Method and equipment for cyclic utilization of ammonia gas for stable solidification of electrolytic manganese residues

Abstract

The invention discloses a method and equipment for cyclic utilization of ammonia gas for stable solidification of electrolytic manganese residues, and relates to the technical field of electrolytic manganese residues, the equipment comprises a washing tower, an ammonia water pipeline is communicated with an acid leaching pool, an ammonia water pipeline valve is fixedly communicated with the ammonia water pipeline, one end of a conveying pipe is fixedly communicated with a spraying pipe, and the other end of the conveying pipe is fixedly communicated with an acid leaching pool. The bottom of the spray pipe is fixedly communicated with a spray head, a cooling heat exchange device is arranged in the washing tower, a gas-liquid separation device is fixedly mounted at the upper position in the washing tower, and a filler layer is arranged below the spray head in the washing tower. Ammonia in tail gas generated in the stable solidification process of the electrolytic manganese residues is collected through ammonia collecting equipment to prepare ammonia water, then the obtained ammonia water is introduced into an acid leaching pool in the electrolytic manganese residue process, and pH is adjusted to remove Fe < 3 + > in leachate. The method can effectively reduce ammonia consumption, improve the operation environment of the electrolytic manganese residue stable curing site, create economic benefits and facilitate use.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic manganese slag, and in particular to a method and equipment for recycling ammonia gas in stable solidified electrolytic manganese slag. Background Art

[0002] my country is a major manganese producing country, accounting for about 98% of the world's annual manganese production. In recent years, with the rapid development of the electrolytic manganese industry, electrolytic manganese slag, a byproduct of industrial manganese production, has been accumulating. According to relevant statistics, 10-12 tons of electrolytic manganese slag will be produced for every ton of metallic manganese produced. Electrolytic manganese slag contains excessive ammonia nitrogen and heavy metal ions (such as Mn2+, Pb2+, Cu2+, Ni2+ and Zn2+), which has a high risk of leaching during long-term storage, posing a huge threat to human health and the ecological environment.

[0003] In the electrolytic manganese slag process, the manganese ore is acid-leached. In this process, Fe2+ in the manganese ore will also appear in the leaching solution as an impurity, affecting the final electrolysis efficiency and the purity of metallic manganese. Therefore, pyrolusite should be added first to oxidize it to Fe 3+ Then, NH3·H2O was used to adjust the liquid pH to 6.5-7.0, and Fe(OH)3 precipitation was used to remove Fe in the leaching solution. 3+ According to statistics, 0.11 tons of ammonia water are consumed for every ton of manganese metal produced by electrolysis, of which about 45% of ammonia nitrogen exists in the electrolytic manganese slag.

[0004] If the ammonia gas generated during the stabilization / solidification (S / S) process of electrolytic manganese slag using an alkaline solidifying agent can be collected and then used to generate ammonia water in the acid leaching tank of electrolytic manganese slag process, the 3+ The removal of it can not only improve the operating environment at the site of electrolytic manganese slag stabilization and solidification, but also reduce ammonia consumption and create economic benefits. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides a method and apparatus for recycling and stabilizing ammonia in electrolytic manganese slag, which solves the problem that the electrolytic manganese slag contains excessive ammonia nitrogen and heavy metal ions, which has a high risk of leaching during long-term storage and poses a huge threat to human health and the ecological environment.

[0007] (II) Technical solution

[0008] To achieve the above purpose, the present invention is implemented by the following technical scheme: a method and equipment for recycling ammonia in stable solidification of electrolytic manganese slag, comprising: a washing tower, an exhaust port is opened at the top of the washing tower, a gas delivery pipe is fixedly connected at the lower position of the surface of the washing tower, a fan is fixedly installed at one end of the gas delivery pipe, an air inlet pipe is fixedly connected on the surface of the fan, and the air inlet pipe is connected to the tail gas generated during the stable solidification of the electrolytic manganese slag, an ammonia pipeline is fixedly connected at the bottom of the washing tower, the ammonia pipeline is connected to the acid leaching tank, an ammonia pipeline valve is fixedly connected on the ammonia pipeline, a water pump is fixedly connected in the washing tower, a circulating pump is fixedly installed at one end of the water pump, a circulating pipe is fixedly connected at the water outlet of the circulating pump, a delivery pipe is fixedly connected on the circulation pipe, a spray pipe is fixedly connected at one end of the delivery pipe, a nozzle is fixedly connected at the bottom of the spray pipe, a cooling and heat exchange device is arranged in the washing tower, a gas-liquid separation device is fixedly installed at the upper position inside the washing tower, and a packing layer is arranged below the nozzle in the washing tower.

