Method for efficiently recycling ammonium sulfate in electrolytic manganese residues

Abstract

The invention discloses a method for efficiently recycling ammonium sulfate in electrolytic manganese residues. The method comprises the following steps that firstly, 0.5-1.5 parts of the electrolytic manganese residues and 2-4 parts of clear water are taken and put into a stirring machine to be fully and evenly stirred; 2, adding an acidic reagent into the slurry obtained in the step 1 after fully and uniformly stirring, adjusting the pH value, and then continuously stirring to obtain slurry; 3, the slurry obtained in the step 2 is pumped into a filter press for solid-liquid separation, filtrate and filter residues are obtained, and the filtrate is collected for standby application; 4, the filtrate in the step 3 is returned to the step 1 to replace 2-4 parts of clear water, and then 0.5-1.5 parts of electrolytic manganese residues are taken and put into a stirrer to be fully and evenly stirred; 5, repeating the step 2 and the step 3 on the slurry in the step 4 to obtain filtrate for later use; the invention aims to solve the problems that the electrolytic manganese residue recovery device in the prior art needs to be washed for multiple times, the water consumption is large, other impurities are always remained in water after washing, and the subsequent treatment difficulty is increased.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic manganese recovery, and in particular to a method for efficiently recovering ammonium sulfate from electrolytic manganese slag. Background Art

[0002] Electrolytic manganese is one of the main methods for producing manganese metal and is widely used in steel, aluminum alloys, and other industrial fields. The production process of electrolytic manganese produces a large amount of electrolytic manganese slag. Electrolytic manganese slag is mainly composed of quartz, gypsum, and a small amount of metallic impurities, often containing ammonium sulfate as a byproduct. During the production process, ammonium sulfate and ammonia water are often added to adjust the pH value of the electrolyte or maintain stable operation of the electrolytic cell. As a result, ammonium sulfate is enriched in the adjusted waste slag. If this ammonium sulfate is directly discharged into the environment, it may cause environmental pollution problems such as eutrophication of water bodies. Therefore, recovering ammonium sulfate from electrolytic manganese slag can not only reduce environmental pollution but also allow it to be recycled as a fertilizer or industrial chemical, generating additional economic value.

[0003] During the electrolytic manganese production process, a large amount of electrolytic manganese slag is produced, which contains recyclable components such as ammonium sulfate. With increasingly stringent environmental protection requirements and the growing awareness of resource recycling, how to efficiently recover ammonium sulfate from electrolytic manganese slag has become a focus of industry attention. Traditional recovery methods have many drawbacks, such as low recovery rate, high energy consumption, and complex process flow. These methods not only waste resources but also may cause secondary pollution to the environment. Therefore, it is urgent to develop a method for efficiently recovering ammonium sulfate from electrolytic manganese slag, which is of great significance for improving resource utilization, reducing production costs, and reducing environmental pollution.

[0004] Patent application number CN201911374625.3, publication number CN110981231A (hereinafter referred to as "Prior Art 1") discloses equipment and methods for the coordinated processing of electrolytic manganese slag in a dry rotary kiln cement production line. The equipment primarily comprises a rotary kiln, a kiln tail smoke chamber, and a decomposition furnace. It also includes a manganese slag metering and conveying device, an air-locking feeder, and a discharge end of the manganese slag metering and conveying device connected to the inlet of the air-locking feeder. The discharge end of the air-locking feeder is connected to the kiln tail smoke chamber, which is in turn connected to the rotary chamber and decomposition furnace. The present invention also includes a method for processing electrolytic manganese slag using the equipment.

