Industrial waste hydrochloric acid purification equipment and purification method thereof

Abstract

The invention discloses an industrial waste hydrochloric acid purification device and a purification method thereof, comprising a purification tank, a hydrochloric acid inlet, a hydrochloric acid outlet, and also comprising: a resin storage structure, comprising a bearing basket arranged in the middle of the purification tank, the bearing basket comprising a bearing area for bearing resin, and a flow area for allowing hydrochloric acid to pass through, the lower end of the bearing area is connected to a connecting pipe, the connecting pipe penetrates to the outside of the purification tank, a material guide cylinder is arranged on the connecting pipe located at the outer part of the purification tank, a punching piece is arranged at the end of the connecting pipe, and a heat preservation component is arranged in the connecting pipe; a supporting shaking material structure, comprising an external bonding component arranged on the outer side of the bearing basket, a shaking shaft is fixedly connected to the top of the external bonding component, and an oscillation component is arranged on the top of the shaking shaft. The invention can use waste acid to purify and recycle ternary battery powder, and can use resin to reduce alkali consumption during neutralization, and can also be more convenient during recycling and regeneration.

Description

Technical Field

[0001] The invention relates to hydrochloric acid purification equipment, in particular to industrial waste hydrochloric acid purification equipment 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 ternary battery powder uses fresh hydrochloric acid as leaching acid, which is relatively expensive. Therefore, some engineers apply waste acid to the recovery of ternary battery powder to make full use of industrial waste acid and achieve maximum economic benefits. However, it is found that the alkali consumption is too large during neutralization and the overall cost is high. Therefore, the resin adsorption of waste hydrochloric acid is introduced to reduce the COD in the waste hydrochloric acid. However, in the process of resin adsorption of waste hydrochloric acid, the resin is always in a solid state, and its contact efficiency is poor. It will be discharged together with the purified hydrochloric acid, which not only increases the difficulty of subsequent filter pressing, but also has a high loss rate.

[0004] Therefore, this case aims to provide an industrial waste hydrochloric acid purification equipment and a purification method thereof, which can not only use waste acid to purify and recycle ternary battery powder, but also use resin to reduce the alkali consumption during neutralization, and can keep the resin in a molten state and mix it with hydrochloric acid more evenly, and it can also be more convenient to recycle and regenerate. Summary of the invention

[0005] The present invention provides an industrial waste hydrochloric 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 hydrochloric acid purification device comprises a purification tank for introducing waste hydrochloric acid, the top of the purification tank is provided with a plurality of hydrochloric acid inlets, the bottom of the purification tank is provided with a hydrochloric acid outlet, and the industrial waste hydrochloric acid purification device also comprises:

[0008] The resin storage structure comprises a carrying basket arranged in the middle of the purification tank, the carrying basket comprises a carrying area for carrying the resin, and a flow area for passing the hydrochloric acid, the lower end of the carrying area is connected to a connecting pipe, the connecting pipe penetrates to the outside of the purification tank, a material guide cylinder is arranged on the connecting pipe located at the outer part of the purification tank, a material punching piece is arranged at the end of the connecting pipe, a heat preservation component is arranged in the connecting pipe, the external resin is driven into the connecting pipe through the material guide cylinder, the resin in the connecting pipe is kept in a molten state and gradually piled up in the carrying area, when the resin is filled to a preset amount, the material punching piece is pushed into the connecting pipe to block the position of the material guide cylinder to prevent the resin from retreating;

[0009] The supporting material shaking structure includes an external bonding component arranged on the outside of the carrying basket, two shaking shafts are fixedly connected to the top of the external bonding component, an oscillation component is arranged on the top of the shaking shaft, the oscillation component is located on the top of the purification tank and the top cover of the oscillation component is provided with an isolation cover, when the oscillation component is started, the shaking shaft is driven to shake, and when the shaking shaft shakes, the external bonding component and the carrying basket supported by it are driven to shake.

[0010] As a further improvement, the bearing area is made of high nickel-molybdenum steel, and the thickness of the bearing area is 8 mm to 12 mm.

