Industrial waste sulfuric acid purification equipment and purification method thereof

Abstract

The invention discloses an industrial waste sulfuric acid purification device and a purification method thereof, comprising a purification tank, a sulfuric acid inlet, a sulfuric acid outlet, and also comprising: an activated carbon containing component, the activated carbon containing component comprising a swing shaft and a flip containing plate, the flip containing plate is hollow and filled with activated carbon and a gear, and a moving part is meshed on the outer side of the gear; an external docking component, a connecting part is arranged on the side of the flip containing plate, and the external docking component comprises a docking part arranged on the outer side of the purification tank; an anti-vibration component, comprising a carrier plate arranged at the bottom of a guide rail, and a vibration table that can move up and down is arranged on the upper end of the carrier plate. The invention can not only use waste acid to purify and recycle lithium iron phosphate battery powder, but also use activated carbon to reduce alkali consumption during neutralization, and the activated carbon can be easily recycled and regenerated after use.

Description

Technical Field

[0001] The invention relates to a purification device, in particular to an industrial waste sulfuric acid purification device and a purification method thereof. Background Art

[0002] In industrial production, waste acid is produced in the processes of nitration, esterification, sulfonation, alkylation, catalysis and gas drying of organic matter, or in the processes of titanium dioxide production, steel pickling and gas drying. The output of industrial waste acid increases year by year. In order to protect the environment and realize the comprehensive utilization of resources, the purification and reuse of waste acid has become a focus of policy planning and industry development.

[0003] Traditional lithium iron phosphate battery powder recycling processes all use fresh sulfuric acid as leaching acid, which is relatively expensive. Therefore, some engineers apply waste acid to the recycling of lithium iron phosphate battery powder to make full use of industrial waste acid and achieve maximum economic benefits. However, it was found that the alkali consumption was too large during neutralization and the overall cost was high. Therefore, the method of activated carbon adsorbing waste sulfuric acid was introduced to reduce the COD in waste sulfuric acid. However, in the process of activated carbon adsorbing waste sulfuric acid, it was found that the activated carbon would float above the sulfuric acid, and the used activated carbon was more difficult to recycle and would be mixed in the iron phosphate mixed slag at the back end, making it difficult to reuse.

[0004] Therefore, this case aims to provide an industrial waste sulfuric acid purification equipment and a purification method thereof, which can not only use waste acid to purify and recycle lithium iron phosphate battery powder, but also use activated carbon to reduce the alkali consumption during neutralization, and can make the activated carbon evenly mixed with waste sulfuric acid, and the activated carbon can be easily recycled and regenerated after use. Summary of the invention

[0005] The present invention provides an industrial waste sulfuric acid purification device and a purification method thereof, which can effectively solve the above problems.

[0006] The present invention is achieved in that:

[0007] An industrial waste sulfuric acid purification device comprises a purification tank for introducing waste sulfuric acid, the top of the purification tank is provided with a plurality of sulfuric acid inlets, the bottom of the purification tank is provided with a sulfuric acid outlet, and the industrial waste sulfuric acid purification device also comprises:

[0008] An activated carbon containing assembly, wherein two guide rails are arranged on the inner side of the purification tank, and the activated carbon containing assembly comprises a swing shaft movably inserted in the two guide rails, a flip containing plate is fixedly connected to the middle position of the swing shaft, the flip containing plate is hollow and filled with activated carbon, and two sides of the flip containing plate are respectively provided with a gear fixed to the swing shaft, and a moving part is meshed on the outer side of the gear, and when the moving part drives the gear to move, the gear drives the flip containing plate on the swing shaft to rotate and stir the waste sulfuric acid in the purification tank, so that the waste sulfuric acid is fully in contact with the activated carbon in the flip containing plate;

[0009] An external docking assembly, wherein a connecting piece is disposed on the side of the flip receiving plate, and the external docking assembly comprises a docking piece disposed on the outside of the purification tank. When the sulfuric acid in the purification tank is emptied, the docking piece is inserted into the purification tank and pushed into the inside of the connecting piece, so that the flip receiving plate is docked with the external feeding structure;

[0010] The anti-vibration component includes a carrier plate arranged at the bottom of the guide rail, and a vibration table which can move up and down is arranged at the upper end of the carrier plate. After the flipping receiving tray descends and applies pressure to the vibration table, the vibration table vibrates the activated carbon in the flipping receiving tray, so that the activated carbon shakes in the flipping receiving tray and partially leaks out of the flipping receiving tray.

