Device and method for recovering metal gallium in lime slag

Abstract

The invention discloses a device and method for recycling metal gallium in lime slag, the device comprises a reaction kettle, a stirring frame is rotatably arranged in the reaction kettle, a stirring wheel is rotatably arranged on the stirring frame, and the stirring wheel is elastically and slidably arranged along the stirring center pointing to the stirring frame; the stirring wheel abuts against the inner circumferential wall of the reaction kettle in the rotating process, and the section, perpendicular to the axis direction of the stirring frame, of the inner wall of the reaction kettle is oval. In the scattering process, the stirring wheel can be close to and far away from the stirring center of the stirring frame in a reciprocating manner, so that slurry (a mixture of a filter cake and alkali liquor) in the reaction tank is fully scattered, and most of precipitates positioned near the inner wall of the reaction tank and a few of precipitates far away from the inner wall of the reaction tank can be fully mixed; and the recovery effect of the metal gallium is ensured.

Description

Technical Field

[0001] The present application relates to the field of metallurgical technology, and in particular to a device and method for recovering metallic gallium from lime slag. Background Art

[0002] In the gallium production process, the main method for extracting gallium from the mother liquor is the resin adsorption method, which uses the special functional groups on the resin to interact with gallium ions, and then uses the desorption liquid to displace the gallium ions from the resin, thereby extracting the gallium ions from the mother liquor. However, since the resin can not only interact with gallium ions, but also with other impurity elements, such as organic matter, vanadium, S2-, etc., they will also enter the subsequent process.

[0003] In order to remove impurities, improve the quality of the solution, and ensure stable production operation and product quality, quicklime needs to be added during the impurity removal stage. After it fully reacts in the tank, it is filtered through a plate and frame filter press. The filter cake is washed with water and then unloaded. The filter cake is discharged and stored centrally, which is lime slag. Although the plate and frame filter cake is washed in the process, the washing effect is general, and the amount of gallium recovered in the lime slag is limited. The filter cake is usually washed in the following way: the filter cake is left inside the filter plate of the plate and frame filter press and washed 1-2 times with 75°C hot water. Since the filter cake is agglomerated and distributed between the filter plates of the plate and frame filter press and cannot be dispersed, there is a lot of gallium-rich liquid remaining in the filter cake, resulting in a high gallium content in the lime slag, averaging 2.0%. About 1.5 tons of gallium are lost with the lime slag every year, causing great losses. Summary of the invention

[0004] The purpose of the present application is to provide a device and method for recovering metallic gallium from lime slag in order to solve the above-mentioned problem.

[0005] To achieve the above purpose, the technical solution of this application is: In a first aspect, the present application provides a device for recovering metallic gallium from lime slag, comprising a reactor, wherein a stirring frame is rotatably provided inside the reactor, a stirring wheel is rotatably provided on the stirring frame, and the stirring wheel is elastically slidably arranged along a stirring center pointing to the stirring frame; the stirring wheel abuts against the inner circumferential wall of the reactor during rotation, and the cross-section of the inner wall of the reactor perpendicular to the axis of the stirring frame is elliptical.

[0006] Preferably, the stirring frame comprises a first connecting rod and a second connecting rod which are radially arranged, the first connecting rod is elastically sleeved and connected to the second connecting rod, and the stirring wheel is rotatably arranged at an end of the second connecting rod away from the first connecting rod.

[0007] Preferably, the stirring wheel includes a connecting handle and a connecting shaft, the connecting handle is cross-shaped, the center of the connecting handle is rotatably connected to the second connecting rod, and the end of the connecting shaft is connected to the end of the connecting handle; a crimping part is hingedly provided on the connecting shaft, and a protrusion that cooperates with the crimping part is provided on the inner circumferential wall of the reactor.

[0008] Preferably, the crimping portion comprises a plurality of crimping units arranged at intervals along the axial direction of the connecting shaft, and the crimping units comprise elastic plates and non-elastic plates arranged at intervals along the circumferential direction of the connecting shaft.

