Iron removal device for nickel-cobalt-manganese sulfate solution and method for continuously removing iron ions in nickel-cobalt-manganese sulfate solution at low temperature

Abstract

Iron removal equipment for nickel-cobalt-manganese sulfate solution and nickel-cobalt-manganese sulfate solution A method for continuously removing iron ions from nickel-cobalt-manganese sulfate solutions at low temperatures is provided. In the iron device, a deferrous reactor (2) and an aging reactor (9) are provided, and the deferrous reactor (2) An agitator (3) is provided in the reactor (9), and an agitator (7) is provided in the reactor (9). The iron removal reactor inner cylinder (5) is provided in the iron removal reactor (2), and the iron removal reactor (2) and the iron removal reaction A mixture supply pipe (12) and a carbonate solution supply pipe (4) are provided between the intermediate layer and the inner tube (5). The mixer (1) of the preheating device is provided at the top of the mixture supply pipe (12), and the mixer (1) The reactor (9) is provided with a compressed air inlet (11) and a liquid supply port (10) for removing iron. An automatic stone powder supply device (8) is provided. A method for removing iron is also provided. The requirements for equipment are low, Energy saving is achieved, continuous production is possible, production capacity and efficiency are greatly improved, and oxidizing agent is added. It is possible to oxidize divalent iron ions to trivalent iron ions without any oxidation, and the iron removal rate is 99.5% or more. There are advantages to this.

Description

Technical Field

[0001] The present invention belongs to the technical field of non-ferrous metal hydrometallurgy, and particularly relates to a method for removing iron from nickel-cobalt-manganese sulfate solution.

Background Art

[0002] In industrial production, common methods for removing iron from solution are the goethite method and the jarosite sodium lithium method. These two methods need to be carried out under high-temperature conditions of 85 °C or above, and it is necessary to add an oxidant during the process to control the valence number of iron ions in the solution. In addition, the presence of certain concentrations of other ions such as sodium and ammonium in the solution is also required. The above two iron removal methods need to add various reagents step by step during operation and control the reaction time constantly. Generally, only single-tank operation can be carried out. In the patent with the patent publication number CN111187922A and the publication date of May 22, 2020, a method for selectively leaching nickel from high-nickel copper sulfonium under normal pressure is disclosed, and the iron removal technology of the leachate is disclosed, that is, the leachate obtained in step (1) is returned, and leaching is continued until the iron ion concentration in the leachate reaches 30-36 g / L. Then, hydrogen peroxide and potassium sulfate are added to the leachate, and filtered to obtain the post-iron-removal liquid and the iron-removal slag. The post-iron-removal liquid is a nickel sulfate solution, and the iron-removal slag becomes jarosite slag after being washed and filtered. The usage amount of hydrogen peroxide is twice the theoretical amount required for the reaction with iron, and the usage amount of potassium sulfate is 1.2 times the theoretical amount required for the reaction with iron. The iron removal temperature is 90-95 °C, and the iron removal time is 2-4 hours. When the iron removal temperature is high, not only a large amount of energy is consumed, but also the reaction time is long and the production efficiency is poor. Also, excessive Since a large amount of hydrogen sulfide and potassium sulfate are consumed, the production cost increases.

Summary of the Invention

Problems to be Solved by the Invention

[0003] An object of the present invention is to solve the drawbacks and defects described in the above background art, with a low iron removal temperature, low energy consumption, high production efficiency, no need to use auxiliary materials such as hydrogen peroxide and potassium sulfate, low production cost, an iron removal device for nickel-cobalt-manganese sulfate solution, and a method for continuously removing iron ions in nickel-cobalt-manganese sulfate solution at low temperature are disclosed. That is.

