Apparatus for electrolytic recovery of antimony and method for electrolytic recovery of antimony using same

Abstract

The present invention provides an electrolytic recovery apparatus for electrolytically recovering antimony from a solution containing antimony, the electrolytic recovery apparatus comprising: an electrolytic cell configured to accommodate the solution; at least one cathode disposed within the electrolytic cell; at least one anode disposed within the electrolytic cell; and at least one diaphragm separating a cathode-side region including the at least one cathode from an anode-side region including the at least one anode. The present invention also provides a method for electrolytically recovering antimony, the method comprising: (A) a leaching step of leaching an antimony-containing raw material with a lixiviant to produce a leachate containing antimony; and (B) an electrolysis step of introducing the leachate into the aforementioned electrolytic recovery apparatus to electrodeposit antimony.

Description

Electrolytic recovery apparatus for antimony and electrolytic recovery method for antimony using the same

[0001] The present invention relates to an antimony electrolytic recovery apparatus and a method for electrolytically recovering antimony using the same.

[0002] Antimony (Sb) is attracting attention as a material for compound semiconductors, and its demand is increasing. Conventionally, crude antimony is produced by a dry method through a smelting process using antimony-containing pyrophosphate (Sb2S3) as a raw material, and then antimony is obtained by methods such as electrolysis.

[0003] However, in the case of antimony production by this dry method, a large amount of antimony is lost during the production process, the energy cost consumed when recovering antimony is high, and the problem of air pollution emissions arose due to the operation of the dry furnace for the dry method.

[0004] The present invention aims to provide an electrolytic recovery apparatus and method for antimony that has lower antimony loss compared to the dry method, and lowers energy costs and air pollution emissions.

[0005] In addition, the present invention aims to provide an apparatus and method for the electrolytic recovery of antimony that can prevent the problem of reduced antimony recovery rate caused by redissolving electrodeposited antimony with by-products (e.g., thiosulfates, etc.) during the process of electrolytically recovering antimony.

[0006] In addition, the present invention aims to provide an antimony electrolytic recovery apparatus and method capable of reducing electrolytic short circuits while increasing current efficiency in the electrolytic reaction.

[0007] In addition, the present invention aims to provide an electrolytic recovery method for antimony that can reduce the amount of auxiliary materials used and process costs by reusing the trace liquid generated during electrolysis as a leachate.

[0008] One aspect of the present invention relates to an electrolytic recovery apparatus for electrolytically recovering antimony from an antimony-containing solution, comprising: an electrolytic cell for receiving said solution; one or more cathodes disposed within said electrolytic cell; one or more anodes disposed within said electrolytic cell; and one or more diaphragms separating a cathode-side region including said one or more cathodes and an anode-side region including said one or more anodes.

[0009] One embodiment of the present invention may provide an electrolytic recovery device in which the diaphragm is made of an ion-exchangeable polymer.

[0010] One embodiment of the present invention may provide an electrolytic recovery device in which the catholyte and the anolyte are separated by the diaphragm.

[0011] One embodiment of the present invention may provide an electrolytic recovery device in which an anode and an anode-side electrolyte are disposed inside the diaphragm, and a cathode and a cathode-side electrolyte are disposed outside the diaphragm.

[0012] One embodiment of the present invention can provide an electrolytic recovery device in which the level of the anode-side electrolyte inside the diaphragm is lower than the level of the cathode-side electrolyte outside the diaphragm.

[0013] One embodiment of the present invention may provide an electrolytic recovery device in which the diaphragm is fixed by a frame and mounted inside the frame.

[0014] One embodiment of the present invention may provide an electrolytic recovery device for an antimony aqueous solution, wherein the edge portion of the diaphragm is stitched and masked.

[0015] One embodiment of the present invention may provide an electrolytic recovery device in which the cathode is formed as a cathode plate which is a plate-shaped electrode, and a plurality of holes or concave portions are formed on the surface of the cathode plate.

[0016] One embodiment of the present invention may provide an electrolytic recovery device in which the plurality of concave portions are formed to extend in the longitudinal direction of the cathode plate and are regularly arranged in the width direction of the cathode plate.

[0017] One embodiment of the present invention may provide an electrolytic recovery device in which the plurality of concave portions are a grid-shaped concave portion formed by combining a plurality of rows of concave portions extending in the longitudinal direction of the cathode plate and a plurality of rows of concave portions extending in the width direction of the cathode plate.

