Device and method for efficiently recycling chemically crystallized antimony

Abstract

The invention provides a device for efficiently recovering chemically-crystallized antimony, which comprises a hollow closed container, an upper cover, a lower cover and a lower cover, and is characterized in that the hollow closed container comprises an upper hollow cavity and a lower hollow cavity; a first crystal discharge port is formed in the side wall of the bottom of the lower hollow cavity; the rotating motor penetrates through the wall surface of the upper hollow cavity and then drives a disc which is horizontally suspended in the upper hollow cavity to rotate; a stirring rod is arranged on the lower surface of the disc; the conical top straw-hat-shaped component is arranged below the stirring rod, and the lower bottom edge of the conical top straw-hat-shaped component is fixed at the joint of the upper hollow cavity and the lower hollow cavity through an annular sealing ring; a water passing hole is formed in the upper half part of the cone top of the cone top straw-hat-shaped component; the aeration disc is supported by one end of an aeration pipe extending into the bottom of the hollow closed container and is communicated with the hollow closed container; the other end of the aeration pipe is communicated with a gas outlet of the water-gas dual-purpose pump; aeration holes are formed in the upper surface of the aeration disc; the water-gas dual-purpose pump is also communicated with a residual liquid return pipe; the device has the characteristics of intelligent control, monitoring, secondary efficient recovery and the like.

Description

Technical Field

[0001] The invention belongs to the field of crystal separation, and in particular relates to a highly efficient device for recovering chemical crystallized antimony. Background Art

[0002] Antimony in water comes from a variety of sources. Natural weathering of antimony ore, mining, smelting, burning of fossil fuels and widespread use of antimony compounds increase the concentration of antimony in the geochemical environment, causing air, water and soil pollution. There is a large amount of metallic antimony pollution in the printing and dyeing industry, which mainly comes from polyester fiber, the printing and dyeing raw material, and additives such as ethylene glycol antimony added during the printing and dyeing process. At present, the more common way to deal with antimony in the environment is to remove antimony, usually by adsorption and coagulation / flocculation. However, the large amount of low-density sludge produced by the iron salt coagulation method is hazardous waste. There is secondary pollution.

[0003] In 2010, about 20% of the global antimony supply came from secondary utilization. At present, the recycling of antimony is mainly limited to the recovery of antimony-containing lead alloys from lead-acid battery recycling plants. Secondary antimony sources also include waste products such as antimony-containing flame retardant plastics, antimony glass and phosphors produced by waste fluorescent lamps. Antimony can also be recovered from catalytic cracking (FCC) catalysts or catalysts used to produce PET polymers. The above antimony recovery methods usually involve the separation of antimony-lead alloys, resulting in complex recovery steps and low production purity. In addition, the existing antimony crystallization recovery device draws on other crystallization reactors and has many defects: lack of automatic control and online monitoring functions, and insufficient intelligent operation; the control of parameters such as temperature, pH value, solution concentration, etc. during the reaction process may not be accurate enough, resulting in large fluctuations in product quality and difficulty in stable control; there may be environmental pollution problems such as incomplete wastewater treatment, low purity of crystallized products, and difficulty in controlling crystal forms, which affect the safety and health of the production environment and the surrounding environment.

[0004] Therefore, a new antimony recovery device with the characteristics of intelligent control, monitoring, and secondary efficient recovery needs to be developed urgently. Summary of the invention

[0005] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a new antimony recovery device with the characteristics of intelligent control, monitoring, secondary high-efficiency recovery, etc.

[0006] To achieve the above-mentioned purpose and other related purposes, the present invention provides a highly efficient chemical crystallization antimony recovery device, comprising a hollow closed container for containing an antimony solution to be crystallized, characterized in that the hollow closed container comprises an upper and a lower hollow cavity with different inner diameters, the inner diameter of the upper hollow cavity is larger than the inner diameter of the lower hollow cavity; a first crystallization discharge port is provided on the side wall of the bottom of the lower hollow cavity; a crystallization discharge port valve is provided on the first crystallization discharge port; a rotating motor passes through the wall of the upper hollow cavity and drives a disc horizontally suspended in the upper hollow cavity to rotate, and a plurality of stirring rods extending below the liquid surface are provided on the lower surface of the disc; the plurality of stirring rods are sequentially spaced along the first diameter of the disc;