[0011] As a further improvement, the flow area includes a first folded section that is in contact with the inner wall of the purification tank, the first folded section is extended downwardly to have a second folded section, the bottom of the second folded section is connected to the bearing area, and the opening size on the second folded section is larger than the opening size on the first folded section.

[0012] As a further improvement, a feed port is provided at the top of the connecting pipe, and the material guide cylinder includes an inclined bucket connected to the feed port, the inclined bucket is connected to a pump cavity, and a connecting bucket is integrally formed on the pump cavity, and the connecting bucket is connected to an external delivery pump.

[0013] As a further improvement, the punching piece includes a punching column arranged on the inner side of the end of the connecting tube, the punching column is connected to a boosting motor, and the fixed end of the boosting motor is fixedly connected to the connecting tube.

[0014] As a further improvement, the heat preservation component includes a conductive member arranged on the inner side wall of the connecting tube, the conductive member is attached to an electric heating glass plate, and the heating side of the electric heating glass plate faces the cavity of the connecting tube.

[0015] As a further improvement, the external fitting component includes a first shaking ring clamped on the top of the outer side of the load-bearing area, and a second shaking ring is also arranged at the bottom of the outer side of the load-bearing area. The first shaking ring and the second shaking ring are connected by an external rib, and a gasket is also arranged at the bottom of the second shaking ring between the connecting tube and the load-bearing area, and the shaking axis passes through the first folding section, the first shaking ring and the second shaking ring.

[0016] As a further improvement, the oscillation component includes a polarization motor connected to the shaking axis, and the two sides of the bottom of the polarization motor are connected to the top of the purification tank through two groups of return springs.

[0017] The present invention also provides a method for purifying industrial waste hydrochloric acid, comprising the above-mentioned industrial waste hydrochloric acid purification equipment, comprising the following steps:

[0018] S1: passing industrial waste hydrochloric acid into a purification device with resin, allowing the resin to adsorb the waste hydrochloric acid, reducing the COD in the waste hydrochloric acid from 1000-5000 mg / L to 100-500 mg / L;

[0019] S2: react the purified industrial waste hydrochloric acid with the slurried ternary battery powder at 80-95°C for 8-12h, add a reducing agent during the reaction to reduce the insoluble high-valent cobalt and manganese, and filter through a filter press after the reaction to obtain graphite slag and a leachate rich in nickel, cobalt, manganese, lithium, iron, copper and aluminum, and the pH of the leachate is controlled at 0.5-2.5;

[0020] S3: Add a metal element with stronger activity than copper metal to the leaching solution according to the copper content in the solution and the amount of liquid inlet to replace and remove copper, so that the copper content is ≤100-200mg / L;

[0021] S4: the copper-removed solution 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 content of iron ions is less than 100 mg / L;

[0022] S5: After the COD removal is qualified, the qualified liquid is heated to 60-80℃, and the soda ash solution is added at a rate of 0.15-0.5m³ / h. The end point pH is controlled at 4.0-5.0, so that the iron ion content is less than 30mg / L and the aluminum ion content is less than 30mg / L;

[0023] S6: The feed liquid of S5 after the reaction is finely filtered and then passed through a precision filter, and the subsequent feed liquid is extracted to obtain qualified nickel chloride, cobalt chloride, and manganese chloride products.

[0024] As a further improvement, the step S1 specifically includes: injecting the molten resin into the connecting tube through the material guide barrel, the resin in the connecting tube is kept in a molten state and gradually piled up in the load-bearing area, and when the resin is filled to a preset amount, the punch is pushed into the connecting tube to block the position of the material guide barrel to prevent the resin from retreating, and the resin is always located in the load-bearing area to react with hydrochloric acid.