[0009] Preferably, a boost valve is provided on the delivery pipe, the delivery pipe and the spray pipe are provided in no less than two groups, and the nozzle circular array is located at a lower position on the surface of the spray pipe.

[0010] Preferably, the cooling and heat exchange device comprises a heat exchange plate, and the heat exchange plate is below the packing layer, and a cooling medium inlet and the heat exchange plate are fixedly connected on the surface of the heat exchange plate.

[0011] Preferably, an upper ammonia liquid level gauge and a lower ammonia liquid level gauge are sequentially arranged on the surface of the washing tower from top to bottom, and a pure water inlet pipe is fixedly connected to the surface of the washing tower, and a one-way valve is arranged on the pure water inlet pipe.

[0012] Preferably, a concentration meter is fixedly installed on the surface of the washing tower, and the concentration meter penetrates the surface of the washing tower and extends to the inside of the washing tower.

[0013] Preferably, support legs are symmetrically arranged at the bottom of the washing tower, and the circulation pipe, the delivery pipe and the spray pipe are configured as high-pressure resistant pipes.

[0014] A method and device for recycling stable solidified electrolytic manganese slag ammonia. The method for recycling stable solidified electrolytic manganese slag ammonia has the following specific steps:

[0015] A certain amount of pure water is added into the washing tower through the pure water inlet pipe as the absorption liquid.

[0016] Start the circulation pump and fan to send the ammonia-containing gas into the scrubber for circulation washing. The ammonia-containing gas is sent to the lower part of the scrubber through the gas pipe. Under the action of the circulation pump, water is sprayed from the nozzle and flows downward through the packing layer. When the ammonia-containing gas flows through the packing layer, the ammonia quickly dissolves in the water because the packing layer provides a large gas-liquid contact area.

[0017] The generated ammonia water drips downward due to gravity, and takes away the heat generated during the dissolution of the ammonia gas after passing through the cooling and heat exchange device. The remaining gas is discharged after the liquid is removed through the gas-liquid separation device. The cooled ammonia water flows into the bottom of the device and is then pumped out by the circulating pump as the absorption liquid for repeated circulation and absorption.

[0018] When the concentration meter detects that the value is basically unchanged, turn off the circulation pump, open the ammonia pipeline valve at the bottom of the washing tower, and pass the ammonia water into the acid leaching tank in the electrolytic manganese slag process to adjust the pH of the leaching solution to remove Fe in the leaching solution. 3+ .

[0019] (III) Beneficial effects

[0020] The present invention provides a method and device for recycling and stabilizing ammonia gas in electrolytic manganese slag, which has at least the following beneficial effects compared with the prior art:

[0021] Start the circulation pump and fan to send the ammonia-containing gas into the scrubbing tower for circulating washing. The ammonia-containing gas is sent to the lower part of the scrubbing tower through the gas pipe. Under the action of the circulation pump, water is sprayed out from the nozzle and flows downward through the packing layer. When the ammonia-containing gas flows through the packing layer, the ammonia quickly dissolves in the water because the packing layer provides a large gas-liquid contact area. The generated ammonia water drips downward due to gravity, and after passing through the cooling and heat exchange device, it takes away the heat generated during the dissolution of the ammonia gas. The remaining gas is discharged after the liquid is removed by the gas-liquid separation device. The cooled ammonia water flows into the bottom of the device and is then pumped out by the circulation pump as an absorption liquid for repeated absorption. When the concentration meter detects that the value is basically unchanged, turn off the circulation pump, open the ammonia water pipeline valve at the bottom of the scrubbing tower, and pass the ammonia water into the acid leaching tank in the electrolytic manganese slag process to adjust the pH of the leachate to remove Fe in the leachate. 3+ .

[0022] The tail gas generated during the stabilization and solidification of electrolytic manganese slag is collected through an ammonia collection device to prepare ammonia water, and then the obtained ammonia water is passed into the acid leaching tank in the electrolytic manganese slag process to adjust the pH to remove Fe in the leaching solution. 3+ The method can effectively reduce ammonia consumption, improve the operating environment of the electrolytic manganese slag stabilization and solidification site, create economic benefits, and is easy to use. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of the structure of the present invention;

[0024] Figure 2 It is a three-dimensional cross-sectional view of the present invention;

[0025] Figure 3 It is a structural schematic diagram of the bottom of the washing tower of the present invention;

[0026] Figure 4 It is a schematic diagram of the structure inside the washing tower of the present invention;

[0027] Figure 5 It is a structural schematic diagram of the spray pipe of the present invention;

[0028] Figure 6 It is a process flow chart of the present invention.

