Reaction device for recycling electrolytic manganese metal electrolysis waste residues

Abstract

The utility model discloses an electrolytic manganese metal electrolysis waste residue recycling reaction device which comprises a reaction barrel, a stirrer is arranged in the reaction barrel, a discharging pipeline is arranged at the bottom of the reaction barrel, a discharging valve is installed on the discharging pipeline, a feeding hopper is installed at a feeding port of the reaction barrel through a valve body, a screening machine is arranged on one side of the feeding hopper, and a discharging valve is installed on the screening machine. Waste residues screened out by the screening machine are fed into the feeding hopper, and the feeding hopper feeds the waste residues into the feeding hopper through the elevator. According to the reaction device and method for recycling the electrolytic manganese metal electrolysis waste residues, the waste residues are ground and screened, so that the waste residues entering the reaction barrel are smaller than 100 meshes, the waste residues can be reacted through the reaction barrel, and meanwhile the defects that the waste residues are accumulated, blocked and abraded in the reaction barrel and the reaction is uneven and incomplete can be overcome; hydrogen is independently recovered and treated, and an anti-static tail gas treatment tower is arranged to treat hydrogen-containing tail gas, so that the production safety is improved.

Description

Technical Field

[0001] The utility model relates to the technical field of metal manganese production, in particular to a recycling reaction device and a recycling method for electrolytic waste slag of electrolytic metal manganese. Background Art

[0002] Manganese metal production is a typical hydrometallurgical industry. The waste slag produced during the electrolytic production process is called electrolytic waste slag. Since there has been no effective treatment method, most domestic electrolytic manganese companies choose to transport the waste slag to the yard and build dams for storage. This method occupies a large amount of land resources. At the same time, high-concentration wastewater leaching will cause heavy metal pollution in the soil and soil compaction. Under leaching and rainwater leaching, it will also cause excessive ammonia nitrogen in the surface water, endangering the safety of the surrounding environment.

[0003] Therefore, the reasonable and effective treatment of electrolytic waste slag, minimizing the hazards of manganese waste slag, and utilizing the waste slag as a resource have become bottleneck problems that need to be urgently solved in the electrolytic manganese industry. Due to the unsuitability of reaction equipment, the electrolytic waste slag contains impurities and large particles. When put into existing reaction equipment, not only will the reaction be incomplete due to the difference in waste slag size, but it will also cause a large impact during the equipment stirring process, shortening the equipment life. The tail gas and hydrogen generated in the production process cannot be safely and recyclably treated, and this application is proposed for this purpose. Utility Model Content

[0004] The utility model aims to provide a reaction device for recycling electrolytic manganese electrolytic waste slag to solve the problems raised in the above background technology.

[0005] In order to achieve the above purpose, the utility model provides the following technical solutions:

[0006] A reaction device for recycling electrolytic manganese electrolytic waste residue comprises a reaction barrel, an agitator is arranged inside the reaction barrel, a discharge pipeline is arranged at the bottom of the reaction barrel, a discharge valve is installed on the discharge pipeline, a feed hopper is installed at the feed inlet of the reaction barrel through a valve body, a screening machine is arranged on one side of the feed hopper, the waste residue screened by the screening machine is sent to an upper hopper, and the upper hopper sends the waste residue into the feed hopper through a hoist.

[0007] As a further solution of the utility model: the screen of the screening machine is 100 mesh, the waste residue passing through the 100 mesh screen enters the feed hopper, and the filtered waste residue is sent back to the previous grinding process.

[0008] As a further solution of the utility model: the feed hopper is fed into the reaction barrel through a valve body, and after the waste residue is fed, the valve body is closed to prevent gas leakage.

[0009] As a further solution of the utility model: a water inlet pipeline, an additive pipeline, an exhaust gas pipeline and an air blowing pipeline are arranged on the top of the reaction barrel, and the output end of the air blowing pipeline is connected to a low blow pipe extending into the interior of the reaction barrel.

[0010] As a further solution of the utility model: the output end of the low blow pipe is lower than the liquid level of the reaction material in the reaction barrel, and an air valve and a compressor are installed on the air blowing pipeline.