[0007] A conical straw hat-shaped component is arranged below the stirring rod, and its lower bottom edge is fixed to the connection between the upper and lower hollow cavities through an annular sealing ring; the upper half of the conical top of the conical straw hat-shaped component is provided with a plurality of water holes;

[0008] An aeration plate is provided coaxially below the conical straw hat-shaped component, and the aeration plate is supported and connected with one end of an aeration pipe extending from the bottom of the hollow closed container; the other end of the aeration pipe passes through the hollow closed container and is connected with the air outlet of the water-air dual-purpose pump; a plurality of aeration holes are provided on the upper surface of the aeration plate;

[0009] The water inlet and the water outlet of the water-gas dual-purpose pump are respectively connected with the residual liquid outlet arranged on the side wall of the bottom of the upper hollow cavity and the residual liquid inlet arranged on the side wall of the bottom of the lower hollow cavity through the residual liquid reflux pipe.

[0010] Preferably, the plurality of stirring rods are disposed on the lower surface of the disk on both sides of the symmetry axis with a second diameter perpendicular to the first diameter as the symmetry axis.

[0011] Preferably, the angle between the stirring rod and the lower surface of the disk is 30 to 60°, and the stirring rods on both sides of the symmetry axis are arranged on the lower surface of the disk on both sides of the symmetry axis in opposite directions; the stirring rod is L-shaped, including a long arm and a short arm, and the angle between the two arms is 90 to 150°; the long arm is a straight rod or a curved rod, and the short arm is a straight rod.

[0012] Preferably, a pH sensor is inserted into a detection tube extending from the side wall of the upper hollow cavity; and a pH detector is electrically connected to the pH sensor.

[0013] Preferably, the residual liquid reflux pipe connected to the water-gas dual-purpose pump and the residual liquid water inlet is provided with an antimony solution water injection port, and a water injection valve is provided on the port.

[0014] Preferably, a alkali liquid tank is connected to the lower hollow cavity through a alkali liquid pipe; and a alkali liquid control pump is provided on the alkali liquid pipe.

[0015] Preferably, the alkali solution control pump is electrically connected to the pH detector.

[0016] Preferably, a drainage outlet is provided on the wall surface of the lower hollow cavity at the same height as the residual liquid water inlet.

[0017] Preferably, a second crystallization outlet is further provided on the wall surface of the lower hollow cavity at a height lower than the residual liquid water inlet: the hollow closed container is suspended on a bracket; and the second crystallization outlet is provided with a crystallization outlet valve.

[0018] A method for recovering chemically crystalline antimony using the above-mentioned high-efficiency chemically crystalline antimony recovery device comprises the following steps:

[0019] S1: Close all valves, open the water injection valve, inject the antimony solution to be crystallized into the device from the antimony solution water injection port, the liquid level is higher than the top of the lower hollow cavity and lower than the residual liquid outlet, and close the water injection valve;

[0020] S2: adding seed crystals in advance into the lower cavity, turning on the rotary motor and the water-air dual-purpose pump, and aerating the air into the device through the aeration disk;

[0021] S3: During the reaction crystallization process, the pH detector and the pH sensor cooperate to monitor the pH value in the device in real time, and control the amount of alkali solution pumped into the device by adjusting the alkali solution control pump;

[0022] S4: After the water in the device circulates for a certain period of time, the rotating motor and the water-gas dual-purpose pump are turned off; the crystallized antimony will flow to the bottom of the upper and lower hollow cavities respectively, and most of the water will be discharged by opening the drainage valves at the drainage outlets; after opening all the crystallization outlet valves, the crystallized antimony will be discharged through the first crystallization outlet and the second crystallization outlet.