Means for Solving the Problems

[0004] As one of the technical solutions of the present invention, an iron removal reactor and an aging reactor are provided. A first stirrer is provided in the iron removal reactor, and a second stirrer is provided in the aging reactor. The iron removal reactor and the aging reactor are connected through an overflow port connecting pipe. An iron removal device for nickel-cobalt-manganese sulfate solution, wherein, an inner cylinder of the iron removal reactor is provided in the iron removal reactor. A mixing supply pipe and a carbonate solution supply pipe are provided between the iron removal reactor and the intervening layer of the inner cylinder of the iron removal reactor. A mixer is provided at the top of the mixing supply pipe. A compressed air inlet and a liquid to be iron-removed supply port are provided on the mixer. An automatic limestone supply device is provided for the aging reactor. Further, the mixer is provided with a mixing tank having a spatula-like structure with a large upper part and a small lower part. An electric heating part is provided on the lower surface of the mixing tank. The compressed air inlet is provided at the top of the mixing tank. The liquid to be iron-removed supply port is arranged such that the liquid to be iron-removed is tangent to the compressed air from the side in the mixing tank. is provided.

[0005] Furthermore, the mixer is provided with a mixing tank having a spatula-like structure with a large upper part and a small lower part. An electric heating part is provided on the lower surface of the mixing tank. The compressed air inlet is provided at the top of the mixing tank. The liquid to be iron-removed supply port is arranged such that the liquid to be iron-removed is tangent to the compressed air from the side in the mixing tank. is provided at the top of the mixing tank, and the liquid to be iron-removed supply port is arranged such that the liquid to be iron-removed is tangent to the compressed air from the side in the mixing tank. It is provided on the side of the tank, and the diameter of the outlet at the bottom of the mixing tank is 1 / 2 of the diameter of the bottom of the mixing tank, and the outlet at the bottom of the mixing tank is connected to the mixing supply pipe, and the mixing supply pipe penetrates through the electric heating part .

[0006] Furthermore, the height of the mixing tank accounts for 25-35%, preferably 30% of the total height of the mixer. Function: Ensure the heating and heat preservation time of the mixed material in the mixer. If the heating time increases or decreases due to this height, the heating effect will be affected.

[0007] Furthermore, the bottom end of the mixing supply pipe is 30-40 cm, preferably 35 cm away from the bottom surface of the iron removal reactor, and the direction of the outlet of the mixing supply pipe is in contact with the stirring direction of the stirrer. Function: Make the inlet of the mixed material lower than the stirring paddle, and while strengthening the mixing by the suction force of the stirring paddle, since the inlet of the mixed material is tangent to the stirring direction, the supplied material can be quickly mixed with the material in the reactor, which is beneficial to increasing the reaction speed.

[0008] Furthermore, the supply pipe of the mixer and the carbonate solution supply pipe are symmetrically arranged. Thereby, due to the symmetrical distribution of the mixed liquid and the carbonate solution, in the stirring state, a certain reaction time is given, the stability of the PH value is improved. If both are too close, a region with too high a PH value will occur in the reactor, and the main element will be lost.

[0009] Furthermore, the aspect ratio of the iron removal reactor is 1.0-2.5:1, preferably 1.5-2 .0:1. Function: The aspect ratio mainly ensures that after the reaction between the mixed liquid and the carbonate occurs at the bottom of the reactor, it is only retained in the reactor for a predetermined reaction time under the action of the stirring force. Otherwise, It is considered that it cannot flow to the flow port and then into the aging reactor.

[0010] Furthermore, the first stirrer consists of two parts, a motor and a stirring paddle, and the stirring paddle uses a cross-shaped two-layer stirring blade, the maximum diameter of the stirring blade is 1 / 3 of the diameter of the iron removal reactor, and the blades of the lower layer of the stirring paddle are 50 - 80 cm, preferably 60 - 70 cm away from the bottom of the reactor, and the distance between the two stirring blades above and below is 50 - 115 cm, preferably 60 - 100 cm, 70 - 90 cm, 80 cm. Function: The distance of the blades from the bottom is because the blades are maintained above the inlet of the mixed liquid and the carbonate solution. The length of the blades mainly ensures the stirring intensity. If the length of the blades is too large, it will increase the load on the motor. On the other hand, due to excessive stirring intensity, the fluid in the reactor will be disturbed and the mixing effect will be adversely affected. The distance between the blades of the two-layer stirring paddle is to ensure a predetermined stirring intensity. If this distance is too small, the mixing intensity at the upper part of the reactor will be insufficient. If the distance is too large, two laminar flows will occur up and down, the reaction will become non-uniform, which is disadvantageous for the iron removal reaction.