[0029] In the figure: 1. washing tower; 2. exhaust port; 3. fan; 4. air inlet pipe; 5. air delivery pipe; 6. ammonia pipeline valve; 7. ammonia pipeline; 8. water extraction pipe; 9. circulation pump; 10. circulation pipe; 11. boost valve; 12. delivery pipe; 13. spray pipe; 14. nozzle; 15. cooling and heat exchange device; 1501. cooling medium inlet; 1502. heat exchange plate; 1503. cooling medium outlet; 16. packing layer; 17. gas-liquid separation device; 18. support leg; 19. ammonia lower level gauge; 20. ammonia upper level gauge; 21. pure water inlet pipe; 22. concentration meter. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Embodiment 1:

[0032] See also Figure 1-4The present invention provides a technical solution: a washing tower 1, an exhaust port 2 is provided at the top of the washing tower 1, an air delivery pipe 5 is fixedly connected at the lower position of the surface of the washing tower 1, a fan 3 is fixedly installed at one end of the air delivery pipe 5, an air inlet pipe 4 is fixedly connected to the surface of the fan 3, the air inlet pipe 4 is connected to the tail gas generated during the stable solidification process of the electrolytic manganese slag, an ammonia water pipeline 7 is fixedly connected to the bottom of the washing tower 1, the ammonia water pipeline 7 is connected to the acid leaching tank, an ammonia water pipeline valve 6 is fixedly connected on the ammonia water pipeline 7, a water pumping pipe 8 is fixedly connected in the washing tower 1, a circulating pump 9 is fixedly installed at one end of the water pumping pipe 8, a circulating pipe 10 is fixedly connected to the water outlet of the circulating pump 9, a delivery pipe 12 is fixedly connected on the circulation pipe 10, a spray pipe 13 is fixedly connected at one end of the delivery pipe 12, a nozzle 14 is fixedly connected at the bottom of the spray pipe 13, a cooling and heat exchange device 15 is arranged in the washing tower 1, a gas-liquid separation device 17 is fixedly installed at the upper position inside the washing tower 1, and a packing layer 16 is arranged below the nozzle 14 in the washing tower 1.

[0033] Analysis of the above content: Start the circulation pump 9 and the fan 3, send the ammonia-containing gas into the washing tower 1 for circulating washing, the ammonia-containing gas is sent to the lower position of the washing tower 1 through the gas pipe 5, under the action of the circulation pump 9, water is sprayed from the nozzle 14, and flows downward through the packing layer 16. When the ammonia-containing gas flows through the packing layer 16, the ammonia is quickly dissolved in the water because the packing layer 16 provides a large gas-liquid contact area; the generated ammonia water drips downward due to gravity, and after passing through the cooling heat exchange device 15, it takes away the heat generated during the dissolution of the ammonia gas, and the remaining gas is discharged after the liquid is removed by the gas-liquid separation device 17. The cooled ammonia water flows into the bottom of the device and is then extracted by the circulation pump 9 as an absorption liquid, and is repeatedly absorbed in a cycle. Stabilizing and solidifying tail gas from electrolytic manganese slag refers to the ammonia-containing gas generated when electrolytic manganese slag is harmlessly treated using alkaline substances such as chemical reagents such as calcium oxide, magnesium oxide, calcium hydroxide, or alkaline solid waste materials such as carbide slag and magnesium slag as a solidifying agent.

[0034] Embodiment 2:

[0035] See also Figure 1-4 The present invention provides a technical solution based on the first embodiment: a boost valve 11 is arranged on the delivery pipe 12, at least two groups of delivery pipes 12 and spray pipes 13 are arranged, and the nozzles 14 are arranged in a circular array at a lower position on the surface of the spray pipe 13.

[0036] Analysis of the above contents: a booster valve 11 is provided to increase the water spraying pressure of the nozzle 14, and multiple groups of delivery pipes 12 and spray pipes 13 are provided to increase the contact area between ammonia and water, thereby improving the absorption effect of ammonia.

