Method for separating and recycling manganese and lead in electrolytic manganese anode slime

Abstract

The invention relates to a method for separating and recycling manganese and lead in electrolytic manganese anode slime, and belongs to the technical field of electrolytic manganese metal. Adding sulfuric acid and glucose into the electrolytic manganese anolyte, uniformly stirring, and heating to 90-95 DEG C to obtain an organic acid leaching solution; the electrolytic manganese anode slime is added into the organic acid leaching solution, leaching is conducted for 2 h at the temperature of 90-95 DEG C at the speed of 300 rpm, and then filtering is conducted to obtain a first-stage leaching solution; electrolytic manganese anode slime is added into the first-section leaching solution according to the liquid-solid ratio of 6.5-7: 1 m < 3 > / t, and a leaching solution and first-section leaching residues are obtained; adding the first-stage leaching residues into an organic acid leaching solution to obtain a second-stage leaching solution and leaching residues; activated carbon is added into a leaching solution obtained after first-stage leaching, stirring is conducted for 30 min at the normal temperature at the speed of 300 rpm, and residual organic matter in the leaching solution is adsorbed and removed; and leaching residues obtained after second-stage leaching are washed with water and dried, and lead concentrate with the lead grade ranging from 40 wt% to 50 wt% is obtained. The method has the advantages of low acid consumption, high manganese leaching rate, low treatment cost and the like.

Description

Technical Field

[0001] The invention relates to a method for separating and recovering manganese and lead in electrolytic manganese anode mud, belonging to the technical field of electrolytic manganese metal. Background Art

[0002] Electrolytic manganese anode mud is a dark brown solid waste produced in the anode chamber during the production of electrolytic manganese metal. The annual production volume is about 75,000-120,000 tons. It is mainly composed of substances such as MnO2, PbSO4, (NH4)2SO4 and MgSO4. The manganese content is generally between 40% and 50%, and the lead content is above 4%. At present, the mainstream treatment methods for electrolytic manganese anode mud are divided into two categories. The first category uses activated carbon, lignite, sulfur and the like as reducing agents to reduce and roast the electrolytic manganese anode mud at high temperature, and then leaches the cold material with sulfuric acid solution to obtain manganese sulfate solution and lead concentrate; the second category uses sulfite, hydrogen peroxide, pyrite, pyrite, sulfur and other inorganic substances and sawdust, corn stalks, glucose, starch and other organic substances as reducing agents to reduce and leach the electrolytic manganese anode mud in an acidic solution system to achieve the recovery of anode mud.

[0003] For example, the article “Reduction Roasting-Acid Leaching Experimental Study of Electrolytic Manganese Anode Mud”, Rare Metals and Cemented Carbides, Zheng Zien, disclosed the research on the reduction-acid leaching of electrolytic manganese anode mud using lignite as a reducing agent.

[0004] The article “Study on wet leaching of manganese from electrolytic manganese anode mud using hydrogen peroxide as a reducing agent”, Journal of Engineering Science, Zhao Junjie et al., discloses the study of wet reduction leaching of electrolytic manganese anode mud using hydrogen peroxide as a reducing agent.

[0005] The patent application number is 201810787561.9, a method for producing manganese sulfate by reducing electrolytic manganese anode mud with hydroquinone. Water is added to the manganese anode mud to grind and slurry it, the manganese slurry is introduced into a reactor with a cooling device, hydroquinone is added to the manganese slurry, the manganese slurry is heated to 90-130 degrees Celsius, the vaporized hydroquinone is collected, the manganese slurry is separated and filtered through a filter press to obtain lead-tin slag and manganese sulfate solution, the purified manganese sulfate solution is heated for evaporation and concentration, crystallization separation, and drying to obtain the finished solid manganese sulfate.

[0006] The pyrometallurgical reduction process consumes a lot of energy, and the tail gas contains harmful substances such as sulfur dioxide. The desulfurization cost is high and the equipment corrosion phenomenon is serious, which has a great pollution to the surrounding environment. The wet reduction process has mild reaction conditions, and the reducing agent can achieve excellent results at low temperatures. The reaction temperature can be reached using industrial waste heat, but its cost and cleanliness are greatly affected by the type of reducing agent.