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

[0026] In the conventional recycling process of ternary battery powder, most of them adopt new hydrochloric acid, but the cost of this method is extremely high. If waste hydrochloric acid is used, due to the high COD in the waste hydrochloric acid, too much soda ash will be needed in the later stage, and the cost is difficult to reduce. Therefore, in the early step, the present invention first uses activated carbon to treat the waste hydrochloric acid, which greatly reduces the COD in the waste hydrochloric acid. In order to allow the resin to contact with the hydrochloric acid in a molten state and avoid the resin from leaching directly into the later solution with the hydrochloric acid, the present invention adds a resin storage structure, and drives part of the resin into the connecting pipe through the guide cylinder. The resin in the connecting tube is kept in a molten state and gradually piled up in the load-bearing area. When the resin is filled to a preset amount, the punching piece is pushed into the connecting tube to block the position of the material guide barrel to prevent the resin from retreating, so that the resin can exist in the load-bearing area in a molten state and contact with the waste hydrochloric acid, and is always heated by the heat preservation component. When regeneration is required, the resin is extracted from the position of the material guide barrel by retreating the punching piece, which simplifies the resin recovery step. Therefore, while the resin reduces the COD of hydrochloric acid, it will not enter the lower leaching stage with the hydrochloric acid and cause further burden on the filtration step.

[0027] Since hydrochloric acid is a strong acid, plastic and other metals are easily corroded. However, if ceramics and glass are used, they cannot have a certain elasticity. Therefore, the bearing area of ​​the present invention adopts high-nickel-molybdenum steel, and its thickness is made thin, so that it can have a certain supporting strength and a certain elasticity that can be affected by external bonding components, thereby improving the practicality of the present invention.

[0028] In order to allow the hydrochloric acid to be largely concentrated in the load-bearing area during the initial material discharge stage, the present invention divides the flow area into two parts, and makes the opening of the first folding section smaller and the opening of the second folding section larger. Whether it is the initial material discharge or the subsequent material flow, the hydrochloric acid can flow more frequently in the second folding section, and can better contact and react with the resin, thereby improving the contact effect between the hydrochloric acid and the resin.

[0029] After the resin is discharged, in order to prevent the resin from retreating from the position of the material guide barrel, the fluid resin needs to be supported by a punching piece. Therefore, the present invention completely seals the end of the entire connecting tube through a punching column provided in the punching piece. On the one hand, it can isolate the position of the material guide barrel and the connecting tube to prevent the resin from retreating, and at the same time, it can prevent hydrochloric acid from flowing out of the position of the material guide barrel after reacting with the resin to cause leakage.

[0030] Although the resin is in a molten state when added to the equipment, it will soon become solid after it is cooled to room temperature and does not come into contact with hydrochloric acid. In order to prevent the resin from becoming solid and clogging in the connecting pipe, the present invention provides a heat preservation component in the connecting pipe, and heats the resin by heating the glass plate that will not be corroded by hydrochloric acid. Even if hydrochloric acid combines with the resin and penetrates into the connecting pipe later, it will not corrode the electric heating glass plate.

[0031] During the reaction stage of the resin and hydrochloric acid, it is inconvenient to set up a stirring structure because hydrochloric acid is a strong acid. Therefore, the reaction of the two mostly relies on time for reaction and mixing. However, if this method is used, if the penetration effect of hydrochloric acid is waited, the coordination speed with the resin is slow. Therefore, the present invention makes the bearing area thinner on the basis of the resin storage structure, and at the same time sets a supporting shaking material structure on the outside of the bearing area. The bearing area is vibrated by the oscillation component through the shaking shaft and the external bonding component. On the one hand, the resin in the bearing area can be activated to make it more fluid and react better with hydrochloric acid. On the other hand, the shaking external bonding component can increase the activity of hydrochloric acid, making it more active, so that it can have more contact with the resin, thereby reducing its COD to a lower level and meeting the COD standard.

[0032] When the resin is oscillated through the external bonding component, the first rocking ring and the second rocking ring are both arranged on the outside of the bearing area, and the only difference is that one is arranged at the bottom and the other is arranged at the top. By surrounding the head and tail positions, the active resin can always be downward during oscillation and is not easy to overflow. In order to avoid excessive deformation of the bearing area, an external rib is further arranged between the first rocking ring and the second rocking ring to standardize the shape of the bearing area and improve the tightness of the entire external bonding component. 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 The present invention Figure 3 Magnified view of area B in FIG.

