipelines, and the antimony-bismuth slurry tank is connected to the second slag outlet of the second filter press; The pre-leaching kettle, the antimony-bismuth precipitation kettle, the copper replacement kettle, the neutralization kettle and the antimony precipitation kettle are all provided with stirring devices.

2. A system for comprehensive recovery of lead anode slime according to claim 1, characterized in that: The hopper opening of the first receiving hopper is arranged below the first slag outlet of the first filter press; the slot opening of the antimony-bismuth slurrying tank is arranged below the second slag outlet of the second filter press.

3. The system for comprehensive recovery of lead anode slime according to claim 1, characterized in that: The liquid outlet of the copper replacement filter tank is externally connected to a first liquid outlet pipe; the antimony precipitation filter tank is externally connected to a second liquid outlet pipe; the copper recovery system also includes a first centrifugal pump arranged on the pipeline between the prepreg kettle and the first filter press, a second centrifugal pump arranged on the pipeline between the antimony bismuth precipitation kettle and the second filter press, and a third centrifugal pump arranged on the first liquid outlet pipe; the antimony bismuth recovery system also includes a fourth centrifugal pump arranged on the pipeline between the antimony bismuth slurry tank and the neutralization kettle, a fifth centrifugal pump arranged between the neutralization filter tank and the antimony precipitation kettle, and a sixth centrifugal pump arranged on the second liquid outlet pipe.

4. A comprehensive system for recovering lead anode slime according to claim 3, characterized in that: The pre-preg kettle, the antimony-bismuth precipitation reactor, the copper replacement kettle, and / or the antimony-bismuth slurry tank are all made of bisphenol A glass fiber reinforced plastic; and / or, The copper replacement filter tank, neutralization filter tank, and antimony precipitation filter tank are all made of steel-lined PO; and / or, The first filter press and the second filter press are both water-washed membrane filter presses; and / or, The neutralization kettle and antimony precipitation kettle are both glass-lined jacketed reactors; and / or, The first centrifugal pump, the second centrifugal pump, the third centrifugal pump, the fourth centrifugal pump, the fifth centrifugal pump and the sixth centrifugal pump are all engineering plastic pumps; and / or, The pipes are all bisphenol A glass fiber reinforced plastic pipes.

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