[0007] Since 2018, my country's environmental protection efforts have been continuously strengthened, the development of pyrometallurgical processes has been restricted, and the industry has gradually tended to study wet reduction leaching processes; using glucose as a reducing agent has low processing costs and is clean and environmentally friendly, but the residual organic matter in the leachate and the excessively high acid concentration are problems to be solved.

[0008] Adsorption method to remove residual organic matter from manganese sulfate solution, Wang Yuhong et al. used waste molasses as a reducing agent to reduce the manganese sulfate solution of pyrolusite in a dilute sulfuric acid solution as a raw material, and when activated carbon was used as an adsorbent, the removal rate of organic matter was only 13.6%. That is, when activated carbon was used as an organic adsorbent in the prior art, the adsorption effect was not good. Summary of the invention

[0009] In view of the problems and shortcomings of the above-mentioned prior art, the present invention provides a method for separating and recovering manganese and lead in electrolytic manganese anode mud. The present invention does not need to add alkaline substances such as calcium oxide, and adopts two-stage countercurrent leaching to reduce the concentration of sulfuric acid in the leachate, so that the concentration of sulfuric acid in the leachate is below 2g / L. The leachate is obtained to obtain a suitable acidity through specific leaching treatment steps. No special treatment is required, and high-quality coconut shell activated carbon is directly added to adsorb and remove residual organic matter. The removal rate can reach more than 90%, and the leached residue can be sold as lead concentrate after washing and drying. The present invention has the advantages of low acid consumption, high manganese leaching rate, and low processing cost. The present invention is achieved through the following technical solutions.

[0010] A method for separating and recovering manganese and lead in electrolytic manganese anode mud, the specific steps of which include:

[0011] Step 1: Prepare organic acid leaching solution

[0012] Add sulfuric acid and glucose to the electrolytic manganese anode solution, stir evenly and heat to 90-95°C to obtain an organic acid leaching solution;

[0013] Step 2: Prepare a first leaching solution

[0014] The electrolytic manganese anode mud is added to the organic acid leaching solution, and the solution is filtered after leaching at 90-95°C and 300 rpm for 2 hours to obtain a leaching solution; wherein the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 6.5-7:1m / s respectively. 3 / t, acid-ore ratio 0.9-1.25:1t / t, sugar-ore ratio 0.13-0.17:1t / t;

[0015] Step 3: Primary leaching

[0016] The electrolytic manganese anode mud is treated at a liquid-to-solid ratio of 6.5-7:1m 3 / t is added into the first-stage leaching solution, leached at 90-95°C and 300rpm for 2h and filtered to obtain the leaching solution and the first-stage leaching residue;

[0017] Step 4: Secondary leaching

[0018] The first-stage leaching residue is added to the organic acid leaching solution, leached at 90-95°C and 300rpm for 2h and filtered to obtain the second-stage leaching solution and leaching residue, wherein the ratio of each substance in the organic acid leaching solution to the first-stage leaching residue is 6.5-7:1m / s respectively. 3 / t, acid-ore ratio 0.9-1.25:1t / t, sugar-ore ratio 0.13-0.17:1t / t;

[0019] Step 5: Adsorption

[0020] Add activated carbon to the leachate of the first stage leaching at a solid-liquid ratio of 3-6:1000 g / mL, and stir at 300 rpm for 30 minutes at room temperature to adsorb and remove residual organic matter in the leachate;

[0021] Step 6: Wash and dry

[0022] The leaching residue from the second stage leaching is added into clean water at a liquid-solid ratio of 4-6:1 g / mL and stirred at 300 rpm for 30 minutes to remove soluble salts such as ammonium sulfate by elution, and a lead concentrate with a lead grade of 40wt%-50wt% is obtained after drying.

[0023] In step 1, industrial sulfuric acid with a purity of more than 93 wt% is used, glucose is food grade glucose monohydrate, and the sulfuric acid content of electrolytic manganese anolyte is 40-45 g / L, Mn 2+ Content 14-22g / L, ammonium sulfate content 90-100g / L.

[0024] In step 2, the manganese content in the electrolytic manganese anode mud is 40wt%-45wt%, and the lead content is 4wt%-8wt%; the physical phase of manganese is mainly manganese dioxide, and the physical phase of lead is mainly lead sulfate.

[0025] In step 4, the second stage leaching solution is added to the first stage leaching solution to carry out the first stage leaching of step 3.