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

[0039] Figure 6 It is a schematic diagram of the structure of the shaking shaft and the oscillation component of the present invention.

[0040] Figure 7 It is a schematic structural diagram of the external bonding component of the present invention (first viewing angle).

[0041] Figure 8 It is a schematic structural diagram of the external bonding component of the present invention (second viewing angle).

[0042] In the figure:

[0043] Purification tank 1, hydrochloric acid inlet 2, hydrochloric acid outlet 3, resin storage structure 10, carrying basket 11, carrying area 111, flow area 112, first folding section 1121, second folding section 1122, connecting pipe 12, material guide cylinder 13, inclined bucket 131, pump material cavity 132, connecting bucket 133, punching piece 14, punching column 141, booster motor 142, heat preservation component 15, conductive part 151, electric heating glass plate 152, supporting shaking material structure 20, external bonding component 21, first shaking ring 211, second shaking ring 212, external rib 213, gasket 214, shaking shaft 22, oscillation component 23, polarization motor 231, reset spring 232, isolation cover 24. DETAILED DESCRIPTION

[0044] 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.

[0045] 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.

[0046] Reference Figures 1 to 8 As shown, an industrial waste hydrochloric acid purification device comprises a purification tank 1 for introducing waste hydrochloric acid, the top of the purification tank 1 is provided with a plurality of hydrochloric acid inlets 2, the bottom of the purification tank 1 is provided with a hydrochloric acid outlet 3, and the industrial waste hydrochloric acid purification device also comprises: a resin storage structure 10, comprising a carrying basket 11 arranged in the middle of the purification tank 1, the carrying basket 11 comprises a carrying area 111 for carrying resin, and a flow area 112 for passing hydrochloric acid, the lower end of the carrying area 111 is connected to a connecting pipe 12, the connecting pipe 12 passes through the outside of the purification tank 1, a material guide cylinder 13 is arranged on the connecting pipe 12 located at the outer part of the purification tank 1, a punching piece 14 is arranged at the end of the connecting pipe 12, a heat preservation component 15 is arranged in the connecting pipe 12, and the external resin passes through The material guide cylinder 13 is driven into the connecting tube 12, and the resin in the connecting tube 12 is kept in a molten state and gradually piled up in the bearing area 111. When the resin is filled to a preset amount, the punching piece 14 is pushed into the connecting tube 12 to block the position of the material guide cylinder 13 to prevent the resin from retreating; a supporting shaking structure 20 includes an external bonding component 21 arranged on the outside of the bearing basket 11, and two shaking shafts 22 are fixedly connected to the top of the external bonding component 21. An oscillation component 23 is arranged on the top of the shaking shaft 22. The oscillation component 23 is located at the top of the purification tank 1 and the top cover of the oscillation component 23 is provided with an isolation cover 24. When the oscillation component 23 is started, it drives the shaking shaft 22 to shake, and when the shaking shaft 22 shakes, it drives the external bonding component 21 and the bearing basket 11 supported by it to shake.

[0047] In the conventional recycling process of ternary battery powder, most of them adopt new hydrochloric acid, but the cost of this method is extremely high. If waste hydrochloric acid is used, due to the high COD in the waste hydrochloric acid, too much soda ash will be needed in the later stage, and the cost is difficult to reduce. Therefore, in the early step, the present invention first uses activated carbon to treat the waste hydrochloric acid, which greatly reduces the COD in the waste hydrochloric acid. In order to make the resin contact with the hydrochloric acid in a molten state and avoid the resin from being leached directly into the later solution with the hydrochloric acid, the present invention adds a resin storage structure 10, and the resin is driven into the connecting pipe 12 through the guide cylinder 13. The resin is kept in a molten state and gradually piled up in the load-bearing area 111. When the resin is filled to a preset amount, the punching piece 14 is pushed into the connecting tube 12 to block the position of the guide barrel 13 to prevent the resin from retreating, so that the resin can exist in the load-bearing area 111 in a molten state and contact with the waste hydrochloric acid, and is always heated by the heat preservation component 15. When regeneration is required, the resin is extracted from the position of the guide barrel 13 by retreating the punching piece 14, which simplifies the resin recovery step. Therefore, while the resin reduces the COD of hydrochloric acid, it will not cause further burden on the filtration step when it enters the lower leaching stage with the hydrochloric acid.

