A method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials

Abstract

This invention belongs to the field of solid waste treatment technology, specifically a method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials. It fully utilizes the environmental resource interaction attributes of aluminum electrolysis waste refractory materials and electrolytic manganese slag, and achieves the tiered recycling of all components through a combination of green and low-cost agents and simple processes. While achieving efficient detoxification, it also generates a variety of high-value products. Moreover, the entire co-processing process is simple and generates no secondary pollutants, resulting in significant environmental and economic benefits and broad market prospects.

Description

Technical Field

[0001] This invention relates to the field of solid waste treatment technology, specifically to a method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials. Background Technology

[0002] Currently, the production of 1 ton of metallic manganese generates 8-12 tons of electrolytic manganese slag. Electrolytic manganese slag contains significant amounts of heavy metals (Mn, Cu, Cd, Hg) and ammonia nitrogen (NH4). + -N) leaching toxicity causes serious pollution to surrounding soil, water sources, and air. Electrolytic manganese slag is mainly composed of CaSO4, SiO2, Fe2O3, and MnO, and the vast majority can only be disposed of in the building materials industry, lacking potential for high-value utilization. Domestic and international strategies for the disposal of electrolytic manganese slag can be categorized as follows:

[0003] The first disposal strategy is slag storage, which mainly involves storing electrolytic manganese slag in a dedicated area lined with impermeable materials and equipped with leachate treatment facilities. Soluble Mn is then treated using technologies such as chemical precipitation, adsorption, and electrochemical processes. 2+ and NH4 + -N, thus avoiding environmental pollution. Its disadvantages are that it occupies a large area of ​​land, the seepage prevention material is prone to soil and water pollution after corrosion, a large number of valuable materials are idle, and the resource utilization rate is low.

[0004] The second disposal strategy is stabilization and solidification, which mainly utilizes alkaline agents such as CaO, MgO, Na3PO4, and Na2CO3 to convert soluble manganese into manganese hydroxide or low-solidity manganese salts, thereby achieving stable solidification of soluble manganese and efficient removal of ammonia nitrogen. Its disadvantages are that it fails to fully utilize the high-value component Mn, and the electrolytic manganese slag still needs to be transported to a slag storage facility after disposal, thus occupying a large area of ​​land while failing to achieve large-scale disposal.

[0005] The third disposal strategy is the use of building materials. This mainly utilizes the abundant calcium sulfate dihydrate and ferrosilicon components in electrolytic manganese slag as cement admixtures and retarders, or for the preparation of non-fired cementitious materials, thereby achieving the solidification of soluble heavy metals and the release of ammonia nitrogen. Its disadvantage is that the large amount of sulfate in electrolytic manganese slag can cause efflorescence in building materials, affecting their performance, and it cannot be used in high-volume applications.

[0006] The fourth disposal strategy is the recovery of valuable components. This mainly involves using microbial methods, acid leaching, and water washing and precipitation to convert soluble manganese into manganese metal, manganese hydroxide, manganese sulfate, and other manganese-containing compounds, thereby achieving effective recovery of manganese components from electrolytic manganese slag. Its disadvantage is that the recovery process only considers the recovery of manganese components and does not involve the simultaneous utilization of other components in the electrolytic manganese slag. Furthermore, the waste gas, waste residue, and waste liquid generated during the recovery process all pose a serious risk of secondary pollution. Summary of the Invention

[0007] To address the problems existing in the prior art, the present invention aims to provide a method for the co-processing of electrolytic manganese slag from aluminum electrolysis waste refractory materials. Based on the environmental resource interaction properties of aluminum electrolysis waste refractory materials and electrolytic manganese slag, this method enables the tiered resource utilization of soluble components (sodium fluoride, manganese, and ammonia nitrogen) and aluminum-silicon-calcium components in the two solid wastes. It features low disposal costs, high product value, and a simple process.