[0026] The activated carbon in step 5 is high-quality coconut shell activated carbon, wherein the fixed carbon content is 81.45wt%, the volatile matter content is 5.50wt%, the ash content is 8.54wt%, and the moisture content is 4.51wt%.

[0027] The sulfuric acid concentration in the leachate of the above-mentioned first-stage leaching is reduced to 0.3-2 g / L.

[0028] The manganese content in the first-stage leaching residue is 1wt%-4wt%, and the lead content is 32wt%-36wt%; the main physical phases of manganese are manganese sulfate and manganese dioxide, and the physical phase of lead is lead sulfate.

[0029] The beneficial effects of the present invention are:

[0030] (1) The present invention uses a sulfuric acid + grape system to leach electrolytic manganese anode mud, which can reduce the high-valent manganese in the anode mud to Mn 2+ After entering the solution, the total manganese leaching rate can reach up to 99.1% during the reduction leaching process.

[0031] (2) The present invention uses a sulfuric acid system to leach electrolytic manganese anode mud, so that most of the lead is retained in the leaching residue in the form of lead sulfate, and the lead retention rate is above 99.6%.

[0032] (3) The present invention reduces the amount of sulfuric acid used by two-stage countercurrent leaching, and the sulfuric acid concentration of the leachate can be controlled below 2 g / L after completion.

[0033] (4) The present invention uses activated carbon to adsorb and remove the residual organic matter in the leaching solution. During the adsorption process, the organic matter adsorption rate is greater than 90%, and Mn 2+ The recovery rate is greater than 95%, which overcomes the problem of low adsorption rate of residual organic matter in manganese sulfate leaching solution adsorbed by activated carbon in the prior art.

[0034] (5) The lead content of the leaching slag of the present invention is 32%-36%, and the manganese content is less than 4%. After washing and removing impurities, the lead grade can be increased to more than 40%, and can be sold as lead concentrate.

[0035] (6) The present invention adopts a specific feed design, which can reduce the amount of acid used and reduce the content of residual acid and organic matter in the leaching solution. The effect is stable, environmentally friendly and efficient, and has certain promotion value in production in this field. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0037] The present invention will be further described below in conjunction with the accompanying drawings and specific implementation methods.

[0038] In this embodiment, the manganese leaching rate is calculated by the following formula:

[0039] Leaching rate = first stage leaching rate + second stage leaching rate

[0040] Example 1

[0041] like Figure 1 As shown, the method for separating and recovering manganese and lead in electrolytic manganese anode mud comprises the following specific steps:

[0042] Step 1: Prepare organic acid leaching solution

[0043] Add sulfuric acid (industrial sulfuric acid with a purity of more than 93 wt %) and glucose (food grade glucose monohydrate) to the electrolytic manganese anolyte (sulfuric acid content of electrolytic manganese anolyte is 41.4 g / L, Mn 2+ content 22g / L, ammonium sulfate content 90g / L), after stirring evenly, heating to 90°C to obtain an organic acid leaching solution;

[0044] Step 2: Prepare a first leaching solution

[0045] The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 45.64wt%, the lead content is 6.35wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the leaching is carried out at 90°C and 300rpm for 2h, and then filtered to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 45.64wt%, and the lead content is 6.35wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) 2+ The concentration of sulfuric acid is 82.59g / L, and the concentration of sulfuric acid is 44.26g / L); the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 6.5:1m 3 / t, acid ore ratio 1.15:1t / t, sugar ore ratio 0.13:1t / t;

[0046] Step 3: Primary leaching

[0047] The electrolytic manganese anode mud is treated at a liquid-to-solid ratio of 6.5:1m 3 / t was added to a first leaching solution, leached at 90 °C and 300 rpm for 2 h and filtered to obtain a leaching solution (Mn 2+ concentration is 95.04g / L, sulfuric acid concentration is 0.3g / L) and first-stage leaching residue (the manganese content in the first-stage leaching residue is 32.56wt%, and the lead content is 8.90wt%);

[0048] Step 4: Secondary leaching

[0049] The first-stage leaching residue was added to the organic acid leaching solution, leached at 90°C and 300 rpm for 2 h and filtered to obtain the second-stage leaching solution (Mn 2+ The concentration of organic acid leaching solution is 78.87g / L, the concentration of sulfuric acid is 82.5g / L) and the leaching residue (the manganese content in the leaching residue is 2.99wt%, the lead content is 52.45wt%), and the ratio of each substance in the organic acid leaching solution to the first-stage leaching residue is 6.5:1m 3 / t, acid ore ratio 1.15:1t / t, sugar ore ratio 0.13:1t / t;