[0009] Preferably, the stirring frame comprises a rotating sleeve, the rotating sleeve is arranged at an end of the first connecting rod away from the second connecting rod, a rotating shaft is rotatably provided in the rotating sleeve, and a turning plate is provided on the rotating shaft.

[0010] Preferably, the flipping plate is arranged in an arc shape, and the concave side of the flipping plate faces the tangent direction of the rotation direction of the flipping plate.

[0011] Preferably, a hinge shaft is provided on the connecting handle, one end of the hinge shaft is connected to the connecting handle, and the other end passes through the second connecting rod; the hinge shaft passing through the second connecting rod is provided with a first rotating wheel at one end, and a second rotating wheel is provided on the rotating shaft, and the first rotating wheel and the second rotating wheel are connected by a transmission belt, and the transmission belt is elastic.

[0012] Preferably, the stirring wheels are symmetrically provided in two groups, wherein the diameter of the first rotating wheel corresponding to one group of the stirring wheels is smaller than the diameter of the second rotating wheel, and the diameter of the first rotating wheel corresponding to the other group of the stirring wheels is larger than the diameter of the second rotating wheel.

[0013] In the second aspect, the present application also provides a method for recovering metallic gallium in lime slag, using any of the above-described devices, including: Step 1: After the impurity removal and filtration are completed, the newly built plate and frame filter press is switched to the water washing process, and is rinsed with hot water 1 to 2 times, and the rinse water is recovered for rehydration, and then the filter cake is blown dry with compressed air; Step 2: Heat the alkaline solution in the reaction tank of the reactor, put the washed and dried filter cake into the reaction tank, and start stirring to break it up; Step 3: Start steam heating, raise the temperature to 100°C, and keep the reaction warm for 4 hours; Step 4: After the reaction is completed, the slurry in the reaction tank is sent to the original plate and frame filter press for filtration, and the filtered filtrate is transported to the filtrate buffer tank, the filter cake is dispatched, and stored centrally.

[0014] Preferably, the temperature of the hot water in step one is 65 to 75° C.; the pressure of the compressed air is ≥0.5 MPa; and the concentration of the alkali solution in step two is 100 to 200 g / L.

[0015] The present application discloses a device for recovering gallium from lime slag. During the process of breaking up, the stirring wheel will reciprocate to and from the stirring center of the stirring frame, so as to fully break up the slurry (mixture of filter cake and alkali solution) in the reaction tank, so that both the majority of precipitates located near the inner wall of the reaction tank and the minority of precipitates far from the inner wall of the reaction tank can be fully mixed, thereby ensuring the recovery effect of gallium. The method for recovering gallium from lime slag adopted by the above-mentioned device utilizes secondary washing to recover gallium from lime slag. The filtrate after the reaction can be used as alkali solution to neutralize the desorption liquid, and the recovered gallium is introduced into the gallium production process. The operation is simple and easy to implement. It is conducive to improving the secondary recovery rate and the output of gallium, reducing production costs, and improving the market competitiveness of enterprises. In addition, the washed lime slag can be sold as a by-product to increase the economic benefits of the enterprise. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the overall structure of the reactor in this application; Figure 2 This is a schematic diagram of the stirring frame and stirring wheel structure of this application; Figure 3 for Figure 2 A partial enlarged schematic diagram; Figure 4 This is a schematic diagram of the structure of the connection between the first connecting rod and the second connecting rod in this application; Figure 5 A flow chart of the recovery method in this application; Figure 6 It is the detection value of gallium content in lime slag before alkali washing, and the detection value and recovery rate of gallium content after alkali washing under the guidance of this application.