[0018] One embodiment of the present invention may provide an electrolytic recovery device in which the plurality of holes are regularly arranged in a grid-shaped two-dimensional arrangement.

[0019] One embodiment of the present invention may provide an electrolytic recovery device in which the width of the hole or concave portion is 2 to 15 mm.

[0020] One embodiment of the present invention can provide an electrolytic recovery device in which the spacing between the plurality of holes or concave portions is uniform.

[0021] One embodiment of the present invention may provide an electrolytic recovery device in which the spacing between the plurality of holes or concave portions is 2 to 5 cm.

[0022] One embodiment of the present invention may provide an electrolytic recovery device in which the anode has a plurality of electrode rods extending in the longitudinal direction.

[0023] One embodiment of the present invention may provide an electrolytic recovery device in which the diameter of the electrode rod is 2 to 25 mm.

[0024] One embodiment of the present invention can provide an electrolytic device for an antimony aqueous solution in which the spacing between the electrode rods is uniform.

[0025] One embodiment of the present invention may provide an electrolytic recovery device in which the number of electrode rods is 10 to 15.

[0026] One embodiment of the present invention may provide an electrolytic recovery device in which the surface area of ​​the anode is 30% or less of the surface area of ​​the cathode.

[0027] One embodiment of the present invention may provide an electrolytic recovery device in which antimony is electrodeposited on the cathode.

[0028] Another aspect of the present invention relates to an electrolytic recovery method for electrolytically recovering antimony from an antimony-containing solution, comprising: (A) a leaching process in which a raw material containing antimony is leached into a leaching solution to produce a leaching solution containing antimony; and (B) an electrolytic process in which the leaching solution is introduced into the electrolytic recovery device described above to electrodeposit antimony.

[0029] One embodiment of the present invention may provide an electrolytic recovery method in which the raw material containing the antimony is antimony trioxide (Sb2O3), antimony trisulfide (Sb2S3), or a mixture thereof.

[0030] One embodiment of the present invention may provide an electrolytic recovery method in which the leaching solution is caustic soda (NaOH), sodium hydroxide (NaSH), or a mixture thereof.

[0031] One embodiment of the present invention may provide an electrolytic recovery method in which the leaching liquid comprises Na3SbS3.

[0032] One embodiment of the present invention can provide an electrolytic recovery method in which caustic soda and sodium hydroxide are recovered in the electrolytic process and reused as a leachate in the leaching process.

[0033] According to the present invention, by leaching a raw material containing antimony into the electrolytic drainage solution, antimony loss is reduced compared to the dry method, and energy costs and air pollution emissions can be reduced.

[0034] According to the present invention, by including a diaphragm to prevent the mixing of electrolyte between the anode and the cathode, the redissolution of antimony by by-products (e.g., thiosulfate, etc.) can be prevented.

[0035] According to the present invention, current efficiency in an electrolytic reaction can be increased by using a cathode and an anode of a specific structure.

[0036] According to the present invention, by adjusting the arrangement of the diaphragm, the electrolytic short phenomenon can be reduced.

[0037] According to the present invention, the amount of auxiliary materials used and process costs can be reduced by reusing the microliquid generated during electrolysis as a leachate for leaching antimony. When the microliquid is reused, the amount of new electrolyte added can be reduced, and an eco-friendly effect can also be obtained by reducing the amount of wastewater generated when adding new electrolyte.

[0038] FIG. 1 is a diagram showing the entire process of electrolytically recovering antimony according to one embodiment of the present invention.

[0039] FIG. 2 is a schematic diagram of an electrolytic recovery device for electrolytically recovering antimony according to one embodiment of the present invention.

[0040] FIG. 3 is a schematic diagram showing a diaphragm included in an electrolytic recovery device according to one embodiment of the present invention mounted inside a frame.

[0041] FIG. 4 is a schematic diagram showing a cathode plate included in an electrolytic recovery device according to one embodiment of the present invention.

[0042] FIG. 5 is a schematic diagram showing an anode included in an electrolytic recovery device according to one embodiment of the present invention.

[0043] Figure 6 is a photograph of a structure in which a cathode is placed inside a diaphragm.

[0044] Figure 7 is a photograph of a cathode with antimony electrodeposited when an anode is placed inside a diaphragm and the diaphragm is mounted outside the frame.

[0045] Figure 8 is a photograph showing a comparison of electrodeposition results when the shape of the cathode plate is different.

[0046] Figure 9 is a photograph showing a comparison of electrodeposition results when the shape of the cathode plate is different.