[0050] Step 5: Adsorption

[0051] Activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45 wt%, a volatile matter content of 5.50 wt%, an ash content of 8.54 wt%, and a moisture content of 4.51 wt%) was added to the first-stage leaching solution at a solid-liquid ratio of 3:1000 g / mL, and the organic matter remaining in the leaching solution was removed by adsorption at 300 rpm and room temperature for 30 min. 2+ The concentration is 94.73 g / L, and the sulfuric acid concentration is 0.2 g / L;

[0052] Step 6: Wash and dry

[0053] The leaching residue from the second stage leaching was added into clean water at a liquid-to-solid ratio of 5:1 g / mL and stirred at 300 rpm for 30 min to remove soluble salts such as ammonium sulfate. After drying, a lead concentrate with a manganese content of 1.43 wt% and a lead grade of 41.66 wt% was obtained.

[0054] In this embodiment, the leaching rate of manganese reaches 98.72%, the sulfuric acid concentration of the leaching solution is 0.3 g / L, the organic matter adsorption rate is greater than 90%, and the manganese recovery rate is greater than 95%.

[0055] Comparative Example 1

[0056] The configuration of the organic acid leaching solution in step 1 of this comparative example is the same as that in Example 1, except that the electrolytic manganese anode mud is subjected to one leaching. The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 45.64wt%, the lead content is 6.35wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the solution is filtered after leaching at 90°C and 300rpm for 2h to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 45.64wt%, and the lead content is 6.35wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate). 2+ concentration is 90.51g / L, sulfuric acid concentration is 60.17g / L) and leaching residue; the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 6.5:1m 3 / t, acid ore ratio 1.25:1t / t, sugar ore ratio 0.13:1t / t;

[0057] The first stage of the leaching solution in this comparative example 1 was added with activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45wt%, a volatile content of 5.50wt%, an ash content of 8.54wt%, and a moisture content of 4.51wt%) at a solid-liquid ratio of 3:1000g / mL, and stirred at 300rpm for 30min to remove the residual organic matter in the leaching solution. After adsorption, the Mn content in the leaching solution was 2+ The concentration is 89.03 g / L, and the sulfuric acid concentration is 59.38 g / L;

[0058] In this comparative example, the leaching rate of manganese reached 97.57%, the sulfuric acid concentration of the leaching solution was 60.17 g / L, the organic matter adsorption rate was 60.42%, and the manganese recovery rate was 98.36%.

[0059] From the method of the present invention and the comparative example, after the two-stage countercurrent leaching of the present invention, the usage of 0.1 t / t sulfuric acid is reduced, the adsorption efficiency of organic matter is significantly improved, and the sulfuric acid concentration in the leaching solution of the present invention is controlled below 2 g / L.

[0060] Example 2

[0061] like Figure 1 As shown, the method for separating and recovering manganese and lead in electrolytic manganese anode mud comprises the following specific steps:

[0062] Step 1: Prepare organic acid leaching solution

[0063] Add sulfuric acid (industrial sulfuric acid with a purity of more than 93 wt%) and glucose (food grade glucose monohydrate) to the electrolytic manganese anolyte (sulfuric acid content of electrolytic manganese anolyte is 42.2 g / L, Mn 2+ content of 15.6 g / L and ammonium sulfate content of 100 g / L), and after being stirred evenly, heated to 95° C. to obtain an organic acid leaching solution;

[0064] Step 2: Prepare a first leaching solution

[0065] The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 44.26wt%, the lead content is 6.33wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the leaching is carried out at 95°C and 300rpm for 2h, and then filtered to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 44.26wt%, and the lead content is 6.33wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) 2+ The concentration is 71.87g / L, and the concentration of sulfuric acid is 43.68g / L); the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 7:1m 3 / t, acid ore ratio 1.05:1t / t, sugar ore ratio 0.14:1t / t;