[0017] In the figure: 1. Reactor; 10. Notch; 2. First connecting rod; 3. Second connecting rod; 30. Articulated shaft; 31. First rotating wheel; 32. Connecting arm; 33. Connecting shaft; 34. Elastic plate; 35. Non-elastic plate; 36. Slot; 37. Pin; 38. Sliding hole; 39. Spring; 4. Rotating shaft; 40. Turning plate; 41. Second rotating wheel; 42. Rotating sleeve; 5. Connecting handle. DETAILED DESCRIPTION

[0018] The present application is now described in further detail in conjunction with the accompanying drawings. The accompanying drawings are simplified schematic diagrams, which only illustrate the basic structure of the present application in a schematic manner, and therefore only show the components related to the present application.

[0019] like Figure 1-6As shown, in the first aspect, the present application provides a device for recovering metallic gallium in lime slag, comprising a reactor 1, wherein a stirring frame is rotatably provided inside the reactor 1, a stirring wheel is rotatably provided on the stirring frame, and the stirring wheel is elastically slidably arranged along a stirring center pointing to the stirring frame; the stirring wheel abuts against the inner circumferential wall of the reactor 1 during rotation, and the cross-section of the inner wall of the reactor 1 in the direction perpendicular to the axis of the stirring frame is elliptical.

[0020] The reactor 1 is a columnar structure as a whole, with an opening arranged at the top. The opening has a certain length along the axial direction of the reactor 1. Due to the opening having a certain length, the interior of the reactor 1 is also called a reaction tank, and the opening is also called a notch 10. A cover is arranged on the notch 10.

[0021] The cover is not directly arranged on the outer peripheral wall of the reactor 1 , and the notch 10 protrudes from the outer peripheral wall of the reactor 1 in a rectangular frame structure.

[0022] It should be noted that the width of the opening is smaller than the minimum radial width of the reactor 1 , and the length of the opening is smaller than the length of the reactor 1 , so as to prevent the stirring frame from completely breaking away from the abutment with the inner wall of the reactor 1 during the rotation process.

[0023] The stirring wheel on the stirring frame is used to break up the filter cake and fully mix the filter cake with the alkali solution.

[0024] The stirring wheel is always in elastic contact with the inner wall of the reaction tank during rotation. When the stirring wheel contacts the short diameter position of the elliptical structure, the stirring wheel is elastically compressed toward the rotation center of the stirring frame. At this time, the abutment between the stirring wheel and the inner wall of the reaction tank increases. When the stirring wheel contacts the long diameter position of the elliptical structure, the stirring wheel elastically extends toward the rotation center of the stirring frame. At this time, the abutment between the stirring wheel and the inner wall of the reaction tank decreases. As the stirring frame continues to rotate, the stirring wheel and the inner wall of the reaction tank are in reciprocating contact, thereby fully disrupting and breaking up the filter cake, and at the same time fully mixing it with the alkali solution.

[0025] During the dispersion process, the stirring wheel will reciprocate towards and away from the stirring center of the stirring frame, thereby fully dispersing the slurry (a mixture of filter cake and alkali solution) in the reaction tank, so that both the majority of precipitates located near the inner wall of the reaction tank and the minority of precipitates far from the inner wall of the reaction tank can be fully mixed, ensuring the recovery effect of metallic gallium.

[0026] In some further embodiments, the stirring frame includes a radially arranged first connecting rod 2 and a second connecting rod 3, the first connecting rod 2 is elastically sleeved and connected to the second connecting rod 3, and the stirring wheel is rotatably arranged at one end of the second connecting rod 3 away from the first connecting rod 2.

[0027] The first connecting rod 2 is relatively close to the center of the stirring frame, and the second connecting rod 3 is relatively close to the stirring wheel.

[0028] A sliding hole 38 is extended inwardly from one end of the second connecting rod 3 close to the first connecting rod 2, and the first connecting rod 2 is slidably inserted in the sliding hole 38. At the same time, a spring 39 is arranged inside the sliding hole 38 to realize the extension and retraction of the stirring wheel and the relative hinge frame.