[0008] According to one aspect of the present invention, the present invention provides the following technical solution:

[0009] A method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials includes the following steps:

[0010] S1. The waste refractory materials from aluminum electrolysis and the electrolytic manganese slag are separated by particle size refinement to obtain raw material one and raw material two to be used;

[0011] S2. Raw material 1 and raw material 2 are respectively loaded into wet leaching apparatus 1 and wet leaching apparatus 2, and leaching solution is added for wet leaching. After wet leaching is completed, leaching residue 1, leaching solution 1, leaching residue 2, and leaching solution 2 are obtained by solid-liquid separation. The leaching solution 1 contains concentrated solution 1 and dilute solution 1, and the leaching solution 2 contains concentrated solution 2 and dilute solution 2.

[0012] S3. Slowly add concentrated solution one to concentrated solution two, filter and separate to obtain metal impurities and primary filtrate, then add alkaline regulator to primary filtrate, filter and separate to obtain manganese-containing product and secondary filtrate.

[0013] S4. Add the component regulator to the secondary filtrate, filter and separate to obtain the fluorine-containing product and the tertiary filtrate, then add the acid regulator to the tertiary filtrate and obtain the ammonia-containing product by low-temperature evaporation.

[0014] S5. Mix leaching residue one and leaching residue two, then add quicklime and aluminum powder, and proceed with curing, autoclaving and shaping processes to prepare non-fired cementitious material.

[0015] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S1, the particle size distribution of raw material one and raw material two is any one or more of 3mm~1mm, 1mm~0.15mm, 0.15mm~0.074mm, and <0.074mm.

[0016] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S2, the liquid-to-solid ratio of the leaching solution to raw material one or raw material two to be used is (5~80) mL:1g.

[0017] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S2, the wet leaching temperature is 20~80℃ and the wet leaching time is 10~240min.

[0018] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S2, the leaching solution is one or more of water, hydrogen peroxide solution, and sodium hypochlorite solution.

[0019] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S2, the concentrated solution is used for high-value product extraction, and the dilute solution is recycled for the wet leaching process.

[0020] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S2, the leachate one is different fluoride-containing solutions generated after multiple leachings of aluminum electrolysis waste refractory materials. The concentration of fluoride ions in the solution is used as an evaluation index. The concentration of fluoride ions is the highest after the first leaching, which is regarded as concentrated solution one, and the subsequent leachings are regarded as dilute solution one. The concentration of fluoride ions in concentrated solution one is ≥2000mg / L; the rest are dilute solution one.

[0021] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S2, the second leaching solution is a solution with different manganese and ammonia nitrogen contents produced by multiple water leachings of electrolytic manganese slag. The concentrations of manganese and ammonia nitrogen in the solution are used as evaluation indicators. The concentrations of manganese and ammonia nitrogen are the highest after the first leaching, which is regarded as concentrated solution one, and the leaching solutions after that are regarded as dilute solution two. The manganese concentration of concentrated solution one is ≥600mg / L and the ammonia nitrogen concentration is ≥300mg / L; the rest are dilute solution two.

[0022] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S3, the volume ratio of concentrated solution one to concentrated solution two is (0.1~1):1.

[0023] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S3, the alkaline regulator is one or more of ammonia, sodium hydroxide, and sodium carbonate, and the pH value is adjusted to 8-12 by adding the alkaline regulator.

[0024] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S4, the component regulator is one or more of sodium aluminate, aluminum hydroxide, and aluminum fluoride, and the amount of component regulator added is 1 to 10 wt% of the secondary filtrate.

[0025] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S4, the acidity regulator is one or more of hydrofluoric acid, ammonium fluoride, and hydrogen fluoride, and the pH value is adjusted to 2-8 by adding the acidity regulator.

[0026] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S4, the low-temperature evaporation temperature is 30~70℃, and the water vapor is reused in the wet leaching process after condensation.

[0027] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S5, the mass ratio of leaching residue one to leaching residue two is 20:80~80:20.

[0028] As a preferred embodiment of the method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials according to the present invention, in step S5, the amount of quicklime added is 5-20 wt% of the total amount of leaching residue one and leaching residue two; the amount of aluminum powder added is 0.1-1 wt% of the total amount of leaching residue one and leaching residue two.