[0066] Step 3: Primary leaching

[0067] The electrolytic manganese anode mud is treated at a liquid-to-solid ratio of 7:1m 3 / t was added to a first leaching solution, leached at 90 °C and 300 rpm for 2 h and filtered to obtain a leaching solution (Mn 2+ concentration is 90.83g / L, sulfuric acid concentration is 0.6g / L) and first-stage leaching residue (the manganese content in the first-stage leaching residue is 43.66wt%, and the lead content is 8.92wt%);

[0068] Step 4: Secondary leaching

[0069] The first-stage leaching residue was added to the organic acid leaching solution, leached at 90°C and 300 rpm for 2 h and filtered to obtain the second-stage leaching solution (Mn 2+ The concentration of organic acid leaching solution is 58.93g / L, the concentration of sulfuric acid is 63.27g / L) and the leaching residue (the manganese content in the leaching residue is 2.58wt%, the lead content is 33.17wt%), and the ratio of each substance in the organic acid leaching solution to the first-stage leaching residue is 7:1m 3 / t, acid ore ratio 1.05:1t / t, sugar ore ratio 0.14:1t / t;

[0070] Step 5: Adsorption

[0071] Activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45wt%, a volatile matter content of 5.50wt%, an ash content of 8.54wt%, and a moisture content of 4.51wt%) was added to the first-stage leaching solution at a solid-liquid ratio of 4:1000g / mL, and the organic matter remaining in the leaching solution was removed by adsorption at 300rpm and room temperature for 30min. 2+ The concentration is 88.32 g / L, and the sulfuric acid concentration is 0.4 g / L;

[0072] Step 6: Wash and dry

[0073] The leaching residue from the second stage leaching was added into clean water at a liquid-to-solid ratio of 6:1 g / mL and stirred at 300 rpm for 30 min to remove soluble salts such as ammonium sulfate. After drying, a lead concentrate with a manganese content of 0.87 wt% and a lead grade of 43.07 wt% was obtained.

[0074] In this embodiment, the leaching rate of manganese reaches 98.51%, the sulfuric acid concentration of the leaching solution is 0.6 g / L, the organic matter adsorption rate is greater than 90%, and the manganese recovery rate is greater than 95%.

[0075] Comparative Example 2

[0076] The configuration of the organic acid leaching solution in step 1 of this comparative example is the same as that in Example 2, except that the electrolytic manganese anode mud is subjected to one leaching. The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 44.26wt%, the lead content is 6.33wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the solution is filtered after leaching at 95°C and 300rpm for 2h to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 44.26wt%, and the lead content is 6.33wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate). 2+ concentration is 77.34g / L, sulfuric acid concentration is 62.93g / L) and leaching residue; the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 7:1m 3 / t, acid ore ratio 1.15:1t / t, sugar ore ratio 0.14:1t / t;

[0077] The first leaching solution in Comparative Example 2 was added with activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45wt%, a volatile matter content of 5.50wt%, an ash content of 8.54wt%, and a moisture content of 4.51wt%) at a solid-liquid ratio of 4:1000g / mL, and stirred at 300rpm for 30min to remove the residual organic matter in the leaching solution by adsorption. 2+ The concentration is 75.93 g / L, and the sulfuric acid concentration is 62.05 g / L;

[0078] In this comparative example, the leaching rate of manganese reached 97.64%, the sulfuric acid concentration of the leaching solution was 62.93 g / L, the organic matter adsorption rate was 58.69%, and the manganese recovery rate was 98.17%.

[0079] From the method of the present invention and the comparative example, after the two-stage countercurrent leaching of the present invention, the usage of 0.1 t / t sulfuric acid is reduced, the adsorption rate of organic matter is significantly improved, and the sulfuric acid concentration in the leaching solution of the present invention is controlled below 2 g / L.

[0080] Example 3

[0081] like Figure 1 As shown, the method for separating and recovering manganese and lead in electrolytic manganese anode mud comprises the following specific steps:

[0082] Step 1: Prepare organic acid leaching solution

[0083] Add sulfuric acid (industrial sulfuric acid with a purity of more than 93 wt%) and glucose (food grade glucose monohydrate) to the electrolytic manganese anolyte (sulfuric acid content of electrolytic manganese anolyte 45.2 g / L, Mn 2+ content of 14.3 g / L and ammonium sulfate content of 100 g / L), and after being stirred evenly, heated to 90° C. to obtain an organic acid leaching solution;