[0005] The specification of prior art 1 discloses an apparatus and method for collaboratively processing electrolytic manganese slag based on a dry rotary kiln cement production line. However, in actual application, multi-stage dissolution and water washing recovery is used. This is a common physical and chemical separation method that recovers soluble components by dissolving the electrolytic manganese slag in water. However, the existing water washing process often requires multiple flushings, consumes a lot of water, and after washing, other impurities often remain in the water, increasing the difficulty of subsequent processing. Summary of the Invention

[0006] The present invention provides a method for efficiently recovering ammonium sulfate from electrolytic manganese slag, aiming to solve the problems in the prior art that an electrolytic manganese slag recovery device needs to be flushed multiple times, consumes a large amount of water, and often leaves other impurities in the water after washing, which increases the difficulty of subsequent treatment.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is: A method for efficiently recovering ammonium sulfate from electrolytic manganese slag comprises the following steps: Step 1: Take 0.5-1.5 parts of electrolytic manganese slag and 2-4 parts of clean water and put them into a blender and mix thoroughly; Step 2: After being fully stirred, an acidic reagent is added to the slurry in step 1 to adjust the pH value, and then the mixture is continuously stirred to obtain a slurry; Step 3: The slurry in step 2 is pumped into a filter press for solid-liquid separation to obtain a filtrate and a filter residue, and the filtrate is collected for later use; Step 4: The filtrate in step 3 is returned to step 1 to replace 2-4 parts of clean water, and then 0.5-1.5 parts of electrolytic manganese slag is placed in a blender and stirred thoroughly; Step 5: Repeat steps 2 and 3 with the slurry in step 4 to obtain a filtrate for later use; Step 6: Repeat steps 4 and 5 with the filtrate from step 5; Step 7: The filtrate in step 6 is collected and crystallized into an MVR system to obtain ammonium sulfate crystals.

[0008] Furthermore, in step 1, the acidic reagent is concentrated sulfuric acid.

[0009] Furthermore, the amount of concentrated sulfuric acid is 0.01-0.05 parts.

[0010] Furthermore, in step 2, it is necessary to stabilize the pH value of the slurry at 4-5 after adding an acidic reagent.

[0011] Furthermore, in step 2, the slurry needs to be continuously stirred for 20-40 minutes.

[0012] Furthermore, in step six, step six is not performed until the ammonia nitrogen concentration in the filtrate reaches 18-25 g / L.

[0013] Furthermore, the ammonium sulfate is recovered by a recovery device; the recovery device includes a stirring component, a solid-liquid separation component and an evaporation component, and the stirring component, the solid-liquid separation component and the evaporation component are interconnected. Among them, the stirring assembly includes a tank body, a stirring rod and a stirring blade. The tank body has a feed port, a water inlet and a discharge port. A weighing structure is provided on the feed port, which is used to weigh the electrolytic manganese slag. The water inlet is connected to the clean water source, and the discharge port is connected to the solid-liquid separation assembly through a discharge pump. The stirring rod is rotatably installed inside the tank body, and the stirring blade is fixedly installed on the stirring rod. A motor is also provided on the tank body. The fixed end of the motor is fixedly connected to the tank body, and the output shaft passes through the tank body and is rotatably sealed with the tank body. After the output shaft passes through the tank body, it is fixedly connected to the stirring rod.

[0014] Furthermore, the weighing structure includes a slide, a sealing seat, a telescopic assembly and a weight sensor. The telescopic assembly is arranged on the feed port, the movable end of the telescopic assembly is connected to the upper end surface of the slide, the outer wall of the slide is slidably connected to the inner wall of the feed port, the sealing seat is connected to the bottom surface of the slide through a number of connecting rods, and a unloading area is formed between the slide and the sealing seat. The unloading area has an inclined structure. The weight sensor is arranged on the sealing seat, and the weight sensor is connected to the telescopic assembly through a controller.

[0015] Furthermore, a lower hopper is provided on the feed port, and the lower hopper is fixedly mounted on the upper end surface of the feed port. The telescopic assembly passes through the lower hopper and is fixedly connected to the slide cylinder.

[0016] Furthermore, a guide rod is provided on the slide cylinder, and a guide hole is provided on the lower hopper, and the guide rod is used to slide inside the guide hole.