[0047] Figure 10 is a photograph showing a comparison of electrodeposition results when the shape of the anode is different.

[0048] The embodiments of the present invention are illustrative for the purpose of explaining the technical concept of the present invention. The scope of rights according to the present invention is not limited to the embodiments presented below or the specific description thereof.

[0049] The embodiments of the present invention are illustrative for the purpose of explaining the technical concept of the present invention. The scope of rights according to the present invention is not limited to the embodiments presented below or the specific description thereof.

[0050] In this specification, the length direction of "A" refers to the vertical direction of "A", the width direction of "A" refers to the horizontal direction of "A", and the length direction and width direction of "A" are perpendicular to each other.

[0051] The present invention will be described below with reference to the drawings.

[0052] FIG. 1 is a diagram showing the entire process of electrolytically recovering antimony according to one embodiment of the present invention.

[0053] Referring to FIG. 1, a method can be provided for leaching an antimony-containing raw material through a series of processes and electrolytically recovering antimony through an electrolytic process. According to this method, antimony can be recovered with high efficiency even at low energy costs, and the amount of auxiliary raw material used and process costs can be reduced. Below, each process will be described in detail with reference to FIG. 1.

[0054] Leaching process (S10)

[0055] Referring to FIG. 1, an electrolytic recovery method for electrolytically recovering antimony from an antimony-containing solution according to one embodiment of the present invention includes a leaching process (S10) in which a raw material containing antimony is leached into a leaching solution to produce a leaching solution containing antimony.

[0056] For example, the raw material containing the antimony above may be antimony trioxide (Sb2O3), antimony trisulfide (Sb2S3), or a mixture thereof.

[0057] For example, the above leachate may be caustic soda (NaOH), sodium hydroxide (NaSH), or a mixture thereof.

[0058] For example, when antimony trioxide is leached in caustic soda and sodium hydroxide, the leaching solution may contain Na3SbS3, for example, an aqueous solution of Na3SbS3, and the dissolution reaction during leaching is as shown in Reaction Scheme 1 below.

[0059] [Reaction Equation 1]

[0060] Sb2O3+ 6NaSH + 6NaOH → 2Na3SbS3+ 6NaOH + 3H2O

[0061] Since the caustic soda produced by the reaction can be reused as a leachate, the amount of auxiliary raw materials used is reduced.

[0062] Antimony can be electrodeposited using the generated Na3SbS3 aqueous solution by the electrolytic process (S20) described later, and thus recovered, for example, as antimony metal. At this time, sodium hydroxide is also generated along with caustic soda and can be reused as a leaching solution, thereby reducing the overall input and usage of auxiliary raw materials and reducing process costs.

[0063] For example, when antimony trisulfide is leached with caustic soda and sodium hydroxide, the leaching solution may contain Na3SbS3, for example, an aqueous solution of Na3SbS3, and the dissolution reaction during leaching is as shown in Reaction Scheme 2 below.

[0064] [Reaction Equation 2]

[0065] Sb2S3+ 3NaSH + 3NaOH → 2Na3SbS3+ 3H2O

[0066] Antimony can be electrodeposited using the generated Na3SbS3 aqueous solution by the electrolytic process (S20) described later, and thus, for example, antimony metal can be recovered. At this time, sodium hydroxide is also generated along with caustic soda, and since it can be reused as a leaching solution, the overall input and usage of auxiliary raw materials are reduced, thereby reducing process costs.

[0067] In addition, in the case of antimony trisulfide, sodium hydroxide is also produced along with caustic soda by the electrolytic process (S20) described later, and considering reaction equation 2, it can be seen that sodium hydroxide (NaSH) actually increases by the electrolytic process (see reaction equation 3). Therefore, when the concentration of sodium hydroxide in the leaching solution and electrolyte decreases, sodium hydroxide can be generated by leaching antimony trisulfide and electrolyzing it to control the concentration of sodium hydroxide.

[0068] Therefore, since almost no auxiliary materials are used during electrolytic electrodeposition by leaching antimony into caustic soda and sodium hydroxide, if only the initial amount is input, it can be continuously reused as a leaching solution and electrolyte.

[0069] Electrolysis process (S20)

[0070] Referring to FIG. 1, an electrolytic recovery method for electrolytically recovering antimony from an antimony-containing solution according to one embodiment of the present invention includes an electrolytic process (S20) in which the leaching solution from the leaching process (S10) is introduced into an electrolytic recovery device described later to electrodeposit antimony.