[0084] Step 2: Prepare a first leaching solution

[0085] The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 42.57wt%, the lead content is 6.88wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the leaching is carried out at 90°C and 300rpm for 2h, and then filtered to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 42.57wt%, and the lead content is 6.88wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) 2+ The concentration is 62.95g / L, and the concentration of sulfuric acid is 44.51g / L); the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 7:1m 3 / t, acid ore ratio 1.0:1t / t, sugar ore ratio 0.15:1t / t;

[0086] Step 3: Primary leaching

[0087] The electrolytic manganese anode mud is treated at a liquid-to-solid ratio of 7:1m 3 / t was added to a first leaching solution, leached at 90 °C and 300 rpm for 2 h and filtered to obtain a leaching solution (Mn 2+ concentration is 81.19g / L, sulfuric acid concentration is 1.94g / L) and first-stage leaching residue (the manganese content in the first-stage leaching residue is 43.57wt%, and the lead content is 10.04wt%);

[0088] Step 4: Secondary leaching

[0089] The first-stage leaching residue was added to the organic acid leaching solution, leached at 90°C and 300 rpm for 2 h and filtered to obtain the second-stage leaching solution (Mn 2+ The concentration of organic acid leaching solution is 56.31g / L, the concentration of sulfuric acid is 60.84g / L) and the leaching residue (the manganese content in the leaching residue is 1.43wt%, the lead content is 35.72wt%), and the ratio of each substance in the organic acid leaching solution to the first-stage leaching residue is 7:1m 3 / t, acid ore ratio 1.0:1t / t, sugar ore ratio 0.15:1t / t;

[0090] Step 5: Adsorption

[0091] Activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45 wt%, a volatile matter content of 5.50 wt%, an ash content of 8.54 wt%, and a moisture content of 4.51 wt%) was added to the first-stage leaching solution at a solid-liquid ratio of 5:1000 g / mL, and the organic matter remaining in the leaching solution was removed by adsorption at 300 rpm and room temperature for 30 min. 2+ The concentration is 79.85 g / L, and the sulfuric acid concentration is 1.2 g / L;

[0092] Step 6: Wash and dry

[0093] The leaching residue from the second stage leaching was added into clean water at a liquid-to-solid ratio of 4:1 g / mL and stirred at 300 rpm for 30 min to remove soluble salts such as ammonium sulfate. After drying, a lead concentrate with a manganese content of 0.74 wt% and a lead grade of 47.02 wt% was obtained.

[0094] In this embodiment, the leaching rate of manganese reaches 99.1%, the sulfuric acid concentration of the leaching solution is 1.94 g / L, the organic matter adsorption rate is greater than 90%, and the manganese recovery rate during the adsorption process is greater than 95%.

[0095] Comparative Example 3

[0096] The configuration of the organic acid leaching solution in step 1 of this comparative example is the same as that in Example 3, except that the electrolytic manganese anode mud is subjected to one leaching. The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 42.57wt%, the lead content is 6.88wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the solution is filtered after leaching at 90°C and 300rpm for 2h to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 42.57wt%, and the lead content is 6.88wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate). 2+ concentration is 73.44g / L, sulfuric acid concentration is 40.32g / L) and leaching residue; the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 7:1m 3 / t, acid ore ratio 1.2:1t / t, sugar ore ratio 0.16:1t / t;

[0097] The first leaching solution in Comparative Example 3 was added with activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45wt%, a volatile matter content of 5.50wt%, an ash content of 8.54wt%, and a moisture content of 4.51wt%) at a solid-liquid ratio of 5:1000g / mL, and stirred at 300rpm for 30min to remove the residual organic matter in the leaching solution by adsorption. 2+ concentration 71.82g / L, sulfuric acid concentration 40.17g / L;

[0098] In this embodiment, the leaching rate of manganese reached 97.24%, the sulfuric acid concentration of the leaching solution was 40.32 g / L, the organic matter adsorption rate was 74.33%, and the manganese recovery rate was 97.8%.

[0099] From the method of the present invention and the comparative example, after the two-stage countercurrent leaching of the present invention, the usage of sulfuric acid is reduced by 0.2 t / t, the adsorption rate of organic matter is significantly improved, and the sulfuric acid concentration in the leaching solution of the present invention is controlled below 2 g / L.