[0011] Furthermore, the carbonate solution supply pipe is 30 - 40 cm, preferably 3 5 cm away from the bottom surface of the iron removal reactor, and the direction of the outlet of the carbonate solution supply pipe is tangent to the stirring direction of the first stirrer. Function: The inlet of the carbonate solution is lower than the stirring paddle, and the mixing is enhanced by the suction force of the stirring paddle while the inlet of the carbonate solution is tangent to the stirring direction, so that the supplied material can be quickly mixed with the material in the reactor, which is advantageous for accelerating the reaction rate.

[0012] Furthermore, the inner cylinder of the iron removal reactor is configured in a cylindrical shape with open upper and lower parts, and is connected by a connecting plate It is fixed to the inner wall of the iron removal reactor, and the diameter of its inner cylinder is 70-80% of the diameter of the iron removal reactor. Function: The inner cylinder of the reactor plays a role in controlling the fluid in the reactor in a state of circulating up and down. The mixed liquid and the carbonate solution are mixed from the bottom upwards by the suction force of stirring, and do not rise without mixing, but rise from the upper end of the cylinder body and flow into the gap between the outside of the cylinder body and the wall of the reactor, and are driven by the fluid in the entire reaction tank to move downwards, and then enter the stirrer from the bottom of the cylinder body again. In this way, a circulating motion state of the fluid is obtained.

[0013] Furthermore, the second stirrer consists of two parts: a motor and a stirring paddle. The stirring paddle uses a cross-shaped double-layer stirring blade, and the diameter of the stirring blade is 1 / 3 of the diameter of the aging reactor. The blades of the lowermost layer of the stirring paddle are 50-80 cm, preferably 60-70 cm away from the bottom of the reactor. The distance between the two stirring blades above and below is 50-115 cm, preferably 60-1 00 cm, 70-90 cm, 80 cm. Function: This reactor is an aging reactor and has the same parameters as the iron removal reactor, but the stirring rotation speed of the aging reactor is much lower than that of the iron reactor. The distance of the blades from the bottom is such that solid particles do not settle to the bottom of the reaction tank during aging. If it is too far from the bottom, sedimentation will occur. If it is too close to the bottom, the load on the motor will increase. The diameter of the blades serves the same function as the distance from the bottom. If this diameter is too small, solid particles are likely to settle. If this diameter is too large, the load on the motor will increase. The distance between the two blades is mainly to ensure the stirring intensity. If the distance is too short, the stirring intensity at the upper part is too low. If the distance is too long, two stirring laminar flows above and below will occur, which is disadvantageous for the aging reaction.

[0014] Furthermore, the stone powder automatic supply device is automatically controlled by a solenoid valve, and controls the supply speed and supply amount through input to automatically perform material supply.

[0015] In the present invention, the mixer 1 is provided with a mixing tank having a spatula-like structure that is large at the top and small at the bottom. Therefore, compressed air is directly injected from the top, and the liquid to be deironed is tangent to the compressed air from the side. As a result, the pressure in the mixing tank suddenly increases, the mixing intensity greatly increases, and the outlet at the bottom of the mixing tank becomes even smaller than 1 / 2 of the diameter of the bottom of the mixing tank. In addition, an electric heating part is provided on the lower surface of the mixing tank, so that the compressed air and the liquid to be deironed become a microbubble-like flow. After being heated, it enters the reactor, and in this way, the oxidation of divalent iron is promoted.