[0071] The electrolytic reaction equation of the electrolytic process (S20) is the same as the following reaction equation 3.

[0072] [Reaction Equation 3]

[0073] 2Na3SbS3+ 6NaOH + 3H2O → 2Sb + 6NaSH + 6NaOH + 3 / 2O2

[0074] Caustic soda and sodium hydroxide are recovered in the electrolytic process (S20) and can be reused as the leachate in the leaching process (S10).

[0075] However, in the electrolytic cell where the electrolytic process is performed, if sodium hydroxide is oxidized while the operation is in progress, Na2S2 is produced (Reaction Scheme 4 below), and Na2S2 is oxidized to produce thiosulfate (Na2S2O3) (Reaction Scheme 5 below).

[0076] [Reaction Equation 4]

[0077] 4NaSH + O2 → 2Na2S2 + 2H2O

[0078] [Reaction Equation 5]

[0079] 2Na2S2 + 3O2 → 2Na2S2O3

[0080] Na2S2 and thiosulfate (Na2S2O3) generated by reaction schemes 4 and 5 redissolve antimony electrodeposited on the cathode (see reaction schemes 6 and 7 below), and the current efficiency and antimony recovery rate are reduced due to the generation of Na2S2 and thiosulfate.

[0081] [Reaction Equation 6]

[0082] 3Na2S2 + 2Sb → 2Na3SbS3

[0083] [Reaction Equation 7]

[0084] 3Na2S2O3+ 2Sb + 3Na2S → 2Na3SbS3+ 3Na2SO3

[0085] Accordingly, in the present disclosure, by using an electrolytic recovery device including a diaphragm, the incorporation of Na2S2 and thiosulfate through diaphragm separation can be prevented, thereby reducing the redissolution of antimony.

[0086] FIG. 2 is a schematic diagram of an electrolytic recovery device for electrolytically recovering antimony according to one embodiment of the present invention.

[0087] Referring to FIG. 2, an electrolytic recovery device (1) for electrolytically recovering antimony from an antimony-containing solution according to one embodiment of the present invention comprises an electrolytic cell (60) for receiving said solution, one or more cathodes (10) disposed within the electrolytic cell (60), one or more anodes (20) disposed within the electrolytic cell (60), and one or more diaphragms (50) dividing a cathode-side region including one or more cathodes (10) and an anode-side region including one or more anodes (20).

[0088] diaphragm (50)

[0089] The process according to the electrolytic recovery device (1) is a diaphragm electrolysis process using a diaphragm (50), and the diaphragm (50) can be made of a polymer capable of ion exchange.

[0090] For example, the diaphragm (50) is made of polypropylene (PP) material and can maintain high chemical stability and durability in alkaline solutions.

[0091] For example, the diaphragm (50) is 0.2cc / cm 2 It has an air permeability of less than 9.5, allowing for stable separation performance while minimizing liquid exchange between the inside and outside of the diaphragm, thereby enabling ion exchange.

[0092] For example, the cathode-side electrolyte (30) and the anode-side electrolyte (40) can be separated by a diaphragm (50). In the electrolytic reaction of FIG. 1 described above, sodium hydroxide (NaSH) and Na2S2 contained in the electrolyte may be oxidized to produce Na2S2 and thiosulfate (Na2S2O3), and finally, thiosulfate may be produced (see reaction schemes 4 and 5 below).

[0093] [Reaction Equation 4]

[0094] 4NaSH + O2 → 2Na2S2 + 2H2O

[0095] [Reaction Equation 5]

[0096] 2Na2S2 + 3O2 → 2Na2S2O3

[0097] Na2S2 and thiosulfate (Na2S2O3) generated by reaction schemes 4 and 5 redissolve the antimony electrodeposited on the cathode (10) (see reaction schemes 6 and 7 below), and the current efficiency and the recovery rate of antimony are reduced due to the generation of Na2S2 and thiosulfate.

[0098] [Reaction Equation 6]

[0099] 3Na2S2 + 2Sb → 2Na3SbS3

[0100] [Reaction Equation 7]

[0101] 3Na2S2O3+ 2Sb + 3Na2S → 2Na3SbS3+ 3Na2SO3

[0102] To solve these problems, the present disclosure performs separation of the cathode layer region and the anode side region by means of a diaphragm (50), thereby preventing the incorporation of Na2S2 and thiosulfate into the cathode layer region including the cathode (10) on which antimony is electrodeposited, and thereby reducing the redissolution of antimony.