[0048] Since hydrochloric acid is a strong acid, plastic and other metals are easily corroded. However, if ceramics and glass are used, they cannot have a certain elasticity. Therefore, the bearing area 111 of this embodiment is high-nickel-molybdenum steel, and the thickness of the bearing area 111 is 8mm~12mm. The bearing area 111 is made of high-nickel-molybdenum steel, and its thickness is made thin, so that it can have a certain supporting strength and a certain elasticity that can be affected by the external bonding component 21, thereby improving the practicality of the present invention. Preferably, the thickness of the bearing area 111 is 9mm.

[0049] In order to allow the hydrochloric acid to be largely concentrated at the position of the supporting area 111 during the initial material discharge stage, the flow area 112 of this embodiment includes a first folding section 1121 that is in contact with the inner wall of the purification tank 1, and the first folding section 1121 is extended downward to provide a second folding section 1122, and the bottom of the second folding section 1122 is connected to the supporting area 111, and the opening size on the second folding section 1122 is larger than the opening size on the first folding section 1121. The flow area 112 is divided into two parts, and the opening of the first folding section 1121 is made smaller, and the opening of the second folding section 1122 is made larger. Whether it is the initial material discharge or the subsequent material liquid flow, the hydrochloric acid can flow more frequently at the position of the second folding section 1122, and can better contact and react with the resin, thereby improving the contact effect between the hydrochloric acid and the resin.

[0050] During the resin loading or unloading stage, unloading is carried out through the material guide barrel 13, and its specific structure is: a feeding port is provided at the top of the connecting tube 12, and the material guide barrel 13 includes an inclined bucket 131 connected to the feeding port, and the inclined bucket 131 is connected to a pumping cavity 132. A connecting bucket 133 is integrally formed on the pumping cavity 132, and the connecting bucket 133 is connected to an external delivery pump. During the loading stage, the feed section of the molten resin is docked with the connecting bucket 133 to inject the resin, and during the material removal stage, the purpose can also be achieved by docking the extraction structure with the connecting bucket 133.

[0051] For ease of display, the connecting tube 12 shown in this embodiment has a relatively thick tube diameter. In actual use, the size of the connecting tube 12 will be set according to the amount of resin used. When the amount of resin used is large, the diameter of the connecting tube 12 can be appropriately increased, thereby increasing the storage capacity while increasing its supporting capacity. When the amount of resin used is small, the diameter of the connecting tube 12 can be reduced so that most of the resin is in the load-bearing area 111.

[0052] After the resin is discharged, in order to prevent the resin from retreating from the position of the material guide barrel 13, the fluid resin needs to be supported by the material punching piece 14. Therefore, the material punching piece 14 of this embodiment includes a material punching column 141 arranged on the inner side of the end of the connecting tube 12, and the material punching column 141 is connected to a booster motor 142. The fixed end of the booster motor 142 is fixedly connected to the connecting tube 12. The material punching column 141 arranged in the material punching piece 14 can completely seal the end of the entire connecting tube 12. On the one hand, it can isolate the position of the material guide barrel 13 and the connecting tube 12 to prevent the resin from retreating, and at the same time, it can prevent hydrochloric acid from flowing out of the position of the material guide barrel 13 after reacting with the resin to cause leakage.

[0053] Although the resin is in a molten state when added to the equipment, it will soon become solid after it is cooled to room temperature and does not react with hydrochloric acid. In order to prevent the resin from becoming solid and clogging in the connecting tube 12, the heat preservation component 15 of this embodiment includes a conductive member 151 arranged on the inner wall of the connecting tube 12, and the conductive member 151 is attached to an electric heating glass plate 152. The heating side of the electric heating glass plate 152 faces the cavity of the connecting tube 12. The heat preservation component 15 is arranged in the connecting tube 12, and the resin is heated by heating the glass plate that will not be corroded by hydrochloric acid. Even if hydrochloric acid combines with the resin and penetrates into the connecting tube 12 later, it will not corrode the electric heating glass plate 152.