[0011] As a further improvement, through holes with a smaller aperture than the activated carbon are provided on the upper and lower sides of the flip containment tray, and a plurality of chutes are provided on the inner side of the flip containment tray, and the length of the chutes is smaller than the inner diameter of the flip containment tray.

[0012] As a further improvement, the moving part includes a fixed tooth plate located on one side of the gear, the top of the fixed tooth plate extends and is fixed to the top of the inside of the purification tank, and a movable tooth plate is meshed on the other side of the gear. The top of the movable tooth plate is connected to a pushing member, and when the pushing member moves, it drives the movable tooth plate to move up or down.

[0013] As a further improvement, the connecting member includes an axial tube fixedly connected to the outer side of the flip accommodating disk, a one-way valve plate is arranged on the inner side of the axial tube, and the axial tube is flush with the docking member after being reset.

[0014] As a further improvement, the docking piece includes a pin with an inner diameter smaller than that of the shaft tube, the pin is driven by a driving motor, and the pin is embedded in the purification tank through a sealing sleeve.

[0015] As a further improvement, the vibration table includes a vibration plate that collides with the flip receiving plate, a plurality of holes are opened on the vibration plate, guide columns that cooperate with guide rails are arranged on both sides of the vibration plate, and the vibration plate is connected to the carrier plate through a plurality of springs.

[0016] As a further improvement, the spring is made of Hastelloy.

[0017] The present invention also provides an industrial waste sulfuric acid purification equipment method, using the industrial waste sulfuric acid purification equipment as described above, comprising the following steps:

[0018] S1: Pass industrial waste sulfuric acid into a purification device with 3%-10% activated carbon, and let the activated carbon adsorb the waste sulfuric acid to reduce the COD in the waste sulfuric acid from 1000-5000mg / L to 100-500mg / L;

[0019] S2: react the purified qualified industrial waste sulfuric acid with the slurried lithium iron phosphate battery powder at 80-95°C for 3-4h, add an oxidant during the reaction to oxidize the divalent iron ions into trivalent iron ions, and after the reaction, filter through a filter press to obtain a graphite and iron phosphate mixed slag and a leachate containing nickel, cobalt, manganese, iron, copper and aluminum, and the pH of the leachate is controlled at 1.5-3.5;

[0020] S3: The leachate is subjected to a Fenton reaction with a Fenton reagent to obtain a qualified feed solution, wherein the COD of the qualified feed solution is controlled at 10-50 mg / L, and the iron content is less than 100 mg / L;

[0021] S4: adding caustic soda flake solution to the qualified feed solution, controlling the pH value at 10.5-12, and the metal ion content less than 30 mg / L;

[0022] S5: The material liquid of S4 after the reaction is finely filtered and then passed through a precision filter, and then the material liquid is subjected to lithium precipitation operation, and the lithium carbonate product is obtained by centrifugation.

[0023] As a further improvement, the step S1 specifically includes: docking the docking piece with the connecting piece to allow the activated carbon to pass into the flip holding tray, driving the moving piece to allow the flip holding tray to reciprocate up and down while stirring the waste sulfuric acid, so that the waste sulfuric acid flows into the flip holding tray and is fully absorbed by the activated carbon.

[0024] As a further improvement, the step S1 further includes: the descending inverted receiving tray collides with the vibration table, and the rebound force of the vibration table causes the sulfuric acid and activated carbon in the inverted receiving tray to shake.