[0011] As a further solution of the utility model: the water inlet pipeline, additive pipeline, tail gas pipeline and air blowing pipeline are all provided with valves to control the flow of fluid inside the pipeline.

[0012] As a further solution of the utility model: the output end of the tail gas pipeline is connected to two branch pipes, and the two branch pipes are respectively a combustion-supporting pipeline and a tail gas treatment tower pipeline.

[0013] Compared with the prior art, the beneficial effects of the utility model are:

[0014] The electrolytic manganese electrolytic waste slag recycling reaction device and method thereof grind and screen the waste slag to make the waste slag entering the reaction barrel below 100 meshes, which not only enables the waste slag to pass through the reaction barrel, but also avoids the defects of waste slag accumulation, blockage, wear and uneven and incomplete reaction inside the reaction barrel. By adding an air inlet pipe, hydrogen is separately recovered and processed, and an anti-static tail gas treatment tower is set to process hydrogen-containing tail gas, thereby improving production safety. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a structural schematic diagram of a reaction device for recycling electrolytic manganese electrolytic waste residue;

[0016] Figure 2 It is a schematic diagram of the installation of a reaction barrel in a reaction device for recycling electrolytic waste slag of electrolytic manganese metal;

[0017] Figure 3 A three-dimensional diagram of a reaction barrel in a reaction device for recycling electrolytic manganese electrolytic waste residue;

[0018] Figure 4 The present invention is a schematic diagram of the structure of a reaction barrel in a reaction device for recycling electrolytic manganese electrolytic waste slag.

[0019] In the figure: 1. reaction barrel; 2. valve body; 3. feed hopper; 4. elevator; 5. upper hopper; 6. screening machine; 7. agitator; 8. discharge valve; 9. discharge pipeline; 10. air valve; 11. low blow pipe; 12. air blowing pipeline; 13. compressor; 14. exhaust gas pipeline; 15. additive pipeline; 16. water inlet pipeline. DETAILED DESCRIPTION

[0020] See also Figures 1 to 4 In the embodiment of the utility model, a reaction device for recycling electrolytic manganese electrolytic waste residue comprises a reaction barrel 1, a stirrer 7 is arranged inside the reaction barrel 1, a feeding pipeline 9 is arranged at the bottom of the reaction barrel 1, a feeding valve 8 is installed on the feeding pipeline 9, a feeding hopper 3 is installed at the feeding port of the reaction barrel 1 through a valve body 2, after the waste residue is fed, the valve body 2 is closed to prevent gas leakage, a screening machine 6 is arranged on one side of the feeding hopper 3, the waste residue screened by the screening machine 6 is sent to the upper hopper 5, and the upper hopper 5 sends the waste residue to the feeding hopper 3 through the elevator 4, the chemical reaction and physical reaction container of the reaction barrel 1, and a stirring device is arranged inside the reaction barrel 1. 7, so large particles of waste slag will not only cause internal wear of the reaction barrel 1 and the agitator 7, but also reduce the stirring efficiency. Therefore, the waste slag is dried and preliminarily screened to remove a part of the complex salt crystal blocks and large foreign impurities, and then ground using the existing grinding equipment to break it into small particles, which are screened below 100 meshes on the screening machine 6 and fed into the reaction barrel 1 through the feed hopper 3. This can not only reduce the particle size of the waste slag, but also reduce the wear on the equipment, increase the contact between the reaction liquid and the waste slag, and improve the reaction rate, so that the waste slag will not cause incomplete reaction and partial unreacted due to the particle size.