[0054] During the reaction stage of the resin and hydrochloric acid, it is inconvenient to set up a stirring structure because hydrochloric acid is a strong acid. Therefore, the reaction of the two mostly relies on time for reaction and mixing. However, if this method is used, if the penetration effect of hydrochloric acid is waited, the coordination speed with the resin will be slow. Therefore, the present invention makes the bearing area 111 thinner on the basis of the resin storage structure 10, and at the same time sets a supporting shaking material structure 20 on the outside of the bearing area 111. The bearing area 111 is vibrated through the shaking shaft 22 and the external bonding component 21 through the oscillation component 23. On the one hand, the resin in the bearing area 111 can be activated to make it more fluid and react better with hydrochloric acid. On the other hand, the shaking external bonding component 21 can increase the activity of hydrochloric acid, making it more active, so that it can have more contact with the resin, thereby reducing its COD to a lower level and meeting the COD standard.

[0055] When the resin is oscillated by the external bonding component 21, two oscillation points are provided. Specifically, the external bonding component 21 includes a first shaking ring 211 clamped on the top of the outer side of the load-bearing area 111, and a second shaking ring 212 is also provided at the bottom of the outer side of the load-bearing area 111. The first shaking ring 211 and the second shaking ring 212 are connected by an external rib 213. The bottom of the second shaking ring 212 is also provided with a gasket ring 214 located between the connecting tube 12 and the load-bearing area 111. The shaking shaft 22 passes through the first folding section 1121, the first shaking ring 211 and the second shaking ring 212. The first rocking ring 211 and the second rocking ring 212 are both arranged on the outside of the bearing area 111, and the only difference is that one is arranged at the bottom and the other is arranged at the top. By surrounding the head and tail positions, the active resin can always be downward during oscillation and is not easy to overflow. In order to prevent the bearing area 111 from being excessively deformed, an outer rib 213 is further arranged between the first rocking ring 211 and the second rocking ring 212 to standardize the shape of the bearing area 111 and improve the tightness of the entire outer bonding component 21. The gasket 214 can increase the strength of the connecting tube 12 to support the entire bearing basket 11.

[0056] During the process of oscillating the bearing area 111 through the oscillation component 23, the oscillation component 23 includes a polarization motor 231 connected to the shaking shaft 22. The two sides of the bottom of the polarization motor 231 are connected to the top of the purification tank 1 through two sets of reset springs 232. When the polarization motor 231 drives the shaking shaft 22 to vibrate during oscillation, it can regulate its left and right formation through the reset spring 232 to prevent the shaking shaft 22 from frequently colliding with the opening of the purification tank 1, thereby preventing acid mist from overflowing from the through position of the shaking shaft 22, so that the shaking shaft 22 only vibrates in the up and down directions, and has less lateral movement.

[0057] Another embodiment of the present invention further provides a method for purifying industrial waste hydrochloric acid, comprising the above-mentioned industrial waste hydrochloric acid purification equipment, including the following steps:

[0058] S1: passing industrial waste hydrochloric acid into a purification device with resin, allowing the resin to adsorb the waste hydrochloric acid, reducing the COD in the waste hydrochloric acid from 1000-5000 mg / L to 100-500 mg / L;

[0059] S2: react the purified qualified industrial waste hydrochloric acid with the slurried ternary battery powder at 80-95°C for 8-12h, add reducing agents such as sodium thiosulfate and hydrogen peroxide during the reaction to reduce some insoluble high-valent cobalt and manganese, and after the reaction, filter through a filter press to obtain graphite slag and a leachate rich in nickel, cobalt, manganese, lithium, iron, copper and aluminum, and the pH of the leachate is controlled at 0.5-2.5;

[0060] S3: Add a metal element with stronger activity than copper metal to the leaching solution according to the copper content in the solution and the amount of liquid inlet to replace and remove copper, so that the copper content is ≤100-200mg / L;