[0029] The beneficial effects of this invention are as follows:

[0030] This invention proposes a method for the co-processing of electrolytic manganese slag from aluminum electrolysis waste refractory materials. It fully utilizes the environmental resource interaction properties of aluminum electrolysis waste refractory materials and electrolytic manganese slag, and achieves the tiered recycling of all components through a combination of green and low-cost agents and simple processes. While achieving efficient detoxification, it also generates a variety of high-value products. Moreover, the entire co-processing process is simple and generates no secondary pollutants, resulting in significant environmental and economic benefits and broad market prospects. Detailed Implementation

[0031] The technical solutions described below in conjunction with the embodiments will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] This invention proposes a method for co-processing electrolytic manganese slag from waste aluminum electrolysis refractory materials. Based on the concept of "treating waste with waste," it utilizes the soluble components (Na, F, Mn, NH4) in waste aluminum electrolysis refractory materials and electrolytic manganese slag. + Leveraging the complementary advantages of resources (-N), and utilizing waste refractory materials from aluminum electrolysis for the co-processing of electrolytic manganese slag, the following advantages are achieved:

[0033] (1) Low-cost leaching solutions were used to perform wet leaching of waste refractory materials from aluminum electrolysis and electrolytic manganese slag, respectively, to achieve green and efficient extraction of soluble components. The dilute solution can be recycled for the wet leaching process, demonstrating significant sustainability advantages. Among them, toxic soluble components F, Mn, and NH4 were extracted. + The leaching rate of -N is ≥99.0%.

[0034] (2) The large amount of soluble fluorine in the leaching solution of aluminum electrolytic waste refractory materials is used to remove Ca and Mg in the leaching solution of electrolytic manganese slag and form CaF2 and MgF2 products, which can be used as additives for the production of electrolytic aluminum for resource utilization. While the metal impurities are targeted to be productized, some soluble fluorides are safely solidified. The removal rates of Ca and Mg are both ≥99.5%.

[0035] (3) By adding an alkaline regulator, both pH regulation and component replenishment (NH4) can be achieved simultaneously. + The extraction of soluble manganese (Mn) can be converted into high-value product one (manganese tetroxide or manganese hydroxide), which has significant economic value. At the same time, it can provide a basis for the subsequent extraction of high-value products two and three, with the extraction rate of Mn ≥ 99.0%.

[0036] (4) By further adjusting the ionic composition of the solution with a preferred aluminum-containing regulator, Na, Al and environmentally unfriendly fluorides were successfully converted into high-value product II (cryolite), avoiding the risk of environmental pollution. The extraction rates of Na and Al were both ≥98.0%.

[0037] (5) Based on the ionic composition of the remaining solution (NH4) + By combining acid-base regulation with low-temperature evaporation, a high-value product (ammonia fluoride) was successfully prepared, thus realizing the high-value utilization of toxic components ammonia nitrogen and fluorine. The water vapor can be recycled for wet leaching after condensation, thereby saving the disposal cost of wet leaching. The purity of the ammonia fluoride product is ≥98.0%.

[0038] (6) Based on the abundant cementing components (alumina and silicon dioxide) in the leaching residue of aluminum electrolytic waste refractory materials and the abundant retarding components (CaSO4) and cementing components (SiO2) in the leaching residue of electrolytic manganese slag, the two leaching residues are innovatively used to prepare non-fired cementitious materials, thereby realizing the synergistic resource utilization of all components of aluminum electrolytic waste refractory materials and electrolytic manganese slag. The compressive strength of the prepared non-fired cementitious materials is ≥3.5MPa.

[0039] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0040] Example 1

[0041] A method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials includes the following steps:

[0042] S1. The waste refractory materials from aluminum electrolysis and the electrolytic manganese slag are separated by particle size refinement to obtain raw material one and raw material two with a particle size distribution of <0.074mm.