[0025] The beneficial effects of the present invention are:

[0026] In the conventional recovery process of lithium iron sulfate, most of them adopt the method of new sulfuric acid, but the cost of adopting this method is extremely high. If waste sulfuric acid is used, due to the high COD in the waste sulfuric acid, too much caustic soda needs to be used in the later stage, and the cost is difficult to reduce. Therefore, in the early step of the present invention, the waste sulfuric acid is first treated with activated carbon, which greatly reduces the COD in the waste sulfuric acid. In order to improve the contact effect between the activated carbon and the sulfuric acid and avoid the activated carbon floating on the top of the sulfuric acid, thereby affecting the absorption effect, the present invention adds an activated carbon containing component to contain the activated carbon in a flip containing plate. The waste sulfuric acid can enter the flip containing plate and the activated carbon will not be lost from the flip containing plate. The flip containing plate can move up and down through the rotating swing shaft and gear when the moving part moves, thereby realizing not only the change of the upper and lower position, but also the change of the circumferential position, and can fully contact with the sulfuric acid. Compared with most stirring structures, the activated carbon can contact and mix with the sulfuric acid in more dimensions, so that the COD of the waste sulfuric acid can be reduced to the required range.

[0027] In order to allow sulfuric acid to be poured into the flip containing plate and to be able to leak out from the flip containing plate after contacting the activated carbon, a through hole smaller than the activated carbon is provided on the flip containing plate of the present invention to allow sulfuric acid to flow in and out freely. In order to provide an attachment area for the activated carbon, a chute is also provided in the flip containing plate to allow the activated carbon to be retained in the chute, thereby preventing the activated carbon from accumulating in a certain area and affecting the contact area.

[0028] When the moving part moves, in order to ensure the accuracy of movement and also to enable the flipping and containing plate to rotate up and down and back and forth, the moving part of the present invention adopts the cooperation of a toothed plate and a gear, and can also realize its own rotation during the up and down movement of the gear, so that the flipping and containing plate can realize the change of height and turnover rate, thereby improving the contact effect between activated carbon and sulfuric acid.

[0029] Since the entire purification tank is basically in a sealed state, it is inconvenient to fill the activated carbon and replace it after use. Therefore, the present invention adds an external docking component, and when the flip receiving disk is reset, the connecting piece will also be reset to the original position. After the connecting piece is reset, the docking piece is connected to the connecting piece, so that the activated carbon can be introduced into the flip receiving disk or pulled out of the flip receiving disk, thereby achieving the purpose of replacing the activated carbon without opening the equipment. Moreover, since the movement of the flip receiving disk mainly depends on the rotation of the gear, the original number of teeth is rotated to reset when it is reset, so the docking effect of the connecting piece and the docking piece can be guaranteed.

[0030] During the matching process between the connecting piece and the docking piece, a one-way valve plate is provided on the shaft tube in the connecting piece. Under normal conditions, sulfuric acid and activated carbon will not overflow from this position. After the ejector pin of the docking piece is connected, the one-way valve plate will be pushed open, thereby allowing the channels of the docking piece and the connecting piece to be connected, so that the activated carbon can be introduced or extracted.

[0031] In the whole process of flipping and stirring the containing plate, the activity amplitude of the activated carbon is actually relatively small. Therefore, in order to increase the activity amplitude of the activated carbon and make it more active, the present invention provides an anti-vibration component on the basis of the activated carbon containing component. When the flip containing plate flips downward to the limit, it will collide with the vibration table on the anti-vibration component, so that the activated carbon inside is vibrated and changes its original position, making it more active, thereby improving the mixing effect with sulfuric acid and ensuring that the COD of the waste sulfuric acid is reduced to 500-1000mg / L.