[0023] The highly efficient chemical crystallization antimony recovery device provided in this case has the following beneficial effects:

[0024] 1) A conical straw hat-shaped component in the device facilitates the flow of crystals to the bottom;

[0025] 2) The alkali solution control pump and the pH detector in the device work together to control the addition of acid and alkali to maintain the pH value in the water at the optimal crystallization state of antimony, thereby improving the crystallization efficiency;

[0026] 3) The water reflux pipe in the device can effectively avoid the problem of secondary pollution caused by the incomplete extraction of antimony in the sewage and its discharge. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the device of the present invention;

[0028] Figure 2 It is a schematic cross-sectional view of the device of the present invention;

[0029] Figure 3 It is a schematic diagram of a conical straw hat-shaped component;

[0030] Figure 4 Left view for the disc and stirring rod connection;

[0031] Figure 5 This is a bottom view of the connection between the disc and the stirring rod;

[0032] Figure 6 This is a top view of the aeration plate;

[0033] Figure 7 It is a schematic diagram when the long arm of the L-shaped stirring rod is a straight rod;

[0034] Figure 8 It is a schematic diagram when the long arm of the L-shaped stirring rod is a curved rod;

[0035] Among them: 1-hollow closed container; 1a-upper hollow cavity; 1b-lower hollow cavity; 2-first crystallization outlet; 2a-crystallization outlet valve; 3-rotating motor; 4-disc; 4a-first diameter; 4b-second diameter; 5-stirring rod; 6-conical straw hat-shaped component; 6a-lower bottom edge; 6b-annular sealing ring; 6c-water hole; 7-residual liquid reflux pipe; 7a-residual liquid outlet; 7b-residual liquid inlet; 8-water and gas dual-purpose pump; 9-pH sensor; 10-detection tube; 11-pH detector; 12-antimony solution injection port; 13-water injection valve; 14-alkali solution tank; 14a-alkali solution control pump; 15-drainage outlet; 16-second crystallization outlet; 17-aeration pipe; 17a-aeration disk; 17b-aeration hole. DETAILED DESCRIPTION

[0036] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0037] See also Figure 1-5 The structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents disclosed in the specification for people familiar with this technology to understand and read, and are not used to limit the limiting conditions for the implementation of the present invention, so they have no substantial technical significance. Any modification of the structure, change of the proportional relationship or adjustment of the size, without affecting the effects and purposes that can be achieved by the present invention, should still fall within the scope of the technical content disclosed by the present invention. At the same time, the terms such as "top", "bottom", "upper", "lower", "inside", "outside", etc. quoted in this specification are only for the convenience of description, and are not used to limit the scope of the implementation of the present invention. The change or adjustment of their relative relationship should also be regarded as the scope of the implementation of the present invention without substantially changing the technical content.

[0038] Embodiment 1:

[0039] like Figure 1-6 As shown, the present invention provides a highly efficient chemical crystallization antimony recovery device, comprising a hollow closed container 1 (the top is easily sealed by a threaded cover, etc., not shown in the figure) for containing an antimony solution to be crystallized, characterized in that the hollow closed container 1 comprises an upper and a lower hollow cavity (1a, 1b) with different inner diameters, the inner diameter of the upper hollow cavity 1a is larger than the inner diameter of the lower hollow cavity 1b; a first crystallization discharge port 2 is provided on the side wall of the bottom of the lower hollow cavity; a crystallization discharge port valve 2a is provided on the first crystallization discharge port 2; a rotating motor 3 passes through the wall of the upper hollow cavity 1a and drives a disc 4 horizontally suspended in the upper hollow cavity 1a to rotate, and a plurality of stirring rods 5 extending below the liquid surface are provided on the lower surface of the disc; the plurality of stirring rods 5 are sequentially spaced along the first diameter 4a of the disc 4;

[0040] A conical straw hat-shaped component 6 (metal part) is arranged below the stirring rod, and its lower bottom edge 6a is fixed to the connection between the upper and lower hollow cavities (1a, 1b) through an annular sealing ring 6b; the upper half of the conical top of the conical straw hat-shaped component 6 is provided with a plurality of water holes 6c, and the diameter of the water holes is adjusted according to the particle size of the crystallized antimony;

[0041] An aeration plate 17a is provided coaxially below the conical straw hat-shaped component 6, and the aeration plate 17a is supported and connected with one end of an aeration pipe extending from the bottom of the hollow closed container; the other end of the aeration pipe 17 passes through the hollow closed container and is connected with the air outlet of the water-air dual-purpose pump; a plurality of aeration holes 17b are provided on the upper surface of the aeration plate;

[0042] The water inlet and outlet of the water-gas dual-purpose pump are respectively connected to the residual liquid outlet 7a arranged on the side wall of the bottom of the upper hollow cavity and the residual liquid inlet 7b arranged on the side wall of the bottom of the lower hollow cavity through the residual liquid reflux pipe 7.