[0103] For example, an anode (20) and an anode-side electrolyte (40) may be placed inside the diaphragm (50), and a cathode (10) and a cathode-side electrolyte (30) may be placed outside the diaphragm (50). For example, (unlike in FIG. 2) a cathode (10) and a cathode-side electrolyte (30) may be placed inside the diaphragm, and an anode (20) and an anode-side electrolyte (40) may be placed outside the diaphragm (50). For example, the anode-side electrolyte (40) and the cathode-side electrolyte (30) may be the same.

[0104] The effect may vary depending on whether the negative electrode (10) or the positive electrode (20) is placed inside the diaphragm (50).

[0105] For example, if a cathode is placed inside the diaphragm, the diaphragm may swell due to the electrodeposition of antimony on the cathode, or the antimony electrodeposited on the cathode may detach and fall to the bottom of the diaphragm (see Fig. 6). Consequently, a short circuit of the electrolytic cell is required to remove the antimony plate that has fallen to the bottom of the diaphragm, and since the process can only be resumed after the antimony plate is removed, productivity may decrease.

[0106] Furthermore, swelling of the diaphragm can cause a short circuit between the diaphragm and the cathode, and antimony may be electrodeposited on the frame in which the diaphragm is placed, potentially reducing the antimony recovery rate. Additionally, the short circuit between the cathode and the diaphragm may be exacerbated by the antimony electrodeposited on the frame.

[0107] On the other hand, as shown in FIG. 2, when the anode (20) is placed inside the diaphragm (50), even if the antimony plate electrodeposited on the cathode (10) falls downward due to a load or other reasons, it falls to the bottom of the electrolytic cell (60), so a short circuit due to the fall of the antimony plate does not occur.

[0108] For example, the level of the positive electrode electrolyte (40) inside the diaphragm (50) may be lower than the level of the negative electrode electrolyte (30) outside the diaphragm (50). By maintaining the level of the negative electrode electrolyte (30) higher than that of the positive electrode electrolyte (40), the amount of the negative electrode electrolyte (30) flowing into the positive electrode electrolyte (40) through the diaphragm (50) can be reduced (for example, only about 10 volume% or less (relative to the content of the negative electrode electrolyte newly flowing into the electrolytic cell)), thereby preventing mixing between the negative electrode electrolyte (30) and the positive electrode electrolyte (40). Accordingly, the mixing of Na2S2 and thiosulfate (Na2S2O3) generated in the positive electrode region into the negative electrode region can be prevented, thereby reducing the redissolution of antimony electrodeposited on the negative electrode (10).

[0109] FIG. 3 is a schematic diagram showing a diaphragm included in an electrolytic recovery device according to one embodiment of the present invention mounted inside a frame.

[0110] Referring to FIG. 3 together with FIG. 2, the diaphragm (50) may be fixed by the frame (70) and mounted inside the frame (70). For example, (unlike in FIG. 3) the diaphragm may be fixed by the frame and mounted outside the frame.

[0111] The effect may vary depending on whether the diaphragm (50) is mounted on the outside or inside of the frame (70).

[0112] For example, when a diaphragm is mounted outside the frame, swelling may occur at the bottom of the diaphragm. Consequently, the diaphragm comes into contact with the cathode, causing a short circuit, which may reduce the production efficiency of antimony electrodeposited on the cathode (see Fig. 7).

[0113] Therefore, by placing the positive electrode (20) inside the diaphragm (50) and mounting the diaphragm (50) inside the frame (70), short circuits can be reduced, and short circuits caused by the falling of the antimony plate from the negative electrode (10) can also be prevented. In addition, when the diaphragm is mounted outside the frame, operation by two or more people is required due to external bending work, whereas when the diaphragm (50) is mounted inside the frame (70), operation by one person is possible because only the replacement of the diaphragm (50) needs to be performed, thus providing ease of operation.

[0114] For example, the edge portion of the diaphragm (50) can be stitched and masked (80). Specifically, the edge portion of the diaphragm (50) can be precisely stitched using durable thread to primarily prevent leakage, and additionally masked to block fine gaps that may not be completely blocked by stitching.

[0115] If stitching and masking are not performed, even a small leak may occur, which may lead to the possibility of remelting and make it difficult to apply to operations.

[0116] Negative electrode (10)

[0117] For example, antimony can be electrodeposited on the cathode (10).

[0118] For example, the material of the cathode (10) is not particularly limited as long as it is used in the industry, but may be stainless steel, rolled steel (SS material), etc. For example, the steel may be SUS316 / 304.