[0029] The sliding hole 38 in the first connecting rod 2 is provided with a narrow groove 36, which connects the inside of the sliding hole 38 with the outside. After the first connecting rod 2 slides into the sliding hole 38, a pin 37 can be arranged to pass through the narrow groove 36 and be connected to the first connecting rod 2 to achieve sliding limitation of the first connecting rod 2 and the second connecting rod 3.

[0030] In some further embodiments, the stirring wheel includes a connecting handle 5 and a connecting shaft 33, the connecting handle 5 is cross-shaped, the center of the connecting handle 5 is rotatably connected to the second connecting rod 3, and the end of the connecting shaft 33 is connected to the end of the connecting handle 5; a crimping part is hingedly provided on the connecting shaft 33, and a protrusion that cooperates with the crimping part is provided on the inner peripheral wall of the reactor 1.

[0031] The stirring wheel is rotatably connected to the second connecting rod 3 so that the stirring wheel can rotate when the stirring frame rotates, thereby further increasing the effect of breaking up the filter cake and simultaneously increasing the mixing effect of the filter cake and the alkali solution.

[0032] The connecting handle 5 is a cross structure, which is essentially formed by two cross-shaped connecting arms 32 , wherein the end of the connecting shaft 33 is connected to the end of the connecting arm 32 .

[0033] The crimping portion can rotate relative to the connecting shaft 33 within a certain range to adapt to the cooperation with the protrusion, thereby avoiding breaking up the filter cake by strong physical force.

[0034] In some further embodiments, the crimping portion includes a plurality of crimping units arranged at intervals along the axial direction of the connecting shaft 33 , and the crimping units include elastic plates 34 and non-elastic plates 35 arranged at intervals along the circumferential direction of the connecting shaft 33 .

[0035] The crimping unit includes an elastic plate 34 and a non-elastic plate 35. The elastic plate 34 can undergo a certain elastic deformation relative to the non-elastic plate 35 to adaptively and gradually break up the filter cake. The elastic plate 34 can be a rubber plate; the non-elastic plate 35 can be used to ensure the breaking up effect of the filter cake to avoid the hard agglomeration of the filter cake being difficult to break up and affecting the recovery of metal gallium. The non-elastic plate 35 can be a wooden or metal plate.

[0036] The connection between the elastic plate 34 and the non-elastic plate 35 and the connecting shaft 33 can be achieved through ear handles and pins. For example, the ear handles can be set on the outer wall of the connecting shaft 33, and the pins can pass through the ear handles and the elastic plate 34 or the non-elastic plate 35.

[0037] When the stirring wheel rotates, due to the existence of centrifugal force, the non-hinged edges of the elastic plate 34 and the non-elastic plate 35 are always in a state of being away from the connecting shaft 33, thereby cooperating with the protrusions on the inner wall of the reaction tank to break up the filter cake.

[0038] In some further embodiments, the stirring frame includes a rotating sleeve 42 , which is disposed at one end of the first connecting rod 2 away from the second connecting rod 3 , a rotating shaft 4 is rotatably disposed in the rotating sleeve 42 , and a turning plate 40 is disposed on the rotating shaft 4 .

[0039] The rotating sleeve 42 is directly connected to the rotating shaft 4 through a bearing so that the rotation of the rotating shaft 4 and the rotation of the stirring frame do not affect each other.

[0040] In other embodiments, it is preferred that the rotation of the rotating sleeve 42 is opposite to the rotation of the rotating shaft 4 .

[0041] One end of the rotating sleeve 42 is driven by a motor, and the other end of the rotating shaft 4 away from the motor is provided with another motor for driving the rotating shaft 4 to rotate.

[0042] The turning plate 40 on the rotating shaft 4 is used to reverse the slurry.

[0043] In some further embodiments, the flipping plate 40 is arranged in an arc shape, and the concave side of the flipping plate 40 faces the tangent direction of the rotation direction of the flipping plate 40 .