[0043] A plurality of stirring rods 5 are disposed on the lower surface of the disk on both sides of the symmetry axis with the second diameter 4b perpendicular to the first diameter 4a as the symmetry axis. The angle between the stirring rod 5 and the lower surface of the disk is 30-60°, and the stirring rods 5 on both sides of the symmetry axis are disposed on the lower surface of the disk on both sides of the symmetry axis in opposite directions. A pH sensor 9 is inserted into a detection tube 10 extending from the side wall of the upper hollow cavity; a pH detector 11 is electrically connected to the pH sensor 9. An antimony solution water injection port 12 is provided on the residual liquid reflux pipe 7 connected to the residual liquid water inlet 7b by the water-gas dual-purpose pump 8, and a water injection valve 13 is provided on the antimony solution water injection port. An alkali liquid tank 14 is connected to the lower hollow cavity through an alkali liquid pipe; an alkali liquid control pump 14a is provided on the alkali liquid pipe. The alkali liquid control pump 14a is electrically connected to the pH detector 11. A water outlet 15 is provided on the wall of the lower hollow cavity 1b at the same height as the residual liquid water inlet 7b. A second crystallization outlet 16 is also provided on the wall surface of the lower hollow cavity 1b at a height lower than the residual liquid inlet 7b. The hollow closed container 1 is suspended on a bracket; the second crystallization outlet 16 is provided with a crystallization outlet valve 2a. The alkali liquid in the alkali liquid tank 14 is one or more of sodium hydroxide, sodium bicarbonate, ammonia water, potassium hydroxide and potassium bicarbonate.

[0044] Embodiment 2:

[0045] The stirring rod in Example 1 is replaced by an L-shaped stirring rod, which includes a long arm and a short arm, and the angle between the two arms is 90-150°; the long arm is a straight rod, and the short arm is a straight rod; the direction of the short arm is consistent with the rotation direction of the disk 4.

[0046] Embodiment 3:

[0047] The long arm in Example 2 is replaced by an arc rod, and the rest remains unchanged.

[0048] Embodiment 4:

[0049] The method for antimony crystallization using any one of the devices in Examples 1 to 3 comprises the following steps:

[0050] S1: Close all valves, open the water injection valve 13, inject the antimony solution to be crystallized into the device from the antimony solution water injection port 12, the liquid level is higher than the top of the lower hollow cavity and lower than the residual liquid outlet 7a, and close the water injection valve 13;

[0051] S2: Add seed crystals in advance into the lower cavity, turn on the rotary motor 3 and the water-air dual-purpose pump, and aerate the air into the device through the aeration disk 17a;

[0052] S3: During the reaction crystallization process, the pH detector 11 cooperates with the pH sensor 9 to monitor the pH value in the device in real time, and controls the amount of alkali solution pumped into the device by adjusting the alkali solution control pump 14a;

[0053] S4: After the water in the device circulates for a certain period of time, turn off the rotating motor 3 and the water-gas dual-purpose pump; the crystallized antimony will flow to the bottom of the upper and lower hollow cavities respectively, and open the drainage valves at the drainage outlets to discharge most of the water; after opening all the crystallization outlet valves 2a, the crystallized antimony will be discharged through the first crystallization outlet 2 and the second crystallization outlet 16.

[0054] The alkali solution in the alkali solution tank 14 is one or more of sodium hydroxide, sodium bicarbonate, ammonia water, potassium hydroxide and potassium bicarbonate.