[0119] FIG. 4 is a schematic diagram showing a cathode plate included in an electrolytic recovery device according to one embodiment of the present invention.

[0120] Referring to FIG. 4 together with FIG. 2, the cathode (10) is formed as a cathode plate, which is a plate-shaped electrode, and a plurality of holes (11) or concave portions (not shown in FIG. 4) may be formed on the surface of the cathode plate. Although not shown in FIG. 4, the cathode plate may be in the form of a flat plate without holes or concave portions formed therein (see FIG. 8).

[0121] Although not illustrated in FIG. 4, for example, a plurality of concave portions may be formed to extend in the longitudinal direction of the cathode plate and may be regularly arranged in the width direction of the cathode plate (see FIG. 8). For example, a plurality of concave portions may be formed to extend in the width direction of the cathode plate and may be regularly arranged in the longitudinal direction of the cathode plate.

[0122] For example, the cross-section of the concave portion may form a U-shape or a polygonal shape. For example, the cross-sections of the plurality of concave portions may all be the same or different.

[0123] For example, the plurality of concave portions may be grid-shaped concave portions formed by combining a plurality of rows of concave portions extending in the longitudinal direction of the cathode plate and a plurality of rows of concave portions extending in the width direction of the cathode plate. The plurality of rows of concave portions extending in the longitudinal direction of the cathode plate may be regularly arranged in the width direction of the cathode plate, and the plurality of rows of concave portions extending in the width direction of the cathode plate may be regularly arranged in the longitudinal direction of the cathode plate.

[0124] For example, the width of the above-mentioned concave portion may be 2 to 15 mm, but is not limited thereto.

[0125] For example, the width of the above-mentioned concave portion may be within the range of 0.5 to 2% based on the width direction length of the cathode plate.

[0126] For example, the spacing between the above-mentioned concave portions can be uniform.

[0127] For example, the spacing between the above-mentioned concave portions may be 2 to 5 cm, but is not limited thereto.

[0128] For example, the spacing between the above-mentioned concave portions may be 3 to 8 times the width of the concave portions.

[0129] For example, the shape of the plurality of holes (11) may be circular or polygonal, as shown in FIG. 4. For example, the shape of the plurality of holes (11) may all be the same or different, as shown in FIG. 4.

[0130] For example, the plurality of holes (11) can be regularly arranged in a grid-shaped two-dimensional arrangement.

[0131] For example, the width (d1) of the hole may be 2 to 15 mm, but is not limited thereto.

[0132] For example, the width (d1) of the hole may be within the range of 0.5 to 2% based on the width direction length (L1) of the cathode plate.

[0133] For example, the spacing (r1) between the plurality of holes (11) can be uniform.

[0134] For example, the spacing (r1) between the plurality of holes (11) may be 2 to 5 cm, but is not limited thereto.

[0135] For example, the spacing (r1) between the plurality of holes (11) may be 3 to 8 times the width (d1) of the holes (11).

[0136] If the gap between the holes or concave portions is within the range described above, if the gap is too wide, electrodeposition of antimony may be difficult, or if the gap is too narrow, more force is required to detach the antimony electrodeposited on the cathode plate using a hammer, etc., thereby preventing the problem of damage to the cathode plate and the hammer caused by impact during detachment.

[0137] <Experimental Example 1>

[0138] To verify the difference in effect when the formation of concave portions and the ratio of the spacing between concave portions and the width of the concave portions were varied, the electrodeposition results were compared by forming a flat plate and a cathode plate with concave portions (grooves) of 10 mm in width and varying spacing (see Fig. 8).

[0139] First, when a flat cathode plate was used, the formation of leaf-like crusts was prominent on the surface of the antimony electrodeposited on the cathode plate, and the electrodeposition efficiency of antimony was significantly low. This is thought to be due to the poor uniformity of the electrodeposition surface during the electrolytic deposition process. Consequently, the antimony electrodeposited on the cathode plate often falls to the bottom of the electrolytic cell, making recovery difficult.

[0140] Next, when a cathode plate with straight grooves at 10cm intervals was used, the electrodeposition efficiency was slightly improved compared to the flat plate, but some rough and cracked bark-like phenomena still appeared on the surface.

[0141] Meanwhile, when a cathode plate with straight grooves at 5 cm intervals is used, although the surface remains rough and cracked, the electrodeposition efficiency can be further improved compared to a cathode plate with straight grooves at 10 cm intervals.