[0017] Compared with the prior art, the present invention has the following beneficial effects: In actual use, the present invention comprises the following steps: taking 0.5-1.5 parts of electrolytic manganese slag and 2-4 parts of clean water, placing them into a stirrer and stirring them evenly; adding an acidic reagent to the slurry after stirring them evenly, adjusting the pH value, and continuously stirring to obtain a slurry; then pumping the slurry into a filter press for solid-liquid separation to obtain a filtrate and a filter residue, and collecting the filtrate for later use; then adding the filtrate into the stirrer again to replace the 2-4 parts of clean water, taking 0.5-1.5 parts of electrolytic manganese slag, placing them into the stirrer and stirring them evenly, pumping the slurry into the filter press again for solid-liquid separation to obtain a filtrate and a filter residue, and collecting the filtrate for later use; and after repeated steps, collecting the filtrate and entering an MVR system for crystallization to obtain ammonium sulfate crystals. The advantages of such a configuration are that the number of repeated solid-liquid separations and stirring times is small, thereby achieving high efficiency in overall recovery of the electrolytic manganese slag, controllable costs, low energy consumption, and less water generated during the recovery process. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1 It is a structural schematic diagram of the present invention.

[0020] Figure 2 It is a cross-sectional view of the present invention.

[0021] Figure 3 For the present invention Figure 2 A partial enlarged view of point A in the middle.

[0022] In the figure, 101-tank body, 102-stirring rod, 103-stirring blade, 104-feed port, 105-water inlet, 106-discharge port, 107-discharge pump, 108-motor, 109-slide, 110-sealing seat, 111-weight sensor, 112-connecting rod, 113-discharge area, 114-discharge hopper, 115-guide rod, 116-guide hole, 117-telescopic assembly. DETAILED DESCRIPTION

[0023] The present invention is further described below with reference to the embodiments. The embodiments described are only a part of the embodiments of the present invention and are not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] See also Figure 1-Figure 3 As shown, this embodiment discloses a method for efficiently recovering ammonium sulfate from electrolytic manganese slag, comprising the following steps: Step 1: Take 0.5-1.5 parts of electrolytic manganese slag and 2-4 parts of clean water and put them into a blender and mix thoroughly; Step 2: After being fully stirred, an acidic reagent is added to the slurry in step 1 to adjust the pH value, and then the mixture is continuously stirred to obtain a slurry; Step 3: The slurry in step 2 is pumped into a filter press for solid-liquid separation to obtain a filtrate and a filter residue, and the filtrate is collected for later use; Step 4: The filtrate in step 3 is returned to step 1 to replace 2-4 parts of clean water, and then 0.5-1.5 parts of electrolytic manganese slag is placed in a blender and stirred thoroughly; Step 5: Repeat steps 2 and 3 with the slurry in step 4 to obtain a filtrate for later use; Step 6: Repeat steps 4 and 5 with the filtrate from step 5; Step 7: The filtrate in step 6 is collected and crystallized into an MVR system to obtain ammonium sulfate crystals.

[0025] In actual use, the present invention comprises the following steps: taking 0.5-1.5 parts of electrolytic manganese slag and 2-4 parts of clean water, placing them into a stirrer and stirring them evenly; adding an acidic reagent to the slurry after stirring them evenly, adjusting the pH value, and continuously stirring to obtain a slurry; then pumping the slurry into a filter press for solid-liquid separation to obtain a filtrate and a filter residue, and collecting the filtrate for later use; then adding the filtrate into the stirrer again to replace the 2-4 parts of clean water, taking 0.5-1.5 parts of electrolytic manganese slag, placing them into the stirrer and stirring them evenly, pumping the slurry into the filter press again for solid-liquid separation to obtain a filtrate and a filter residue, and collecting the filtrate for later use; and after repeated steps, collecting the filtrate and entering an MVR system for crystallization to obtain ammonium sulfate crystals. The advantages of such a configuration are that the number of repeated solid-liquid separations and stirring times is small, thereby achieving high efficiency in overall recovery of the electrolytic manganese slag, controllable costs, low energy consumption, and less water generated during the recovery process.

[0026] As an optional implementation, in this embodiment, the acidic reagent in step 1 is concentrated sulfuric acid.

[0027] As an optional implementation, in this embodiment, the concentrated sulfuric acid is 0.01-0.05 parts.

[0028] In actual use, the amount of concentrated sulfuric acid added is 0.25 parts As an optional implementation, in this embodiment, in step 2, it is necessary to stabilize the pH value of the slurry at 4-5 after adding an acidic reagent.

[0029] As an optional implementation, in this embodiment, in step 2, the slurry needs to be continuously stirred for 20-40 minutes.