[0061] S4: The copper-free solution undergoes a Fenton reaction with the Fenton reagent to obtain a qualified feed solution. The reaction mechanism describes the chemical reaction that occurs in the Fenton reagent: Fe 2+ + H2O2→Fe 3+ +OH - +OH·, Fenton reaction is used for persistent organic matter, especially aromatic compounds and some heterocyclic compounds that are difficult to oxidize with common reagents. In front of Fenton reagent, all of them are non-selectively oxidized and degraded. The COD of qualified feed liquid is controlled at 10-50mg / L, and the content of iron ions is less than 100mg / L;

[0062] S5: After the COD removal is qualified, aluminum removal operation is carried out. The qualified liquid is heated to 60-80℃, and soda solution is added at a rate of 0.15-0.5m³ / h. The end point pH is controlled at 4.0-5.0, so that the iron ion content is less than 30mg / L and the aluminum ion content is less than 30mg / L;

[0063] S6: The liquid of S5 after the reaction is finely filtered and then passed through a precision filter. The liquid is subsequently extracted to obtain qualified finished products such as nickel chloride, cobalt chloride, manganese chloride, etc.

[0064] Furthermore, the step S1 specifically includes: injecting the molten resin into the connecting tube 12 through the material guide barrel 13, the resin in the connecting tube 12 is kept in a molten state and gradually piled up in the bearing area 111, and when the resin is filled to a preset amount, the punching piece 14 is pushed into the connecting tube 12 to block the position of the material guide barrel 13 to prevent the resin from retreating, and the resin is always located in the bearing area 111 to react with hydrochloric acid.

[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 hydrochloric acid purification device, comprising a purification tank (1) for introducing waste hydrochloric acid, the top of the purification tank (1) is provided with a plurality of hydrochloric acid inlets (2), the bottom of the purification tank (1) is provided with a hydrochloric acid outlet (3), characterized in that: The industrial waste hydrochloric acid purification equipment also includes: The resin storage structure (10) comprises a carrying basket (11) arranged in the middle of a purification tank (1), the carrying basket (11) comprising a carrying area (111) for carrying the resin, and a flow area (112) for allowing hydrochloric acid to pass through, the flow area (112) comprising a first folding section (1121) in contact with the inner wall of the purification tank (1), the first folding section (1121) extending downwardly to be provided with a second folding section (1122), the bottom of the second folding section (1122) being connected to the carrying area (111), the size of the opening on the second folding section (1122) being larger than the size of the opening on the first folding section (1121), and the lower end of the carrying area (111) being connected to the A connecting tube (12) is connected, the connecting tube (12) penetrates to the outside of the purification tank (1), a material guide cylinder (13) is arranged on the connecting tube (12) located at the outside of the purification tank (1), a punching piece (14) is arranged at the end of the connecting tube (12), and a heat preservation component (15) is arranged in the connecting tube (12), and external resin is driven into the connecting tube (12) through the material guide cylinder (13), and the resin in the connecting tube (12) is kept in a molten state and gradually piled up in the bearing area (111), and when the resin is filled to a preset amount, the punching piece (14) is pushed into the connecting tube (12) to block the position of the material guide cylinder (13) to prevent the resin from retreating; The material-shaking support structure (20) comprises an external laminating component (21) arranged outside the carrying basket (11), the top of the external laminating component (21) is fixedly connected to two shaking shafts (22), the top of the shaking shaft (22) is provided with an oscillating component (23), the oscillating component (23) is located at the top of the purification tank (1) and the top cover of the oscillating component (23) is provided with an isolation cover (24), when the oscillating component (23) is started, the shaking shaft (22) is driven to shake, and when the shaking shaft (22) is shaken, the external laminating component (21) and the carrying basket (11) supported by it are driven to shake.

2. The industrial waste hydrochloric acid purification equipment according to claim 1, characterized in that: The bearing area (111) is made of high nickel-molybdenum steel, and the thickness of the bearing area (111) is 8 mm to 12 mm.