[0032] There are many holes on the vibrating plate in the vibration table, so that sulfuric acid can flow up and down normally, and the downward flipping containing plate will cause vibration when it touches the vibrating plate, and under the action of the flipping containing plate and the resetting of the vibrating plate, the sulfuric acid will fluctuate up and down. Even if part of it is output through the holes, the wave vibration will make the fluctuation of sulfuric acid larger, thereby promoting the mixing of sulfuric acid and activated carbon without setting a stirring structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 It is a three-dimensional structural schematic diagram of the present invention.

[0035] Figure 2 It is a schematic diagram of the top structure of the present invention.

[0036] Figure 3 The present invention Figure 2 Cross-section view at AA in the middle.

[0037] Figure 4 It is a schematic structural diagram of the activated carbon containing assembly of the present invention.

[0038] Figure 5 It is a structural schematic diagram of the moving part of the present invention.

[0039] Figure 6 It is a structural schematic diagram of the docking piece of the present invention.

[0040] Figure 7 It is a structural schematic diagram of the anti-vibration component of the present invention.

[0041] In the figure:

[0042] Purification tank 1, guide rail 101, sulfuric acid inlet 2, sulfuric acid outlet 3, activated carbon containing component 10, swing shaft 11, flip containing plate 12, shaft tube 121, chute 122, through hole 123, gear 13, moving part 14, fixed gear plate 141, movable gear plate 142, pushing member 143, docking member 21, ejector pin 211, drive motor 212, sealing sleeve 213, anti-vibration component 30, carrier plate 31, vibration table 32, vibration plate 321, hole 322, guide column 323, spring 324. DETAILED DESCRIPTION

[0043] In order to make the embodiments of the present invention, all belong to the scope of protection of the present invention. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents the selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0044] In the description of the present invention, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as referring to the purpose, technical solutions and advantages of the methods. To be more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work indicate or imply relative importance or implicitly indicate the number of indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0045] Reference Figure 1 to Figure 7As shown, an industrial waste sulfuric acid purification device comprises a purification tank 1 for introducing waste sulfuric acid, the top of the purification tank 1 is provided with a plurality of sulfuric acid inlets 2, the bottom of the purification tank 1 is provided with a sulfuric acid outlet 3, and the industrial waste sulfuric acid purification device also comprises: an activated carbon containing component 10, the inner side of the purification tank 1 is provided with two guide rails 101, the activated carbon containing component 10 comprises a swing shaft 11 movably inserted in the two guide rails 101, a flip containing plate 12 is fixedly connected to the middle position of the swing shaft 11, the flip containing plate 12 is hollow and filled with activated carbon, and two sides of the flip containing plate 12 are respectively provided with a gear 13 fixed to the swing shaft 11, and the outer side of the gear 13 is meshed with a moving part 14, when the moving part 14 drives the gear 13 to move, the gear 13 drives the flip on the swing shaft 11 The holding tray 12 rotates and stirs the waste sulfuric acid in the purification tank 1, allowing the waste sulfuric acid to fully contact with the activated carbon in the flip holding tray 12; an external docking component, a connecting piece is arranged on the side of the flip holding tray 12, and the external docking component includes a docking piece 21 arranged on the outside of the purification tank 1. When the sulfuric acid in the purification tank 1 is emptied, the docking piece 21 is inserted into the purification tank 1 and pushed into the inside of the connecting piece, so that the flip holding tray 12 is docked with the external feeding structure; an anti-vibration component 30, including a carrier plate 31 arranged at the bottom of the guide rail 101, and a vibration table 32 that can move up and down is arranged on the upper end of the carrier plate 31. After the flip holding tray 12 descends and applies pressure to the vibration table 32, the vibration table 32 vibrates the activated carbon in the flip holding tray 12, so that the activated carbon shakes in the flip holding tray 12 and partially leaks out of the flip holding tray 12.