[0100] Example 4

[0101] like Figure 1 As shown, the method for separating and recovering manganese and lead in electrolytic manganese anode mud comprises the following specific steps:

[0102] Step 1: Prepare organic acid leaching solution

[0103] Add sulfuric acid (industrial sulfuric acid with a purity of more than 93 wt%) and glucose (food grade glucose monohydrate) to the electrolytic manganese anolyte (sulfuric acid content of electrolytic manganese anolyte 45.2 g / L, Mn 2+ content of 18 g / L and ammonium sulfate content of 100 g / L), and after being stirred evenly, heated to 95° C. to obtain an organic acid leaching solution;

[0104] Step 2: Prepare a first leaching solution

[0105] The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 43.69wt%, the lead content is 6.51wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the leaching is carried out at 95°C and 300rpm for 2h, and then filtered to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 43.69wt%, and the lead content is 6.51wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) 2+ The concentration is 73.79g / L, and the concentration of sulfuric acid is 32.84g / L); the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 6.5:1m 3 / t, acid ore ratio 0.9:1t / t, sugar ore ratio 0.17:1t / t;

[0106] Step 3: Primary leaching

[0107] The electrolytic manganese anode mud is treated at a liquid-to-solid ratio of 6.5:1m 3 / t was added to a first leaching solution, leached at 95°C and 300 rpm for 2 h and filtered to obtain a leaching solution (Mn 2+ concentration is 93.95g / L, sulfuric acid concentration is 0.3g / L) and first-stage leaching residue (the manganese content in the first-stage leaching residue is 45.08wt%, and the lead content is 9.72wt%);

[0108] Step 4: Secondary leaching

[0109] The first-stage leaching residue was added to the organic acid leaching solution, leached at 90°C and 300 rpm for 2 h and filtered to obtain the second-stage leaching solution (Mn 2+ The concentration of organic acid leaching solution is 63.71g / L, the concentration of sulfuric acid is 62.57g / L) and the leaching residue (the manganese content in the leaching residue is 3.77wt%, the lead content is 34.26wt%), and the ratio of each substance in the organic acid leaching solution to the first-stage leaching residue is 6.5:1m 3 / t, acid ore ratio 0.9:1t / t, sugar ore ratio 0.17:1t / t;

[0110] Step 5: Adsorption

[0111] Activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45 wt%, a volatile matter content of 5.50 wt%, an ash content of 8.54 wt%, and a moisture content of 4.51 wt%) was added to the first-stage leaching solution at a solid-liquid ratio of 6:1000 g / mL, and the organic matter remaining in the leaching solution was adsorbed and removed at 300 rpm and room temperature for 30 min. 2+ The concentration is 92.03 g / L, and the sulfuric acid concentration is 0.1 g / L;

[0112] Step 6: Wash and dry

[0113] The leaching residue from the second stage leaching was added into clean water at a liquid-to-solid ratio of 5:1 g / mL and stirred at 300 rpm for 30 min to remove soluble salts such as ammonium sulfate. After drying, a lead concentrate with a manganese content of 2.06 wt% and a lead grade of 44.32 wt% was obtained.

[0114] In this embodiment, the leaching rate of manganese reaches 97.99%, the sulfuric acid concentration of the leaching solution is 0.3 g / L, the organic matter adsorption rate is greater than 90%, and the manganese recovery rate during the adsorption process is greater than 95%.

[0115] Comparative Example 4

[0116] The configuration of the organic acid leaching solution in step 1 of this comparative example is the same as that in Example 4, except that the electrolytic manganese anode mud is subjected to one leaching. The electrolytic manganese anode mud (the manganese content in the electrolytic manganese anode mud is 43.69wt%, the lead content is 6.51wt%; the manganese phase is mainly manganese dioxide, and the lead phase is mainly lead sulfate) is added to the organic acid leaching solution, and the solution is filtered after leaching at 95°C and 300rpm for 2h to obtain a first-stage leaching solution (the Mn content in the first-stage leaching solution is 1.37wt%). 2+ concentration is 82.74g / L, sulfuric acid concentration is 48.62g / L) and leaching residue; the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 6.5:1m 3 / t, acid ore ratio 1.15:1t / t, sugar ore ratio 0.17:1t / t;

[0117] The first leaching solution in Comparative Example 4 was added with activated carbon (high-quality coconut shell activated carbon, with a fixed carbon content of 81.45wt%, a volatile matter content of 5.50wt%, an ash content of 8.54wt%, and a moisture content of 4.51wt%) at a solid-liquid ratio of 6:1000g / mL, and stirred at 300rpm for 30min to remove the residual organic matter in the leaching solution. After adsorption, the Mn content in the leaching solution was 2+ The concentration is 81.49 g / L, and the sulfuric acid concentration is 47.96 g / L;

[0118] In this comparative example, the leaching rate of manganese reached 96.33%, the sulfuric acid concentration of the leaching solution was 48.62 g / L, the organic matter adsorption rate was 68.94%, and the manganese recovery rate during the adsorption process was 98.5%.