[0016] As another technical solution of the present invention, a method for continuously removing iron ions at low temperature in a nickel-cobalt-manganese sulfate solution using an iron removal device for nickel-cobalt-manganese sulfate solution, comprising: preparing a carbonate, that is, first, step a of preparing a carbonate solution or slurry having a carbonate concentration of 120-240 g / L and a temperature controlled at 4 0-45 °C; injecting the solution to be deironed, that is, step b of putting the nickel-cobalt-manganese sulfate solution to be deironed and compressed

[0017] air into the iron removal reactor by a mixer with a preheating device; injecting the carbonate solution, that is, step c of adding the prepared carbonate solution or slurry into the iron removal reactor while injecting the nickel-cobalt-manganese sulfate solution to be deironed, and controlling the pH value during the reaction to be between 2

[0018] .5-3.5; .5 - 3.5;

[0019] Stir and react, that is, when injecting the iron-removal target solution and the carbonate solution, stir while injecting and control the temperature at 40 - 45 °C during that time. When the reactor is filled, step d of flowing the reaction slurry into the aging reactor and

[0020] add limestone powder, that is, after putting the reaction slurry into the aging reactor, stir, and then step e of adding limestone powder (mainly composed of calcium carbonate) by a self-feeding device.

[0021] Filter the solution, that is, when the aging reactor is filled, filter the solution to obtain iron slag as the filter slag and nickel-cobalt-manganese sulfate solution after iron removal as the filtrate in step f, and is characterized by including.

[0022] Furthermore, the carbonate is one or more of cobalt carbonate, nickel carbonate, manganese carbonate, and sodium carbonate.

[0023] Furthermore, the concentration of the carbonate is adjusted to 130 - 220 g / L, preferably 140 - 200 g / L, 150 - 180 g / L, 160 - 170 g / L, or 120 - 130 g / L, 130 - 140 g / L, 140 - 150 g / L, 150 - 160 g / L, 160 - 1 70 g / L, 170 - 180 g / L, 180 - 190 g / L, 190 - 200 g / L, 2 00 - 210 g / L, 210 - 220 g / L, 220 - 230 g / L may also be acceptable.

[0024] Furthermore, the temperature for preparing the carbonate is controlled at 40 - 45 °C, and it may also be 41 - 42 °C, 43 - 44 °C.

[0025] Furthermore, in the step of injecting the iron-removal target solution, the flow rate of the solution is related to the volume of the reactor ​​Based on this, the formula: flow rate = volume V of the reactor (cubic meters meter / (2 to 5.5 hours)) is calculated, and the flow rate of compressed air is 2 to 8 times, preferably 3 to 7 times, 4 to 6 times, 5 times the flow rate of the solution to be deironed.

[0026] The flow rate in this step controls the residence time in the deironing reactor, that is, the reaction time, and enables the reaction to proceed sufficiently to generate iron hydroxide and remove iron from the solution. The flow rate of compressed air determines the degree of oxidation reaction. The experimental data are shown in Table 1 and Table 2.

[0027] Table 1 Comparison of iron removal from solution by the flow rate of a 24.72 cubic meter reactor with 5 times compressed air comparison table

[0028] JPEG0007710126000001.jpg120167

[0029] Table 2 Comparison of iron removal from solution by the flow rate of compressed air in a reactor with a flow rate of 8 m 3 / h and a volume of 24.72 cubic meters comparison table

[0030] JPEG0007710126000002.jpg90134

[0031] Furthermore, in the step of injecting the solution to be deironed, the temperature of the preheating device is controlled at 40 to 45 °C, and it may also be 41 to 42 °C, 43 to 44 °C.

[0032] Furthermore, the addition amount of the stone powder is 0.05 to 0.5 kg / cubic meter per 1 cubic meter of the solution, preferably 0.10 to 0.45 kg / cubic meter, 0.15 to 0.40 kg / cubic meter, 0.20 to 0.35 kg / cubic meter, 0.25 to 0.30 kg / cubic meter.

[0033] This step is performed to remove the iron hydroxide precipitates that formed during aging, and the limestone acts to create a mixture that is easy to filter. The purpose is to produce alloy slag, and the experimental data are shown in Table 3.