[0043] S2. Raw material 1 and raw material 2 are respectively loaded into wet leaching apparatus 1 and wet leaching apparatus 2. Water is added at liquid-to-solid ratios of 40:1 and 20:1, respectively. The reaction temperatures are 80℃ and 60℃, and the reaction times are 60 min and 30 min, respectively. After wet leaching, leaching residue 1, leaching solution 1, leaching residue 2, and leaching solution 2 are obtained through solid-liquid separation. The concentrated solution is used for high-value product extraction, and the dilute solution is recycled for the wet leaching process. F, Mn, NH4 + The leaching rates of -N were 99.85%, 99.78%, and 99.82%, respectively.

[0044] S3. Slowly add concentrated solution one to concentrated solution two at a volume ratio of 0.5:1. Separate the metal impurities and the primary filtrate by filtration. Then add ammonia water to the primary filtrate to make the pH value 11, and separate the manganese-containing product and the secondary filtrate by filtration. The removal rates of Ca and Mg are 99.86% and 99.91%, respectively, and the extraction rate of Mn is 99.90%.

[0045] S4. Sodium aluminate was added to the secondary filtrate at a mass ratio of 5 wt%. The fluorine-containing product and the tertiary filtrate were separated by filtration. Hydrofluoric acid was then added to the tertiary filtrate to a pH of 3. The ammonia-containing product was obtained by low-temperature evaporation at 60°C. The water vapor was condensed and reused in the wet leaching process. The extraction rates of Na and Al were 99.20% and 99.15%, respectively, and the purity of the hydrogen fluoride ammonia product was 98.91%.

[0046] S5. Leaching residue one and leaching residue two are uniformly mixed at a mass ratio of 80:20. Then, 15wt% quicklime and 0.1wt% aluminum powder are added. The mixture is then subjected to curing, autoclaving, and shaping processes to prepare a non-fired cementitious material. The compressive strength of the prepared non-fired cementitious material is 4.5MPa.

[0047] Example 2

[0048] A method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials includes the following steps:

[0049] S1. The waste refractory materials from aluminum electrolysis and the electrolytic manganese slag are separated by particle size refinement to obtain raw material one and raw material two with a particle size distribution of 0.15mm~0.074mm.

[0050] S2. Raw material 1 and raw material 2 are respectively loaded into wet leaching apparatus 1 and wet leaching apparatus 2. Aqueous solutions are added at liquid-to-solid ratios of 50:1 and 25:1, respectively. The reaction temperatures are 70℃ and 60℃, and the reaction times are 60 min and 60 min, respectively. After wet leaching, leaching residue 1, leaching solution 1, leaching residue 2, and leaching solution 2 are obtained through solid-liquid separation. The concentrated solution is used for high-value product extraction, and the dilute solution is recycled for the wet leaching process. F, Mn, NH4 + The leaching rates of -N were 99.80%, 99.72%, and 99.79%, respectively.

[0051] S3. Slowly add concentrated solution one to concentrated solution two at a volume ratio of 0.4:1. Separate the metal impurities and the primary filtrate by filtration. Then add ammonia water to the primary filtrate to make the pH value 12, and separate the manganese-containing product and the secondary filtrate by filtration. The removal rates of Ca and Mg are 99.74% and 99.84%, respectively, and the extraction rate of Mn is 99.81%.

[0052] S4. Sodium aluminate was added to the secondary filtrate at a mass ratio of 4.5 wt%. The fluorine-containing product and the tertiary filtrate were separated by filtration. Hydrofluoric acid was then added to the tertiary filtrate to a pH of 3.5. The ammonia-containing product was obtained by low-temperature evaporation at 50°C. The steam was condensed and reused in the wet leaching process. The extraction rates of Na and Al were 99.12% and 99.04%, respectively, and the purity of the hydrogen fluoride ammonia product was 98.85%.

[0053] S5. Leaching residue one and leaching residue two are uniformly mixed at a mass ratio of 70:30. Then, 15 wt% quicklime and 0.1 wt% aluminum powder are added. The mixture is then subjected to curing, autoclaving, and shaping processes to prepare a non-fired cementitious material. The compressive strength of the prepared non-fired cementitious material is 4.1 MPa.