[0030] In actual use, the slurry is continuously stirred for 30 minutes; As an optional implementation, in this embodiment, in step six, step six is not performed until the ammonia nitrogen concentration in the filtrate reaches 18-25 g / L.

[0031] In some different embodiments, the ammonium sulfate is recovered by a recovery device; the recovery device includes a stirring component, a solid-liquid separation component and an evaporation component, and the stirring component, the solid-liquid separation component and the evaporation component are interconnected. Among them, the stirring assembly includes a tank body 101, a stirring rod 102 and a stirring blade 103. The tank body 101 has a feed port 104, a water inlet 105 and a discharge port 106. The feed port 104 is provided with a weighing structure, which is used to weigh the electrolytic manganese slag. The water inlet 105 is connected to the clean water source, and the discharge port 106 is connected to the solid-liquid separation assembly through the discharge pump 107. The stirring rod 102 is rotatably installed inside the tank body 101, and the stirring blade 103 is fixedly installed on the stirring rod 102. The tank body 101 is also provided with a motor 108. The fixed end of the motor 108 is fixedly connected to the tank body 101, and the output shaft passes through the tank body 101 and is rotatably sealed with the tank body 101. After the output shaft passes through the tank body 101, it is fixedly connected to the stirring rod 102.

[0032] During actual use, the staff passes the electrolytic manganese slag into the feed port 104, the weighing structure detects the weight of the electrolytic manganese slag, and passes it into the tank body 101. At the same time, clean water is added to the water inlet 105, and then the motor 108 is turned on. After the motor 108 rotates, it drives the stirring shaft to rotate, and then drives the stirring blades 103 to mix the slurry and clean water, and finally form a slurry.

[0033] In some embodiments, the weighing structure includes a slide 109, a sealing seat 110, a telescopic assembly 117 and a weight sensor 111. The telescopic assembly 117 is arranged on the feed port 104. The movable end of the telescopic assembly 117 is connected to the upper end surface of the slide 109. The outer wall of the slide 109 is slidably connected to the inner wall of the feed port 104. The sealing seat 110 is connected to the bottom surface of the slide 109 through a number of connecting rods 112. A unloading area 113 is formed between the slide 109 and the sealing seat 110. The unloading area 113 is an inclined structure. The weight sensor 111 is arranged on the sealing seat 110. The weight sensor 111 is connected to the telescopic assembly 117 through a controller.

[0034] During actual use, when the weight of the electrolytic manganese slag reaches the threshold of the weight sensor 111, the weight sensor 111 transmits a signal to the controller, and the controller controls the telescopic component 117 to extend. When the telescopic component 117 extends, it pushes the slide 109 to slide on the inner wall of the feed port 104, so that the slide 109 slides out of the feed port 104, and then the electrolytic manganese slag enters the tank body 101 from the slide 109. At the same time, clean water is added to the water inlet 105, and then the motor 108 is turned on. After the motor 108 rotates, it drives the stirring shaft to rotate, and then drives the stirring blades 103 to mix the slurry and clean water, and finally form a slurry.

[0035] In some embodiments, a lower hopper 114 is further provided on the feed port 104 . The lower hopper 114 is fixedly mounted on the upper end surface of the feed port 104 . The telescopic assembly 117 passes through the lower hopper 114 and is fixedly connected to the slide 109 .

[0036] In actual use, the lower hopper 114 is provided to facilitate the loading of electrolytic manganese slag.

[0037] In some embodiments, a guide rod 115 is further provided on the slide 109 , and a guide hole 116 is provided on the lower hopper 114 . The guide rod 115 is used to slide inside the guide hole 116 .

[0038] In actual use, the guide rod 115 is provided to make the slide 109 more stable when sliding at the feed port 104 .

[0039] In the description of the present invention, it should be understood that the terms "coaxial", "bottom", "one end", "top", "middle", "the other end", "upper", "one side", "top", "inside", "front", "center", "two ends", etc., indicating the orientation or position relationship, are based on the orientation or position relationship shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0040] In addition, the terms "first", "second", "third" and "fourth" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first", "second", "third" and "fourth" may explicitly or implicitly include at least one such feature.