[0044] The concave side of the turning plate 40 is directed toward the tangent direction of the turning direction of the turning plate 40 to increase the turning strength of the slurry and ensure that the slurry is mixed more fully.

[0045] In some further embodiments, an articulated shaft 30 is provided on the connecting handle 5, one end of the articulated shaft 30 is connected to the connecting handle 5, and the other end passes through the second connecting rod 3; one end of the articulated shaft 30 passing through the second connecting rod 3 is provided with a first rotating wheel 31, and a second rotating wheel 41 is provided on the rotating shaft 4, and the first rotating wheel 31 is connected to the second rotating wheel 41 by a transmission belt, and the transmission belt is elastic.

[0046] In actual situations, the rotation of the stirring wheel relative to the second connecting rod 3 is achieved through the cooperation among the connecting handle 5 , the hinge shaft 30 , and the second connecting rod 3 .

[0047] When the rotating shaft 4 rotates, the second rotating wheel 41 rotates, and the first rotating wheel 31 and the second rotating wheel 41 are connected through an elastic transmission belt, thereby synchronously driving the stirring wheel to rotate.

[0048] It should be noted that the inner wall of the reaction tank has a smaller elliptical shape so that the transmission mechanism can be extended and retracted within a smaller range.

[0049] In some further embodiments, two groups of stirring wheels are symmetrically provided, wherein the diameter of the corresponding first rotating wheel 31 in one group of stirring wheels is smaller than the diameter of the second rotating wheel 41 , and the diameter of the corresponding first rotating wheel 31 in the other group of stirring wheels is larger than the diameter of the second rotating wheel 41 .

[0050] Two groups of stirring wheels are provided, and the transmission ratios of the first rotating wheel 31 and the second rotating wheel 41 corresponding to each group are different, so as to realize different rotation speeds of the two stirring wheels.

[0051] It should be noted that there are two sets of first connecting rods 2 and second connecting rods 3 corresponding to each set of stirring wheels.

[0052] In a second aspect, the present application also provides a method for recovering metallic gallium from lime slag, using any of the above devices, comprising: Step 1: After the impurity removal and filtration are completed, the newly built plate and frame filter press is switched to the water washing process, and hot water is used to wash 1 to 2 times, and the washing water is recycled for liquid replenishment, and then the filter cake is blown dry with compressed air; Step 2: Heat the alkali solution in the reaction tank of the reactor 1, put the filter cake after washing and drying into the reaction tank, and start stirring to break it up; Step 3: Start steam heating, raise the temperature to 100°C, and keep the temperature for 4 hours; Step 4: After the reaction is completed, the slurry in the reaction tank is sent to the original plate and frame filter press for filtration, the filtered filtrate is transported to the filtrate buffer tank, the filter cake is dispatched and stored centrally.

[0053] In some further embodiments, the temperature of the hot water in step 1 is 65 to 75° C.; the pressure of the compressed air is ≥ 0.5 MPa; and the concentration of the alkali solution in step 2 is 100 to 200 g / L.

[0054] The centrally stored filter cake can be transported to the lime slag yard.

[0055] Through the technical solution provided in this application, gallium in lime slag can be effectively recovered, the gallium content in the discharged lime slag can be reduced, and gallium loss can be reduced; see Figure 6 It can be seen from the test data that the technical solution provided in this application can reduce the gallium content in lime slag to about 0.50%, and the gallium recovery rate can reach 80%, thereby increasing gallium production, reducing production costs, and increasing economic benefits for the enterprise.

[0056] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the scope of protection created by this application.

Claims

1. A device for recovering metallic gallium from lime slag, comprising a reaction kettle (1), characterized in that: A stirring frame is rotatably provided inside the reactor (1), and a stirring wheel is rotatably provided on the stirring frame. The stirring wheel is elastically slidably arranged along a stirring center pointing toward the stirring frame; the stirring wheel abuts against the inner peripheral wall of the reactor (1) during rotation, and the cross-section of the inner wall of the reactor (1) perpendicular to the axis direction of the stirring frame is elliptical.