[0021] As a further solution of the utility model: the top of the reaction barrel 1 is provided with a water inlet pipeline 16, an additive pipeline 15, an exhaust gas pipeline 14 and an air blast pipeline 12, the output end of the air blast pipeline 12 is connected to a low blow pipe 11 extending inside the reaction barrel 1, the output end of the low blow pipe 11 is lower than the liquid level of the reaction material in the reaction barrel 1, the air valve 10 and the compressor 13 are installed on the air blast pipeline 12, the water inlet pipeline 16, the additive pipeline 15, the exhaust gas pipeline 14 and the air blast pipeline 12 are all provided with valves to control the flow rate of the fluid inside the pipeline, and the reaction of electrolytic waste slag pulping is shown in H 2 O 2 Reduction of Mn 4+ At the same time, oxygen is released. If there is single Mn, single Mn and H in the electrolytic waste slag, + Reaction, hydrogen is produced during the reaction, and hydrogen is discharged together with the tail gas, which poses a safety hazard. Therefore, during the reaction, the equipment is kept closed within the pressure range of the reaction barrel 1. After the reaction is completed, the hydrogen and the tail gas are separated, and air is injected through the low blow pipe 11, and the hydrogen with low density is sent out through the tail gas pipeline 14. The output end of the tail gas pipeline 14 is connected to two branch pipes, which are a combustion-supporting pipeline and a tail gas treatment tower pipeline respectively. The tail gas pipeline 14 is connected to two conveying pipelines, which are a pipeline for furnace body combustion-supporting and a pipeline for tail gas treatment respectively. After the low blow pipe 11 is injected with air, the tail gas with high hydrogen content is sent into the furnace body through the furnace body combustion-supporting pipeline through valve control for combustion-supporting. The remaining hydrogen content is low, and the tail gas with low recovery value is sent to the tail gas treatment tower through the tail gas treatment. The tail gas treatment tower should have anti-static measures.

[0022] A method for recycling electrolytic manganese electrolytic waste slag, using an electrolytic manganese electrolytic waste slag recycling reaction device to recover electrolytic manganese electrolytic waste slag, specifically comprising the following steps:

[0023] S1: After the waste residue is dried, it is screened for the first time to remove part of the double salt crystal blocks and large foreign impurities, and then crushed and ground for the second time to less than 100 mesh;

[0024] S2: Use the existing anolyte to carry out primary acid leaching on the electrolytic waste residue to oxidize the Mn in the waste residue into Mn2+, and then add concentrated sulfuric acid for secondary acid leaching to maximize the leaching of Mn0 and Mn2O3 in the waste residue into Mn2+. Under the conditions of acid leaching, Mn4+ will be born;

[0025] S3: After the reaction is completed, filter pressing is performed, and the filtrate after filter pressing enters the weak acid system. The weak acid system is a two-stage acid leaching of metallic manganese ore powder. The filter residue is a Pb-rich residue that can be processed for resource recovery.

[0026] In a preferred embodiment, the main components of the electrolytic waste slag are total manganese, MnO 2 , Mn 2+ , from the analysis of Mn 4+ and Mn 2+ The sum of is not equal to the total manganese value, so there is always a certain amount of elemental Mn in the electrolytic waste slag;

[0027] The main principle of electrolytic waste slag pulping is: under acidic conditions, adding reducing agent H 2 O 2 Mn 4+ Reduction to Mn 2+ , main reaction:

[0028] Mn0+2H + =Mn 2+ +H 2 Oh,

[0029] Mn 2 O 3 + H 2 O 2 +4H + = 2Mn 2+ +3H 2 O+O 2 ↑,

[0030] MnO 2 + H 2 O 2 +2H + = Mn 2+ +2H 2O+O 2 ↑.

[0031] In a preferred embodiment, from the perspective of electrolytic waste slag pulping reaction, H 2 O 2 Reduction of Mn 4+ At the same time, oxygen is released. If there is single Mn, single Mn and H in the electrolytic waste slag, + reaction:

[0032] Mn+2H + =Mn 2+ +H 2 ↑.

[0033] In a preferred embodiment, the effective volume is 300M 3 Inject 230M into the reaction tank 1 3 Anolyte, turn on the stirrer 7, take samples at multiple points of the electrolytic waste slag for testing of moisture, total manganese, tetravalent manganese, and divalent manganese content, the amount of waste slag added is calculated according to the content of total Mn and Mn4+, and added according to the calculated amount, the added waste slag is approximately 30-40T, the calculated and weighed waste slag is loaded into the hopper by a loading machine, and sent into the reaction barrel 1 through the elevator 4 and the feed hopper 3.