3. The industrial waste hydrochloric acid purification equipment according to claim 1, characterized in that: A material delivery port is provided at the top of the connecting pipe (12); the material guide cylinder (13) comprises an inclined bucket (131) connected to the material delivery port; the inclined bucket (131) is connected to a material pumping cavity (132); a connecting bucket (133) is integrally formed on the material pumping cavity (132); and the connecting bucket (133) is connected to an external delivery pump.

4. The industrial waste hydrochloric acid purification equipment according to claim 3, characterized in that: The punching piece (14) comprises a punching column (141) arranged on the inner side of the end of the connecting tube (12); the punching column (141) is connected to a boosting motor (142); and the fixed end of the boosting motor (142) is fixedly connected to the connecting tube (12).

5. The industrial waste hydrochloric acid purification equipment according to claim 1, characterized in that: The heat preservation component (15) comprises a conductive member (151) arranged on the inner side wall of the connecting tube (12); the conductive member (151) is attached to an electric heating glass plate (152); and the heating side of the electric heating glass plate (152) faces the cavity of the connecting tube (12).

6. The industrial waste hydrochloric acid purification equipment according to claim 1, characterized in that: The outer fitting component (21) comprises a first shaking ring (211) clamped on the top of the outer side of the bearing area (111); a second shaking ring (212) is also provided at the bottom of the outer side of the bearing area (111); the first shaking ring (211) and the second shaking ring (212) are connected via an outer rib (213); a gasket ring (214) is also provided at the bottom of the second shaking ring (212) and is located between the connecting tube (12) and the bearing area (111); and the shaking shaft (22) passes through the first folding section (1121), the first shaking ring (211) and the second shaking ring (212).

7. The industrial waste hydrochloric acid purification equipment according to claim 1, characterized in that: The oscillation component (23) comprises a polarization motor (231) connected to the shaking shaft (22), and the two sides of the bottom of the polarization motor (231) are connected to the top of the purification tank (1) via two sets of return springs (232).

8. A method for purifying industrial waste hydrochloric acid, comprising an industrial waste hydrochloric acid purification device according to any one of claims 1 to 7, characterized in that: The steps include: S1: passing industrial waste hydrochloric acid into a purification device with resin, allowing the resin to adsorb the waste hydrochloric acid, reducing the COD in the waste hydrochloric acid from 1000-5000 mg / L to 100-500 mg / L; S2: react the purified industrial waste hydrochloric acid with the slurried ternary battery powder at 80-95°C for 8-12h, add a reducing agent during the reaction to reduce the insoluble high-valent cobalt and manganese, and filter through a filter press after the reaction to obtain graphite slag and a leachate rich in nickel, cobalt, manganese, lithium, iron, copper and aluminum, and the pH of the leachate is controlled at 0.5-2.5; S3: Add a metal element with stronger activity than copper metal to the leaching solution according to the copper content in the solution and the amount of liquid inlet to replace and remove copper, so that the copper content is ≤100-200mg / L; S4: the solution after copper removal is subjected to Fenton reaction with 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 content of iron ions is less than 100 mg / L; S5: After the COD removal is qualified, the qualified liquid is heated to 60-80℃, and the soda ash solution is added at a rate of 0.15-0.5m³ / h. The end point pH is controlled at 4.0-5.0, so that the iron ion content is less than 30mg / L and the aluminum ion content is less than 30mg / L; S6: The feed liquid of S5 after the reaction is finely filtered and then passed through a precision filter, and the subsequent feed liquid is extracted to obtain qualified nickel chloride, cobalt chloride, and manganese chloride products.

9. A method for purifying industrial waste hydrochloric acid according to claim 8, characterized in that: The step S1 specifically comprises: injecting molten resin into the connecting tube (12) through a material guide cylinder (13), the resin in the connecting tube (12) being kept in a molten state and gradually piled up in the bearing area (111), and when the resin is filled to a preset amount, pushing the punch (14) into the connecting tube (12) to block the position of the material guide cylinder (13) to prevent the resin from retreating, so that the resin is always located in the bearing area (111) to react with the hydrochloric acid.

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