[0041] In the present invention, unless otherwise clearly stipulated and limited, the terms such as "installation", "setting", "connection", "fixation" and "screw-on" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integrated connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. Unless otherwise clearly defined, ordinary technicians in this field can understand the specific meanings of the above terms in the present invention according to the specific circumstances.

[0042] While 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 these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for efficiently recovering ammonium sulfate from electrolytic manganese slag, characterized in that: The steps include: Step 1: Take 0.5-1.5 parts of electrolytic manganese slag and 2-4 parts of clean water and put them into a blender and mix thoroughly; Step 2: After being fully stirred, an acidic reagent is added to the slurry in step 1 to adjust the pH value, and then the mixture is continuously stirred to obtain a slurry; Step 3: The slurry in step 2 is pumped into a filter press for solid-liquid separation to obtain a filtrate and a filter residue, and the filtrate is collected for later use; Step 4: The filtrate in step 3 is returned to step 1 to replace 2-4 parts of clean water, and then 0.5-1.5 parts of electrolytic manganese slag is placed in a blender and stirred thoroughly; Step 5: Repeat steps 2 and 3 with the slurry in step 4 to obtain a filtrate for later use; Step 6: Repeat steps 4 and 5 with the filtrate from step 5; Step 7: The filtrate in step 6 is collected and crystallized into an MVR system to obtain ammonium sulfate crystals.

2. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 1, wherein: In step 1, the acidic reagent is concentrated sulfuric acid.

3. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 2, wherein: The amount of concentrated sulfuric acid is 0.01-0.05 parts.

4. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 1, wherein: In step 2, an acidic reagent needs to be added to stabilize the pH value of the slurry at 4-5.

5. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 1, wherein: In step 2, the slurry needs to be stirred continuously for 20-40 minutes.

6. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 1, wherein: In step 6, continue with step 6 until the ammonia nitrogen concentration in the filtrate reaches 18-25 g / L.

7. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 1, wherein: The ammonium sulfate is recovered by a recovery device; The recovery device includes a stirring component, a solid-liquid separation component and an evaporation component, which are interconnected. The stirring assembly comprises a tank body (101), a stirring rod (102) and a stirring blade (103); the tank body (101) is provided with a feed port (104), a water inlet (105) and a discharge port (106); a weighing structure is provided on the feed port (104), and the weighing structure is used to weigh the electrolytic manganese slag; the water inlet (105) is connected to a clean water source; the discharge port (106) is connected to a solid-liquid separation assembly through a discharge pump (107); Then, the stirring rod (102) is rotatably mounted inside the tank body (101), the stirring blade (103) is fixedly mounted on the stirring rod (102), the tank body (101) is further provided with a motor (108), the fixed end of the motor (108) is fixedly connected to the tank body (101), the output shaft passes through the tank body (101) and is rotatably sealed with the tank body (101), and the output shaft passes through the tank body (101) and is fixedly connected to the stirring rod (102).

8. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 7, wherein: The weighing structure includes a slide (109), a sealing seat (110), a telescopic assembly (117) and a weight sensor (111). The telescopic assembly (117) is arranged on the feed port (104). The movable end of the telescopic assembly (117) is connected to the upper end surface of the slide (109). The outer wall of the slide (109) is slidably connected to the inner wall of the feed port (104). The sealing seat (110) is connected to the bottom surface of the slide (109) through a plurality of connecting rods (112). A feeding area (113) is formed between the slide (109) and the sealing seat (110). The feeding area (113) is an inclined structure. The weight sensor (111) is arranged on the sealing seat (110). The weight sensor (111) is connected to the telescopic assembly (117) through a controller.

9. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 8, wherein: The feed port (104) is also provided with a lower hopper (114), which is fixedly mounted on the upper end surface of the feed port (104). The telescopic assembly (117) passes through the lower hopper (114) and is fixedly connected to the slide cylinder (109).

10. The method for efficiently recovering ammonium sulfate from electrolytic manganese slag according to claim 9, wherein: The slide cylinder (109) is further provided with a guide rod (115), and the lower hopper (114) is provided with a guide hole (116), and the guide rod (115) is used to slide inside the guide hole (116).

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