[0034] In a preferred embodiment, a tail gas treatment tower is provided at the other end of the tail gas pipeline 14. The tail gas treatment tower absorbs the gas generated during the treatment reaction. Hydrogen is generated during the reaction. The tail gas treatment tower has anti-static measures.

[0035] In a preferred embodiment, sulfuric acid is added according to the H + The specific amount of H2O2 is calculated by adding 2.7-5.6T / barrel. After reacting for 3-4 hours, blow air into the barrel to remove H2O2. 2 All discharged, and then sampled for initial Mn 2+ , initial reaction H + .

[0036] In a preferred embodiment, hydrogen peroxide is added according to the test results, and the amount of hydrogen peroxide added is 10M 3 / h, the amount added is about 16-20T / barrel, after 8-10h of reaction, take samples and analyze the end point Mn 2+ , reaction end point H + (reaching Mn 2+ 40±1g / L; NH 4 (SO4) 2 90±1g / L; H + (acid) is ≤1.1g / L), the reaction is completed.

[0037] In a preferred embodiment, the slurry pump is turned on to transport the prepared qualified liquid to a 400M2 filter press for filtration. The filtrate is transported to the weak acid workshop through a chute and enters the liquid preparation system. The slag enters the slag room, and slag samples are taken to analyze the moisture content, total manganese, and tetravalent manganese content of the slag; the Pb content, and the Pb-rich slag is collected for subsequent resource recycling.

[0038] It should be noted that the above embodiments all belong to the same utility model concept, and the description of each embodiment has its own focus. For matters that are not described in detail in some embodiments, reference can be made to the description in other embodiments.

[0039] The above-mentioned embodiments only express the implementation methods of the utility model, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the utility model patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the utility model, and these all belong to the protection scope of the utility model. Therefore, the protection scope of the utility model patent shall be based on the attached claims.

Claims

1. A reaction device for recycling electrolytic manganese electrolytic waste residue, comprising a reaction barrel (1), wherein a stirrer (7) is arranged inside the reaction barrel (1), a discharge pipeline (9) is arranged at the bottom of the reaction barrel (1), and a discharge valve (8) is installed on the discharge pipeline (9), characterized in that: The feed port of the reaction barrel (1) is provided with a feed hopper (3) through a valve body (2); a screening machine (6) is provided on one side of the feed hopper (3); the waste residue screened out by the screening machine (6) is sent to an upper hopper (5); and the upper hopper (5) sends the waste residue to the feed hopper (3) through an elevator (4).

2. The electrolytic manganese electrolytic waste slag recycling reaction device according to claim 1 is characterized in that: The screen of the screening machine (6) is 100 mesh, and the waste residue passing through the 100 mesh screen enters the feed hopper (3), and the filtered waste residue is sent back to the previous grinding process.

3. The electrolytic manganese electrolytic waste slag recycling reaction device according to claim 1, characterized in that: The feed hopper (3) is fed into the reaction barrel (1) through the valve body (2). After the waste residue is fed, the valve body (2) is closed to prevent gas leakage.

4. The electrolytic manganese electrolytic waste slag recycling reaction device according to claim 1, characterized in that: The top of the reaction barrel (1) is provided with a water inlet pipeline (16), an additive pipeline (15), an exhaust gas pipeline (14) and an air blowing pipeline (12); the output end of the air blowing pipeline (12) is connected to a low blow pipe (11) extending into the interior of the reaction barrel (1).

5. The electrolytic manganese electrolytic waste slag recycling reaction device according to claim 4, characterized in that: The output end of the low blow pipe (11) is lower than the liquid level of the reaction material in the reaction barrel (1), and an air valve (10) and a compressor (13) are installed on the air blowing pipeline (12).

6. The electrolytic manganese electrolytic waste slag recycling reaction device according to claim 4, characterized in that: The water inlet pipeline (16), the additive pipeline (15), the tail gas pipeline (14) and the air blowing pipeline (12) are all provided with valves to control the flow of fluids inside the pipelines.

7. The electrolytic manganese electrolytic waste slag recycling reaction device according to claim 4 or 6, characterized in that: The output end of the tail gas pipeline (14) is connected to two branch pipes, which are respectively a combustion-supporting pipeline and a tail gas treatment tower pipeline.

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