[0046] In the process of recycling waste sulfuric acid, the COD therein is as high as 1000-5000 mg / L. After sampling, it is found that the COD in the waste sulfuric acid is 3341 mg / L. After the activated carbon adsorption of this embodiment, the COD in the waste sulfuric acid can be reduced to 100-500 mg / L.

[0047] In the conventional recovery process of lithium iron sulfate, most of them use new sulfuric acid, but the cost of using this method is extremely high. If waste sulfuric acid is used, due to the high COD in the waste sulfuric acid, too much flake caustic soda is used in the later use of caustic soda, and the cost is difficult to reduce. Therefore, in the early step of the present invention, the waste sulfuric acid is first treated with activated carbon, which greatly reduces the COD in the waste sulfuric acid. In order to improve the contact effect between the activated carbon and the sulfuric acid and avoid the activated carbon floating on the sulfuric acid, thereby affecting the absorption effect, the present invention adds an activated carbon containing component 10, and the activated carbon is contained in the flip containing plate 12. The waste sulfuric acid can enter the flip containing plate 12 and the activated carbon will not be lost from the flip containing plate 12. The flip containing plate 12 can move up and down through the rotating swing shaft 11 and the gear 13 when the moving part 14 moves, thereby realizing not only the change of the upper and lower positions, but also the change of the circumferential position, and can fully contact with the sulfuric acid. Compared with most stirring structures, the activated carbon can be contacted and mixed with the sulfuric acid in more dimensions, so that the COD of the waste sulfuric acid can be reduced to the required range.

[0048] In order to allow sulfuric acid to be poured into the flip containing tray 12 and to be able to leak out from the flip containing tray 12 after contacting the activated carbon, the flip containing tray 12 of this embodiment is provided with through holes 123 with a smaller aperture than the activated carbon on the upper and lower sides, and a plurality of chutes 122 are provided on the inner side of the flip containing tray 12, and the length of the chute 122 is less than the inner diameter of the flip containing tray 12, wherein the flip containing tray 12 is provided with through holes 123 smaller than the activated carbon, so that sulfuric acid can flow in and out freely, and in order to provide an attachment area for the activated carbon, a chute 122 is further provided in the flip containing tray 12, so that the activated carbon can be retained in the chute 122, so as to prevent the activated carbon from accumulating in a certain area and affecting the contact area.

[0049] When the moving member 14 moves, in order to ensure the accuracy of movement and to enable the flipping and accommodating plate 12 to rotate up and down and forward and backward, the moving member 14 of this embodiment includes a fixed tooth plate 141 located on one side of the gear 13, and the top of the fixed tooth plate 141 extends and is fixed to the top of the inside of the purification tank 1, and the other side of the gear 13 is meshed with a movable tooth plate 142, and the top of the movable tooth plate 142 is connected to a pushing member 143, and when the pushing member 143 moves, it drives the movable tooth plate 142 to move up or down. The moving member 14 adopts the cooperation of the tooth plate and the gear 13, and can also realize its own rotation during the up and down movement of the gear 13, so that the flipping and accommodating plate 12 can achieve changes in height and turnover, thereby improving the contact effect between the activated carbon and sulfuric acid, wherein the fixed tooth plate 141 is always stationary, and the gear 13 mainly relies on the upward or downward movement of the movable tooth plate 142.

[0050] Since the entire purification tank 1 is basically in a sealed state, it is relatively inconvenient to fill the activated carbon and replace it after use. Therefore, the present invention adds an external docking component, and when the flip receiving disk 12 is reset, its connecting piece will also be reset to its original position. After the connecting piece is reset, the docking piece 21 is connected to the connecting piece, so that the activated carbon can be introduced into the flip receiving disk 12 or pulled out of the flip receiving disk 12, thereby achieving the purpose of replacing the activated carbon without opening the equipment. Moreover, since the movement of the flip receiving disk 12 mainly depends on the rotation of the gear 13, when resetting, it also rotates the original number of teeth to reset, so the docking effect of the connecting piece and the docking piece 21 can be guaranteed.