[0119] From the method of the present invention and the comparative example, after the two-stage countercurrent leaching of the present invention, the usage of 0.1 t / t sulfuric acid is reduced, the adsorption rate of organic matter is significantly improved, and the sulfuric acid concentration in the leaching solution of the present invention is controlled below 2 g / L.

[0120] The specific implementation modes of the present invention are described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above implementation modes, and various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. A method for separating and recovering manganese and lead in electrolytic manganese anode mud, characterized in that The specific steps include: Step 1: Prepare organic acid leaching solution Add sulfuric acid and glucose to the electrolytic manganese anode solution, stir evenly and heat to 90-95°C to obtain an organic acid leaching solution; Step 2: Prepare a first leaching solution The electrolytic manganese anode mud is added to the organic acid leaching solution, and the solution is filtered after leaching at 90-95°C and 300 rpm for 2 hours to obtain a leaching solution; wherein the ratio of each substance in the organic acid leaching solution to the electrolytic manganese anode mud is 6.5-7:1m / s respectively. 3 / t, acid-ore ratio 0.9-1.25:1t / t, sugar-ore ratio 0.13-0.17:1t / t; Step 3: Primary leaching The electrolytic manganese anode mud is treated at a liquid-to-solid ratio of 6.5-7:1m 3 / t was added into the first-stage leaching solution, leached at 90-95°C and 300rpm for 2h and filtered to obtain the leaching solution and the first-stage leaching residue; Step 4: Secondary leaching The first-stage leaching residue is added to the organic acid leaching solution, leached at 90-95°C and 300rpm for 2h and filtered to obtain the second-stage leaching solution and leaching residue, wherein the ratio of each substance in the organic acid leaching solution to the first-stage leaching residue is 6.5-7:1m / s respectively. 3 / t, acid-ore ratio 0.9-1.25:1t / t, sugar-ore ratio 0.13-0.17:1t / t; Step 5: Adsorption Add activated carbon to the leachate of the first stage leaching at a solid-liquid ratio of 3-6:1000 g / mL, and stir at 300 rpm for 30 minutes at room temperature to adsorb and remove residual organic matter in the leachate; Step 6: Wash and dry The leaching residue from the second stage leaching is added into clean water at a liquid-solid ratio of 4-6:1 g / mL and stirred at 300 rpm for 30 minutes to remove the soluble salt of ammonium sulfate by elution, and a lead concentrate with a lead grade of 40wt%-50wt% is obtained after drying.

2. The method for separating and recovering manganese and lead in electrolytic manganese anode mud according to claim 1, characterized in that: In step 1, industrial sulfuric acid with a purity of more than 93 wt% is used, glucose is food grade glucose monohydrate, and the sulfuric acid content of electrolytic manganese anolyte is 40-45 g / L, Mn 2+ Content 14-22g / L, ammonium sulfate content 90-100g / L.

3. The method for separating and recovering manganese and lead in electrolytic manganese anode mud according to claim 1, characterized in that: In step 2, the manganese content in the electrolytic manganese anode mud is 40wt%-45wt%, and the lead content is 4wt%-8wt%; the physical phase of manganese is mainly manganese dioxide, and the physical phase of lead is mainly lead sulfate.

4. The method for separating and recovering manganese and lead in electrolytic manganese anode mud according to claim 1, characterized in that: In step 4, the second stage leaching solution is added to the first stage leaching solution to carry out the first stage leaching of step 3.

5. The method for separating and recovering manganese and lead in electrolytic manganese anode mud according to claim 1, characterized in that: The activated carbon in step 5 is high-quality coconut shell activated carbon, wherein the fixed carbon content is 81.45wt%, the volatile matter content is 5.50wt%, the ash content is 8.54wt%, and the moisture content is 4.51wt%.

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