[0142] <Experimental Example 2>

[0143] To verify the difference in effect when forming concave parts and holes, and when the arrangement of holes is different, the electrodeposition results were compared after forming a cathode plate with concave parts of width 10 mm formed in a grid and a cathode plate with holes of diameter 10 mm with different spacing between them (see Fig. 9).

[0144] First, when a cathode plate with lattice depressions was used, the electrodeposited antimony detached in a square shape. This means that while the pattern of the lattice depressions contributed to the formation of the initial electrodeposited material, it showed limitations in the structural stability of the electrodeposited layer.

[0145] Next, when a cathode plate with circular holes of 10 mm in diameter arranged regularly at intervals of 5 × 10 cm was used, it was confirmed that the detachment of electrodeposited antimony was significantly reduced compared to the case where grid indentations were formed, although the surface was somewhat rough. This means that forming holes can improve the adhesion of the electrodeposited material to the cathode plate.

[0146] Meanwhile, when a cathode plate with 10 mm diameter holes arranged regularly at 5×5 cm intervals was used, it was confirmed that there was almost no detachment from the electrodeposited surface and the uniformity and stability of the electrodeposition were significantly improved. This means that the adhesion of the electrodeposited material to the cathode plate was significantly increased and excellent surface quality was ensured.

[0147] positive electrode (20)

[0148] For example, the material of the anode (20) is not particularly limited as long as it is used in the industry, but may be stainless steel, rolled steel (SS material), etc. For example, the steel may be SUS316 / 304.

[0149] FIG. 5 is a schematic diagram showing an anode included in an electrolytic recovery device according to one embodiment of the present invention.

[0150] Referring to FIG. 5 together with FIG. 2, the anode (20) may have a plurality of electrode rods (21) extending in the longitudinal direction. The anode (20) may have a wire-shaped structure, thereby reducing its surface area; for example, the surface area of ​​the anode (20) may be 30% or less of the surface area of ​​the cathode (10). For example, the surface area of ​​the anode (20) may be 5% or more of the surface area of ​​the cathode (10). Through this, a higher current density can be generated compared to the case where the surface area is the same, thereby increasing current efficiency.

[0151] Although not illustrated in FIG. 5, for example, the cross-section of the electrode rod (21) may have a circular, elliptical, or polygonal shape. For example, the cross-sections of the plurality of electrode rods (21) may all be the same or different.

[0152] For example, the diameter (d2) of the electrode rod (21) may be 2 to 25 mm. For example, the number of electrode rods (21) may be 10 to 15.

[0153] For example, the diameter (d2) of the electrode rod (21) may be in the range of 0.5 to 2% based on the total length (L2) in the width direction of the anode.

[0154] For example, the spacing (r2) between the electrode rods (21) can be uniform.

[0155] For example, the anode (20) may have 10 to 15 electrode rods (21) with a diameter (d2) of 10 to 20 mm.

[0156] If the diameter and number of the electrode rods (21) are within the range described above, the electrodeposition efficiency of antimony can be further increased.

[0157] <Experimental Example 3>

[0158] To verify the difference in effect when the shape of the anode and the spacing or diameter of the electrode rods were varied, plate-shaped anodes and anodes with different diameters and numbers of electrode rods were formed and the electrode deposition results on the cathode plate were compared (see Fig. 10).

[0159] First, when using a plate-type anode, surface roughness of the antimony electrodeposited on the cathode plate was observed, and quality degradation occurred in some areas due to non-uniform electrodeposition. This indicates that the plate-type anode induced non-uniform conditions regarding current density and ion mobility, preventing the electrodeposited material from forming uniformly.

[0160] Next, in the case of the anode using 10 circular rod-shaped electrodes with a diameter of 12 mm, a cracked and somewhat rough appearance resembling tree bark was observed on the antimony surface electrodeposited on the cathode plate, but it was confirmed that the electrodeposited material was attached relatively firmly and did not easily detach. This implies that the electrode rod shape contributed to the stability of the electrodeposited material by maintaining a constant balance between the ion distribution and current density of the electrolyte.

[0161] Meanwhile, in the case of an anode using 13 circular rod-shaped electrodes with a diameter of 16 mm, the electrodeposition surface was formed very smoothly and uniformly, enabling flat electrodeposition. This means that the anode surface area within an appropriate range appropriately disperses the current density and simultaneously improves electrodeposition efficiency and surface uniformity.

[0162] Although embodiments of the present invention have been described above with reference to the attached drawings, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing its technical concept or essential features.