[0054] Example 3

[0055] A method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials includes the following steps:

[0056] S1. The waste refractory materials from aluminum electrolysis and the electrolytic manganese slag are separated by particle size refinement to obtain raw material 1 and raw material 2 with a particle size distribution of 1mm~0.15mm.

[0057] S2. Raw material 1 and raw material 2 are respectively loaded into wet leaching apparatus 1 and wet leaching apparatus 2. Aqueous solutions are added at liquid-to-solid ratios of 30:1 and 15:1, respectively. The reaction temperatures are 60℃ and 60℃, and the reaction times are 30 min and 30 min, respectively. After wet leaching, leaching residue 1, leaching solution 1, leaching residue 2, and leaching solution 2 are obtained through solid-liquid separation. The concentrated solution is used for high-value product extraction, and the dilute solution is recycled for the wet leaching process. F, Mn, NH4 + The leaching rates of -N were 99.08%, 99.12%, and 99.09%, respectively.

[0058] S3. Slowly add concentrated solution one to concentrated solution two at a volume ratio of 0.6:1. Separate the metal impurities and the primary filtrate by filtration. Then add ammonia water to the primary filtrate to make the pH value 11.5, and separate the manganese-containing product and the secondary filtrate by filtration. The removal rates of Ca and Mg are 99.51% and 99.57%, respectively, and the extraction rate of Mn is 99.12%.

[0059] S4. Sodium aluminate was added to the secondary filtrate at a mass ratio of 5 wt%. The fluorine-containing product and the tertiary filtrate were separated by filtration. Hydrofluoric acid was then added to the tertiary filtrate to a pH of 5.5. The ammonia-containing product was obtained by low-temperature evaporation at 60°C. The water vapor was condensed and reused in the wet leaching process. The extraction rates of Na and Al were 98.23% and 98.12%, respectively, and the purity of the hydrogen fluoride ammonia product was 98.08%.

[0060] S5. Leaching residue one and leaching residue two are uniformly mixed at a mass ratio of 60:40. Then, 15wt% quicklime and 0.1wt% aluminum powder are added. The mixture is then subjected to curing, autoclaving, and shaping processes to prepare a non-fired cementitious material. The compressive strength of the prepared non-fired cementitious material is 3.55MPa.

[0061] Example 4

[0062] A method for co-processing electrolytic manganese slag from aluminum electrolysis waste refractory materials includes the following steps:

[0063] S1. The waste refractory materials from aluminum electrolysis and the electrolytic manganese slag are separated by particle size refinement to obtain raw material one and raw material two with a particle size distribution of 0.15mm~0.074mm.

[0064] S2. Raw material 1 and raw material 2 are respectively loaded into wet leaching apparatus 1 and wet leaching apparatus 2. Aqueous solutions are added at liquid-to-solid ratios of 80:1 and 25:1, respectively. The reaction temperatures are 70℃ and 70℃, and the reaction times are 90 min and 60 min, respectively. After wet leaching, leaching residue 1, leaching solution 1, leaching residue 2, and leaching solution 2 are obtained through solid-liquid separation. The concentrated solution is used for high-value product extraction, and the dilute solution is recycled for the wet leaching process. F, Mn, NH4 + The leaching rates of -N were 99.81%, 99.70%, and 99.69%, respectively.

[0065] S3. Slowly add concentrated solution one to concentrated solution two at a volume ratio of 0.5:1. Separate the metal impurities and the primary filtrate by filtration. Then add ammonia water to the primary filtrate to make the pH value 11, and separate the manganese-containing product and the secondary filtrate by filtration. The removal rates of Ca and Mg are 99.77% and 99.82%, respectively, and the extraction rate of Mn is 99.79%.