2. The device for recovering metallic gallium from lime slag according to claim 1, characterized in that: The stirring frame comprises a first connecting rod (2) and a second connecting rod (3) which are arranged radially, the first connecting rod (2) and the second connecting rod (3) being elastically sleeved and connected, and the stirring wheel being rotatably arranged at an end of the second connecting rod (3) away from the first connecting rod (2).

3. The device for recovering metallic gallium from lime slag according to claim 2, characterized in that: The stirring wheel comprises a connecting handle (5) and a connecting shaft (33); the connecting handle (5) is in a cross shape; the center of the connecting handle (5) is rotatably connected to the second connecting rod (3); the end of the connecting shaft (33) is connected to the end of the connecting handle (5); a crimping portion is hingedly provided on the connecting shaft (33); and a protrusion that cooperates with the crimping portion is provided on the inner peripheral wall of the reaction kettle (1).

4. The device for recovering metallic gallium from lime slag according to claim 3, characterized in that: The crimping portion comprises a plurality of crimping units arranged at intervals in the axial direction along the connecting shaft (33), and the crimping units comprise elastic plates (34) and non-elastic plates (35) arranged at intervals in the circumferential direction along the connecting shaft (33).

5. The device for recovering metallic gallium from lime slag according to claim 4, characterized in that: The stirring frame comprises a rotating sleeve (42), the rotating sleeve (42) being arranged at one end of the first connecting rod (2) away from the second connecting rod (3), a rotating shaft (4) being rotatably arranged in the rotating sleeve (42), and a turning plate (40) being arranged on the rotating shaft (4).

6. The device for recovering metallic gallium from lime slag according to claim 5, characterized in that: The turning plate (40) is arranged in an arc shape, and the concave side of the turning plate (40) faces the tangent direction of the turning direction of the turning plate (40).

7. The device for recovering metallic gallium from lime slag according to claim 6, characterized in that: The connecting handle (5) is provided with an articulated shaft (30), one end of the articulated shaft (30) is connected to the connecting handle (5), and the other end passes through the second connecting rod (3); the end of the articulated shaft (30) passing through the second connecting rod (3) is provided with a first rotating wheel (31), and the rotating shaft (4) is provided with a second rotating wheel (41), and the first rotating wheel (31) and the second rotating wheel (41) are connected via a transmission belt, and the transmission belt is elastic.

8. The device for recovering metallic gallium from lime slag according to claim 7, characterized in that: The stirring wheels are symmetrically provided in two groups, wherein the diameter of the first rotating wheel (31) corresponding to one group of stirring wheels is smaller than the diameter of the second rotating wheel (41), and the diameter of the first rotating wheel (31) corresponding to the other group of stirring wheels is larger than the diameter of the second rotating wheel (41).

9. A method for recovering metallic gallium from lime slag, characterized in that: The device according to any one of claims 1 to 8 comprises: Step 1: After the impurity removal and filtration are completed, the newly built plate and frame filter press is switched to the water washing process, and hot water is used to wash 1 to 2 times, and the washing water is recycled for liquid replenishment, and then the filter cake is blown dry with compressed air; Step 2: heating alkali solution in the reaction tank of the reaction kettle (1), placing the filter cake after washing and drying into the reaction tank, and starting stirring to break it up; Step 3: Start steam heating, raise the temperature to 100°C, and keep the temperature for 4 hours; Step 4: After the reaction is completed, the slurry in the reaction tank is sent to the original plate and frame filter press for filtration, the filtered filtrate is transported to the filtrate buffer tank, the filter cake is dispatched and stored centrally.

10. The method for recovering metallic gallium from lime slag according to claim 9, characterized in that: The temperature of the hot water in step 1 is 65 to 75° C.; the pressure of the compressed air is ≥0.5 MPa; and the concentration of the alkali solution in step 2 is 100 to 200 g / L.

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