[0051] During the cooperation between the connecting member and the docking member 21, the connecting member includes a shaft tube 121 fixedly connected to the outer side of the flip accommodating disk 12, and a one-way valve plate is arranged on the inner side of the shaft tube 121. After the shaft tube 121 is reset, it is flush with the docking member 21. The docking member 21 includes a ejector pin 211 with an inner diameter smaller than the shaft tube 121. The ejector pin 211 is driven by a driving motor 212. The ejector pin 211 is embedded in the purification tank 1 through a sealing sleeve 213. Since the shaft tube 121 in the connecting member is provided with a one-way valve plate, sulfuric acid and activated carbon will not overflow from this position under normal conditions. After the ejector pin 211 of the docking member 21 is connected, the one-way valve plate will be pushed open, thereby connecting the channel between the docking member 21 and the connecting member, so that the activated carbon can be introduced or extracted.

[0052] In the whole process of flipping and stirring the holding plate 12, the activity range of the activated carbon is actually relatively small. Therefore, in order to increase the activity range of the activated carbon and make it more active, the present invention further provides an anti-vibration component 30 on the basis of the activated carbon holding component 10. When the flip holding plate 12 flips downward to the limit position, it will collide with the vibration table 32 on the anti-vibration component 30, so that the activated carbon inside is vibrated and changes its original position, making it more active, thereby improving the mixing effect with sulfuric acid and ensuring that the COD of the waste sulfuric acid is reduced to 100-500mg / L.

[0053] Specifically, the vibration table 32 includes a vibration plate 321 that collides with the flip accommodating plate 12, and a plurality of holes 322 are provided on the vibration plate 321. Guide columns 323 that cooperate with the guide rails 101 are provided on both sides of the vibration plate 321. The vibration plate 321 is connected to the carrier plate 31 through a plurality of springs 324. There are many holes 322 on the vibration plate 321 in the vibration table 32, so that sulfuric acid can flow up and down normally. The flip accommodating plate 12 that flips downward will vibrate the flip accommodating plate 12 when it contacts the vibration plate 321, and the sulfuric acid will fluctuate up and down under the action of the flip accommodating plate 12 and the resetting of the vibration plate 321. Even if part of it is output through the holes 322, the wave vibration caused will also increase the fluctuation of sulfuric acid, thereby promoting the mixing of sulfuric acid and activated carbon without providing a stirring structure. Among them, the spring 324 is made of Hastelloy to avoid being corroded by sulfuric acid.

[0054] Another embodiment of the present invention further provides an industrial waste sulfuric acid purification equipment method, using the industrial waste sulfuric acid purification equipment as described above, comprising the following steps:

[0055] S1: Pass industrial waste sulfuric acid into a purification device with 3%-10% activated carbon, and let the activated carbon adsorb the waste sulfuric acid to reduce the COD in the waste sulfuric acid from 1000-5000mg / L to 100-500mg / L;

[0056] S2: react the purified qualified industrial waste sulfuric acid with the slurried lithium iron phosphate battery powder at 80-95°C for 3-4h, the amount of sulfuric acid used is 0.3-0.5 times the sum of the theoretical molar amount of the total amount of iron and lithium in the lithium iron phosphate battery powder, and during the reaction, add oxidants such as hydrogen peroxide and sodium chlorate to oxidize the divalent iron ions into trivalent iron ions. After the reaction, filter press the mixture with a filter press to obtain a leachate containing a small amount of impurities such as graphite and iron phosphate and a small amount of nickel, cobalt, manganese, iron, copper, and aluminum, and the pH of the leachate is controlled at 1.5-3.5;

[0057] S3: The leachate is reacted with Fenton reagent to obtain a qualified liquid. The reaction mechanism describes the chemical reaction in Fenton reagent as follows: Fe 2+ + H2O2→Fe 3+ +OH - +OH·, Fenton reaction for persistent organic matter, especially aromatic compounds and some heterocyclic compounds that are difficult to oxidize with common reagents, are all non-selectively oxidized and degraded in front of Fenton reagent. The COD of qualified feed liquid is controlled at 10-50mg / L, and the iron content is less than 100mg / L;

[0058] S4: adding caustic soda flake solution to the qualified feed solution, controlling the pH value at 10.5-12, and the metal ion content less than 30 mg / L;

[0059] S5: The material liquid of S4 after the reaction is finely filtered and then passed through a precision filter, and then the material liquid is subjected to lithium precipitation operation, and the lithium carbonate product is obtained by centrifugation.