[0163] Therefore, the embodiments described above should be understood as exemplary in all respects and not limiting. The scope of the invention is defined by the claims rather than by the detailed description above, and all modifications or modified forms derived from the meaning and scope of the claims and equivalents thereof should be interpreted as being included within the scope of the invention.

Claims

1. An electrolytic recovery device for electrolytically recovering antimony from an antimony-containing solution, Electrolytic cell for accommodating the above solution, One or more cathodes disposed within the above electrolytic cell, One or more anodes disposed within the above-mentioned electrolytic cell, and An electrolytic recovery device comprising one or more diaphragms dividing a cathode-side region including one or more cathodes and an anode-side region including one or more anodes.

2. In Paragraph 1, The above diaphragm is an electrolytic recovery device made of an ion-exchangeable polymer.

3. In Paragraph 1, Electrolytic recovery device in which the catholyte and anolyte are separated by the above diaphragm.

4. In Paragraph 1, An electrolytic recovery device having an anode and an anode-side electrolyte disposed inside the diaphragm and a cathode and a cathode-side electrolyte disposed outside the diaphragm.

5. In Paragraph 4, Electrolytic recovery device in which the level of the anode-side electrolyte inside the diaphragm is lower than the level of the cathode-side electrolyte outside the diaphragm.

6. In Paragraph 1, The above-mentioned diaphragm is fixed by a frame and is mounted inside the frame, forming an electrolytic recovery device.

7. In Paragraph 1, The edge portion of the above diaphragm is stitched and masked, an electrolytic recovery device.

8. In Paragraph 1, The above cathode is formed as a cathode plate, which is a plate-shaped electrode, and Electrolytic recovery device having a plurality of holes or depressions formed on the surface of the above-mentioned cathode plate.

9. In Paragraph 8, An electrolytic recovery device in which the plurality of concave portions are formed to extend in the longitudinal direction of the cathode plate and are regularly arranged in the width direction of the cathode plate.

10. In Paragraph 8, The electrolytic recovery device, wherein the plurality of concave portions are a grid-shaped concave portion formed by combining a plurality of rows of concave portions extending in the longitudinal direction of the cathode plate and a plurality of rows of concave portions extending in the width direction of the cathode plate.

11. In Paragraph 8, The above-mentioned plurality of holes are regularly arranged in a grid-shaped two-dimensional arrangement, an electrolytic recovery device.

12. In Paragraph 8, An electrolytic recovery device having a hole or depression with a width of 2 to 15 mm.

13. In Paragraph 8, Electrolytic recovery device in which the spacing between the above-mentioned plurality of holes or depressions is uniform.

14. In Paragraph 8, An electrolytic recovery device in which the spacing between the plurality of holes or depressions is 2 to 5 cm.

15. In Paragraph 1, The above-mentioned anode is an electrolytic recovery device having a plurality of electrode rods extending in the longitudinal direction.

16. In Paragraph 15, Electrolytic recovery device having a diameter of 2 to 25 mm for the electrode rod.

17. In Paragraph 15, Electrolytic recovery device in which the spacing between the electrode rods is uniform.

18. In Paragraph 15, An electrolytic recovery device having 10 to 15 electrode rods.

19. In Paragraph 1, An electrolytic recovery device in which the surface area of ​​the anode is 30% or less of the surface area of ​​the cathode.

20. In Paragraph 1, Electrolytic recovery device in which antimony is electrodeposited on the above-mentioned cathode.

21. (A) A leaching process for leaching a raw material containing antimony into a leaching solution to produce a leaching solution containing antimony; and (B) An electrolytic recovery method for electrolytically recovering antimony from an antimony-containing solution, comprising an electrolytic process of electrodepositing antimony by introducing a leaching solution into an electrolytic recovery device according to any one of claims 1 to 20.

22. In Paragraph 21, The above antimony-containing raw material is antimony trioxide (Sb2O3), antimony trisulfide (Sb2S3), or a mixture thereof, in an electrolytic recovery method.

23. In Paragraph 21, The above-mentioned leaching solution is caustic soda (NaOH), sodium hydroxide (NaSH), or a mixture thereof, in an electrolytic recovery method.

24. In Paragraph 21, The above leaching solution is an electrolytic recovery method containing Na3SbS3.

25. In Paragraph 21, Electrolytic recovery method in which caustic soda and sodium hydroxide are recovered in the above electrolytic process and reused as a leachate in the leaching process.

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