[0055] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. An efficient chemical crystallization antimony recovery device, comprising a hollow closed container for containing an antimony solution to be crystallized, characterized in that: The hollow closed container comprises an upper and a lower hollow cavity with different inner diameters, wherein the inner diameter of the upper hollow cavity is larger than the inner diameter of the lower hollow cavity; a first crystal discharge port is provided on the side wall of the bottom of the lower hollow cavity; and a crystal discharge port valve is provided on the first crystal discharge port; A rotating motor passes through the wall of the upper hollow cavity and drives a disk horizontally suspended in the upper hollow cavity to rotate, and a plurality of stirring rods extending below the liquid surface are arranged on the lower surface of the disk; the plurality of stirring rods are sequentially spaced along the first diameter of the disk; A conical straw hat-shaped component is arranged below the stirring rod, and its lower bottom edge is fixed to the connection between the upper and lower hollow cavities through an annular sealing ring; the upper half of the conical top of the conical straw hat-shaped component is provided with a plurality of water holes; An aeration plate is provided coaxially below the conical straw hat-shaped component, and the aeration plate is supported and connected with one end of an aeration pipe extending from the bottom of the hollow closed container; the other end of the aeration pipe passes through the hollow closed container and is connected with the air outlet of the water-air dual-purpose pump; a plurality of aeration holes are provided on the upper surface of the aeration plate; The water inlet and the water outlet of the water-gas dual-purpose pump are respectively connected with the residual liquid outlet arranged on the side wall of the bottom of the upper hollow cavity and the residual liquid inlet arranged on the side wall of the bottom of the lower hollow cavity through the residual liquid reflux pipe.

2. The highly efficient chemical crystallization antimony recovery device according to claim 1 is characterized in that: A plurality of stirring rods are disposed on the lower surface of the disk on both sides of the symmetry axis with a second diameter perpendicular to the first diameter as the symmetry axis.

3. The high-efficiency chemical crystallization antimony recovery device according to claim 2 is characterized in that: The angle between the stirring rod and the lower surface of the disk is 30 to 60 degrees, and the stirring rods on both sides of the symmetry axis are arranged on the lower surface of the disk on both sides of the symmetry axis in opposite directions; the stirring rod is L-shaped, including a long arm and a short arm, and the angle between the two arms is 90 to 150 degrees; the long arm is a straight rod or an arc rod, and the short arm is a straight rod.

4. The highly efficient chemical crystallization antimony recovery device according to claim 3 is characterized in that: A pH sensor is inserted into a detection tube extending from the side wall of the upper hollow cavity; and a pH detector is electrically connected to the pH sensor.

5. The highly efficient chemical crystallization antimony recovery device according to claim 4 is characterized in that: The residual liquid reflux pipe connected to the water-gas dual-purpose pump and the residual liquid water inlet is provided with an antimony solution water injection port, and the antimony solution water injection port is provided with a water injection valve.

6. The highly efficient chemical crystallization antimony recovery device according to claim 5 is characterized in that: A lye tank is connected with the lower hollow cavity through a lye pipe; and a lye control pump is arranged on the lye pipe.

7. The highly efficient chemical crystallization antimony recovery device according to claim 6 is characterized in that: The alkali solution control pump is electrically connected to the pH detector.

8. The highly efficient chemical crystallization antimony recovery device according to claim 7 is characterized in that: A water outlet is arranged on the wall surface of the lower hollow cavity at the same height as the residual liquid water inlet.

9. The highly efficient chemical crystallization antimony recovery device according to claim 8 is characterized in that: A second crystallization outlet is also arranged on the wall surface of the lower hollow cavity at a height lower than the residual liquid water inlet; the hollow closed container is suspended on a bracket; and the second crystallization outlet is provided with a crystallization outlet valve.

10. A method for recovering chemical crystallized antimony using the highly efficient chemical crystallized antimony recovery device according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1: Close all valves, open the water injection valve, inject the antimony solution to be crystallized into the device from the antimony solution water injection port, the liquid level is higher than the top of the lower hollow cavity and lower than the residual liquid outlet, and close the water injection valve; S2: adding seed crystals in advance into the lower cavity, turning on the rotary motor and the water-air dual-purpose pump, and aerating the air into the device through the aeration disk; S3: During the reaction crystallization process, the pH detector and the pH sensor cooperate to monitor the pH value in the device in real time, and control the amount of alkali solution pumped into the device by adjusting the alkali solution control pump; S4: After the water in the device circulates for a certain period of time, the rotating motor and the water-gas dual-purpose pump are turned off; the crystallized antimony will flow to the bottom of the upper and lower hollow cavities respectively, and most of the water will be discharged by opening the drainage valves at the drainage outlets; after opening all the crystallization outlet valves, the crystallized antimony will be discharged through the first crystallization outlet and the second crystallization outlet.

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