[0037] Embodiment three:

[0038] See also Figure 1-4The present invention provides a technical solution based on the first embodiment: the cooling heat exchange device 15 includes a heat exchange plate 1502, the heat exchange plate 1502 is below the packing layer 16, and a cooling medium inlet 1501 and the heat exchange plate 1502 are fixedly connected on the surface of the heat exchange plate 1502.

[0039] Analysis of the above content: The cooling medium flows into the heat exchange plate 1502 through the cooling medium liquid inlet 1501, and is discharged from the cooling medium liquid outlet 1503, absorbing the heat generated by the ammonia water.

[0040] Embodiment 4:

[0041] See also Figure 1-4 The present invention provides a technical solution based on the first embodiment: an upper ammonia level gauge 20 and a lower ammonia level gauge 19 are sequentially arranged on the surface of the washing tower 1 from top to bottom, and a pure water inlet pipe 21 is fixedly connected to the surface of the washing tower 1, and a one-way valve is arranged on the pure water inlet pipe 21.

[0042] Analysis of the above content: an ammonia upper level gauge 20 and an ammonia lower level gauge 19 are set to detect the amount of water at the bottom of the washing tower 1, a one-way valve is set, and pure water is added into the washing tower 1 through the pure water inlet pipe 21 as an absorption liquid.

[0043] Embodiment five:

[0044] See also Figure 1-4 The present invention provides a technical solution based on the first embodiment: a concentration meter 22 is fixedly installed on the surface of the washing tower 1, and the concentration meter 22 penetrates the surface of the washing tower 1 and extends to the inside of the washing tower 1. Support legs 18 are symmetrically arranged at the bottom of the washing tower 1, and the circulation pipe 10, the delivery pipe 12 and the spray pipe 13 are set as high-pressure resistant pipes.

[0045] Analysis of the above content: The concentration of ammonia water is detected by the concentration meter 22. When the concentration meter 22 detects that the value is basically unchanged, the circulation pump 9 is turned off, the ammonia water pipeline valve 6 at the bottom of the washing tower is opened, and the ammonia water is passed into the acid leaching tank in the electrolytic manganese slag process to adjust the pH of the leachate to remove Fe in the leachate. 3+ .

[0046] Embodiment six:

[0047] See also Figure 1-4 Based on the first embodiment, the present invention provides a technical solution: a method and device for recycling stable solidified electrolytic manganese slag ammonia. The specific steps of the method for recycling stable solidified electrolytic manganese slag ammonia are as follows:

[0048] S1. Add a certain amount of pure water as absorption liquid into the washing tower 1 through the pure water inlet pipe 21, start the circulation pump 9 and the fan 3, and send the ammonia-containing gas into the washing tower 1 for circulation washing.

[0049] S2. Ammonia-containing gas is delivered to the lower part of the washing tower 1 through the gas delivery pipe 5. Under the action of the circulating pump 9, water is sprayed out from the nozzle 14 and flows downward through the packing layer 16. When the ammonia-containing gas flows through the packing layer 16, the ammonia is rapidly dissolved in the water because the packing layer 16 increases the gas-liquid contact area.

[0050] S3. The generated ammonia water drips downward due to gravity, and takes away the heat generated during the dissolution of the ammonia gas after passing through the cooling heat exchange device 15. The remaining gas is discharged after the liquid is removed by the gas-liquid separation device 17. The cooled ammonia water flows into the bottom of the device and is then pumped out by the circulation pump 9 as the absorption liquid for repeated circulation absorption.

[0051] S4. When the concentration meter 22 detects that the value is basically unchanged, the circulation pump 9 is turned off, the ammonia pipeline valve 6 at the bottom of the washing tower is opened, and the ammonia water is passed into the acid leaching tank in the electrolytic manganese slag process to adjust the pH of the leachate to remove Fe in the leachate. 3+ The present method can fully absorb the ammonia generated during the stable solidification of electrolytic manganese slag, improve the on-site operating environment, and at the same time, the absorbed ammonia can be reused to adjust the pH of the acid leaching solution in the electrolytic manganese slag process, which can reduce ammonia consumption and has good economic benefits.