[0066] S4. Sodium aluminate was added to the secondary filtrate at a mass ratio of 4 wt%. The fluorine-containing product and the tertiary filtrate were separated by filtration. Hydrofluoric acid was then added to the tertiary filtrate to a pH of 3.5. The ammonia-containing product was obtained by low-temperature evaporation at 50°C. The water vapor was condensed and reused in the wet leaching process. The extraction rates of Na and Al were 99.03% and 98.88%, respectively, and the purity of the hydrogen fluoride ammonia product was 98.76%.

[0067] S5. Leaching residue one and leaching residue two are uniformly mixed at a mass ratio of 75:25. Then, 15wt% quicklime and 0.1wt% aluminum powder are added. The mixture is then subjected to curing, autoclaving, and shaping processes to prepare a non-fired cementitious material. The compressive strength of the prepared non-fired cementitious material is 4.30 MPa.

[0068] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for co-disposal of aluminum electrolytic spent refractory material with electrolytic manganese residue, characterized in that, The method comprises the following steps: S1, respectively refining and sorting the aluminum electrolysis waste refractory material and the electrolytic manganese residue to obtain raw material one and raw material two; S2, loading the raw material one and the raw material two into a wet leaching device one and a wet leaching device two respectively, adding a leaching solution to carry out wet leaching, and after the wet leaching is completed, obtaining leaching residue one, leaching solution one, leaching residue two and leaching solution two through solid-liquid separation; the leaching solution one comprises concentrated solution one and dilute solution one, and the leaching solution two comprises concentrated solution two and dilute solution two; S3, slowly adding the concentrated solution one into the concentrated solution two to obtain metal impurities and primary filtrate through filtration separation, then adding an alkaline control agent into the primary filtrate to obtain a manganese-containing product and secondary filtrate through filtration separation; S4, adding a component control agent into the secondary filtrate to obtain a fluorine-containing product and tertiary filtrate through filtration separation, then adding an acid control agent into the tertiary filtrate to obtain an ammonia-containing product through low-temperature evaporation; S5, mixing the leaching residue one and the leaching residue two, then adding quicklime and aluminum powder, and sequentially carrying out curing, steam pressure and shaping processes to prepare a non-burning cementitious material.

2. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis according to claim 1, characterized in that, In the step S2, the liquid-solid ratio of the leaching solution to the raw material one or the raw material two is (5-80) mL:1 g.

3. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis according to claim 1, characterized in that, In the step S2, the wet leaching temperature is 20-80 DEG C, and the wet leaching time is 10-240 min; the leaching solution is one or more of water, hydrogen peroxide solution and sodium hypochlorite solution.

4. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis according to claim 1, characterized in that, In the step S3, the volume ratio of the concentrated solution one to the concentrated solution two is (0.1-1):

1.

5. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis according to claim 1, characterized in that, In the step S3, the alkaline control agent is one or more of ammonia, sodium hydroxide and sodium carbonate, and the pH value is adjusted to 8-12 by adding the alkaline control agent.

6. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis of claim 1, wherein, In the step S4, the component control agent is one or more of sodium metaaluminate, aluminum hydroxide and aluminum fluoride, and the addition amount of the component control agent is 1-10 wt% of the secondary filtrate.

7. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis according to claim 1, characterized in that, In the step S4, the acid control agent is one or more of hydrofluoric acid, ammonium fluoride and hydrogen fluoride, and the pH value is adjusted to 2-8 by adding the acid control agent.

8. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis of claim 1, wherein, In the step S4, the low-temperature evaporation temperature is 30-70 DEG C, and the water vapor is reused in the wet leaching process after being condensed.

9. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis of claim 1, wherein, In the step S5, the mass ratio of the leaching residue one to the leaching residue two is 20:80-80:

20.

10. The method of co-processing electrolytic manganese residue with spent refractories from aluminum electrolysis of claim 1, wherein, In the step S5, the addition amount of the quicklime is 5-20 wt% of the total amount of the leaching residue one and the leaching residue two, and the addition amount of the aluminum powder is 0.1-1 wt% of the total amount of the leaching residue one and the leaching residue two.