[0060] Furthermore, the step S1 specifically includes: docking the docking member 21 with the connecting member to allow the activated carbon to pass into the flip receiving tray 12, driving the moving member 14 to allow the flip receiving tray 12 to reciprocate up and down while stirring the waste sulfuric acid, so that the waste sulfuric acid flows into the flip receiving tray 12 and is fully absorbed by the activated carbon.

[0061] Furthermore, the step S1 also includes: the descending inverted receiving tray 12 collides with the vibration table 32 , and the rebound force of the vibration table 32 causes the sulfuric acid and activated carbon in the inverted receiving tray 12 to shake.

[0062] Among them, waste sulfuric acid is light yellow and has no turbidity. Gas escapes when the bottle cap is opened. 1% to 5% activated carbon is added for adsorption. The color of the solution is shown in the table below:

[0063]

[0064] From this, it can be seen that the use of 3% activated carbon can make the waste acid reach the conditions of leaching acid, and the COD of waste sulfuric acid has dropped to 458, which is in line with the range of 100-5000mg / L.

[0065] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An industrial waste sulfuric acid purification device, comprising a purification tank (1) for introducing waste sulfuric acid, the top of the purification tank (1) is provided with a plurality of sulfuric acid inlets (2), the bottom of the purification tank (1) is provided with a sulfuric acid outlet (3), characterized in that: The industrial waste sulfuric acid purification equipment also includes: An activated carbon containing assembly (10), wherein two guide rails (101) are arranged on the inner side of the purification tank (1), and the activated carbon containing assembly (10) comprises a swing shaft (11) movably inserted into the two guide rails (101), a flip containing plate (12) is fixedly connected to the middle position of the swing shaft (11), the flip containing plate (12) is hollow and filled with activated carbon, and two sides of the flip containing plate (12) are respectively provided with a gear (13) fixed to the swing shaft (11), and a moving member (14) is meshed on the outer side of the gear (13), and when the moving member (14) drives the gear (13) to move, the gear (13) drives the flip containing plate (12) on the swing shaft (11) to rotate and stir the waste sulfuric acid in the purification tank (1), so that the waste sulfuric acid is fully in contact with the activated carbon in the flip containing plate (12); An external docking assembly, wherein a connecting piece is disposed on the side of the flip receiving plate (12), and the external docking assembly comprises a docking piece (21) disposed on the outside of the purification tank (1). When the sulfuric acid in the purification tank (1) is emptied, the docking piece (21) is inserted into the purification tank (1) and pushed into the interior of the connecting piece, so that the flip receiving plate (12) is docked with the external feeding structure; The anti-vibration assembly (30) comprises a carrier plate (31) arranged at the bottom of the guide rail (101), and a vibration table (32) which can move up and down is arranged at the upper end of the carrier plate (31). After the flipping accommodating plate (12) moves downward and applies pressure to the vibration table (32), the vibration table (32) vibrates the activated carbon in the flipping accommodating plate (12), causing the activated carbon to shake in the flipping accommodating plate (12) and partially leak out of the flipping accommodating plate (12).

2. An industrial waste sulfuric acid purification equipment according to claim 1, characterized in that: Through holes (123) having a smaller diameter than the activated carbon are provided on the upper and lower sides of the flip accommodating plate (12), and a plurality of chutes (122) are provided on the inner side of the flip accommodating plate (12), wherein the length of the chutes (122) is smaller than the inner diameter of the flip accommodating plate (12).