[0052] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0053] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A device for recycling and stabilizing ammonia gas from electrolytic manganese slag, characterized in that: include: A washing tower (1), wherein an exhaust port (2) is provided at the top of the washing tower (1), an air supply pipe (5) is fixedly connected to the lower part of the surface of the washing tower (1), a fan (3) is fixedly installed at one end of the air supply pipe (5), an air intake pipe (4) is fixedly connected to the surface of the fan (3), the air intake pipe (4) is connected to the tail gas generated during the stable solidification process of electrolytic manganese slag, an ammonia water pipeline (7) is fixedly connected to the bottom of the washing tower (1), the ammonia water pipeline (7) is connected to the acid leaching tank, the ammonia water pipeline (7) is fixedly connected to an ammonia water pipeline valve (6), and a pumping valve (7) is fixedly connected to the washing tower (1). A pipe (8) is provided, one end of the water pump pipe (8) is fixedly mounted with a circulation pump (9), the water outlet of the circulation pump (9) is fixedly connected to a circulation pipe (10), the circulation pipe (10) is fixedly connected to a delivery pipe (12), one end of the delivery pipe (12) is fixedly connected to a spray pipe (13), the bottom of the spray pipe (13) is fixedly connected to a nozzle (14), a cooling and heat exchange device (15) is provided in the washing tower (1), a gas-liquid separation device (17) is fixedly mounted at an upper position inside the washing tower (1), and a packing layer (16) is provided in the washing tower (1) below the nozzle (14).

2. The device for recycling and stabilizing ammonia in electrolytic manganese slag according to claim 1, characterized in that: The delivery pipe (12) is provided with a boost valve (11), the delivery pipe (12) and the spray pipe (13) are provided in at least two groups, and the spray heads (14) are arranged in a circular array at a lower position on the surface of the spray pipe (13).

3. The device for recycling and stabilizing ammonia in electrolytic manganese slag according to claim 1, characterized in that: The cooling heat exchange device (15) comprises a heat exchange plate (1502), wherein the heat exchange plate (1502) is below the packing layer (16), and a cooling medium inlet (1501) and the heat exchange plate (1502) are fixedly connected on the surface of the heat exchange plate (1502).

4. The device for recycling and stabilizing ammonia gas from electrolytic manganese slag according to claim 1, characterized in that: An ammonia upper level gauge (20) and an ammonia lower level gauge (19) are sequentially arranged on the surface of the washing tower (1) from top to bottom. A pure water inlet pipe (21) is fixedly connected to the surface of the washing tower (1), and a one-way valve is arranged on the pure water inlet pipe (21).

5. The device for recycling and stabilizing ammonia gas from electrolytic manganese slag according to claim 1, characterized in that: A concentration meter (22) is fixedly mounted on the surface of the washing tower (1), and the concentration meter (22) penetrates the surface of the washing tower (1) and extends into the interior of the washing tower (1).

6. The device for recycling and stabilizing ammonia gas from electrolytic manganese slag according to claim 1, characterized in that: The bottom of the washing tower (1) is symmetrically provided with supporting legs (18), and the circulation pipe (10), the delivery pipe (12) and the spray pipe (13) are configured as high-pressure resistant pipes.

7. A method for recycling ammonia gas from stabilized and solidified electrolytic manganese slag according to any one of claims 1 to 6, characterized in that: The specific steps of the method for recycling and stabilizing the solidified electrolytic manganese slag ammonia are as follows: Adding pure water as absorption liquid into the washing tower (1) through the pure water inlet pipe (21); The circulating pump (9) and the fan (3) are started to send the ammonia-containing gas into the washing tower (1) for circulating washing. The ammonia-containing gas is sent into the lower part of the washing tower (1) through the gas delivery pipe (5). Under the action of the circulating pump (9), water is sprayed out from the nozzle (14) and flows downward through the packing layer (16). When the ammonia-containing gas flows through the packing layer (16), the ammonia is quickly dissolved in the water. The generated ammonia water drips downward due to gravity, and after passing through the cooling heat exchange device (15), the heat generated during the dissolution of the ammonia gas is taken away. The remaining gas passes through the gas-liquid separation device (17) to remove the liquid and then is discharged. The cooled ammonia water flows into the bottom of the device and is then pumped out by the circulation pump (9) as the absorption liquid, and the absorption is repeated in a cycle. When the concentration meter (22) detects that the value remains unchanged, the circulation pump (9) is turned off, the ammonia water pipeline valve (6) at the bottom of the washing tower is opened, and the ammonia water is passed into the acid leaching tank in the electrolytic manganese slag process to adjust the pH of the leaching solution to remove Fe in the leaching solution. 3+ .

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