3. An industrial waste sulfuric acid purification equipment according to claim 1, characterized in that: The moving member (14) comprises a fixed tooth plate (141) located on one side of the gear (13), the top of the fixed tooth plate (141) extending and fixed to the top of the inside of the purification tank (1), and the other side of the gear (13) is meshed with a movable tooth plate (142), the top of the movable tooth plate (142) is connected to a pushing member (143), and when the pushing member (143) moves, it drives the movable tooth plate (142) to move up or down.

4. An industrial waste sulfuric acid purification equipment according to claim 1, characterized in that: The connecting member comprises an axial tube (121) fixedly connected to the outside of the flip accommodating disk (12), a one-way valve plate is arranged on the inside of the axial tube (121), and the axial tube (121) is flush with the docking member (21) after being reset.

5. An industrial waste sulfuric acid purification equipment according to claim 4, characterized in that: The docking piece (21) comprises a pin (211) having an inner diameter smaller than that of the shaft tube (121); the pin (211) is driven by a driving motor (212); and the pin (211) is embedded in the purification tank (1) via a sealing sleeve (213).

6. The industrial waste sulfuric acid purification equipment according to claim 1, characterized in that: The vibration table (32) comprises a vibration plate (321) that collides with the flip receiving plate (12), a plurality of holes (322) are provided on the vibration plate (321), guide posts (323) that cooperate with the guide rails (101) are provided on both sides of the vibration plate (321), and the vibration plate (321) is connected to the carrier plate (31) via a plurality of springs (324).

7. The industrial waste sulfuric acid purification equipment according to claim 6, characterized in that: The spring (324) is made of Hastelloy.

8. A method for purifying industrial waste sulfuric acid, using an industrial waste sulfuric acid purification device as described in any one of claims 1 to 7, characterized in that: The following steps are included: S1: Pass industrial waste sulfuric acid into a purification device with 3%-10% activated carbon, and let the activated carbon adsorb the waste sulfuric acid to reduce the COD in the waste sulfuric acid from 1000-5000mg / L to 100-500mg / L; S2: react the purified qualified industrial waste sulfuric acid with the slurried lithium iron phosphate battery powder at 80-95°C for 3-4h, add an oxidant during the reaction to oxidize the divalent iron ions into trivalent iron ions, and after the reaction, filter through a filter press to obtain a graphite and iron phosphate mixed slag and a leachate containing nickel, cobalt, manganese, iron, copper and aluminum, and the pH of the leachate is controlled at 1.5-3.5; S3: The leachate is subjected to a Fenton reaction with a Fenton reagent to obtain a qualified feed solution, wherein the COD of the qualified feed solution is controlled at 10-50 mg / L, and the iron content is less than 100 mg / L; S4: adding caustic soda flake solution to the qualified feed solution, controlling the pH value at 10.5-12, and the metal ion content less than 30 mg / L; S5: The material liquid of S4 after the reaction is finely filtered and then passed through a precision filter, and then the material liquid is subjected to lithium precipitation operation, and the lithium carbonate product is obtained by centrifugation.

9. A method for purifying industrial waste sulfuric acid according to claim 8, characterized in that: The step S1 specifically comprises: docking the docking member (21) with the connecting member to allow the activated carbon to flow into the flip receiving plate (12), and driving the moving member (14) to allow the flip receiving plate (12) to reciprocate up and down while stirring the waste sulfuric acid, so that the waste sulfuric acid flows into the flip receiving plate (12) and is fully absorbed by the activated carbon.

10. A method for purifying industrial waste sulfuric acid according to claim 9, characterized in that: The step S1 further comprises: the descending inverted receiving tray (12) collides with the vibration table (32), and the rebound force of the vibration table (32) causes the sulfuric acid and activated carbon in the inverted receiving tray (12) to shake.

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