[0034] Table 3. Comparison of filtration times for various calcium loadings

[0035] JPEG0007710126000003.jpg84167

[0036] In the present invention, the liquid to be deironized (nickel-cobalt-manganese sulfate solution) is heated at a low temperature of 40 to 45°C. The iron removal reactor is continuously fed with the combined iron removal solution and carbonate solution or slurry, and compressed air and the removal A large number of microbubbles are generated from the iron solution under the specified ratio and pressure conditions, and the divalent ions in the solution are The iron ions are oxidized to trivalent iron, and the pH value is increased by the action of carbonate, resulting in the precipitation of Fe(OH)3. Once the slurry is filled in the iron removal reactor, it flows continuously into the maturation reactor. By adding calcium to the aging process, the generated iron hydroxide colloid is aged. The calcium oxide is added to the slag to form a mixed slag with excellent filterability. This removes the iron. Effect of the Invention

[0037] The present invention adopts the above technical solutions, and has the following advantages: (1) Low temperature of 40 to 45°C Since iron removal is performed using this method, the requirements for the equipment are low and energy savings are achieved.

[0038] (2) The combined addition method enables continuous production, significantly improving production capacity and efficiency.

[0039] (3) Pressurize the compressed air and the liquid to be deironed to strongly mix them, and generate a large number of micro bubbles in such a process, oxidizing ferrous ions to trivalent without adding an oxidant.

[0040] (4) By the technique of adding calcium during aging, the generated iron hydroxide colloid increases during aging, modifies its surface, and forms a mixed slag with excellent filterability from the added calcium.

[0041] (5) The iron removal rate is 99.5% or more.

Brief Description of the Drawings

[0042]

Figure 1

[0043]

Figure 2

[0044]

Figure 3

[0045] 1 Mixer 2 Iron removal reactor 3 First stirrer 4 Carbonate solution supply pipe 5 Inner cylinder of the iron removal reactor 5 Overflow port connecting pipe 7 Second stirrer 8 Automatic stone powder supply device 9 Aging reactor 10 Liquid supply port to be deironed 11 Compressed air inlet 12 Mixing supply pipe 13 Outlet of the mixing supply pipe 14 Outlet of the carbonate solution supply pipe 15 Mixing tank 16 Heating part 17 Connection plate 18 Brackets

Embodiment for Carrying Out the Invention

[0046] Nickel-cobalt-manganese sulfate solution iron removal apparatus for nickel-cobalt-manganese sulfate The method for continuous low-temperature removal of iron ions in the solution includes the following steps. a. Preparation of carbonate: First, prepare a carbonate solution or slurry with a carbonate concentration of 220 g / L and a temperature controlled at 45°C.

[0047] b. Injection of the solution to be iron-removed: Inject the nickel-cobalt-manganese sulfate solution to be iron-removed and compressed air into the iron removal reactor by a mixer with a preheating device.

[0048] c. Injection of the carbonate solution: While injecting the nickel-cobalt-manganese sulfate solution to be iron-removed, add the prepared carbonate solution or slurry into the iron removal reactor and control the PH value during the reaction to 3.0.

[0049] d. Stirring reaction: When injecting the solution to be iron-removed and the carbonate solution, stir while injecting, control the temperature during that period to 45°C. When the reactor is filled, the reaction slurry enters the aging reactor.

[0050] e. Addition of stone powder: After the reaction slurry enters the aging reactor, stir, and then add stone powder (mainly calcium carbonate) by an automatic feeding device.

[0051] f. Solution filtration: When the aging reactor is filled, filter the solution to obtain iron slag as the filtered slag and the nickel-cobalt-manganese sulfate solution after iron removal as the filtrate.

[0052] In the iron removal apparatus for nickel-cobalt-manganese sulfate solution, the iron removal reactor and the aging reactor are ​​​​​​​A first agitator is provided in the iron removal reactor, and a second agitator is provided in the aging reactor. The iron removal reactor and the maturation reactor are connected through an overflow port connecting pipe, and the iron removal reactor An iron removal reactor inner cylinder is provided in the reactor, and a mixing supply is provided between the iron removal reactor and the intermediate layer of the iron removal reactor inner cylinder. A feed pipe and a carbonate solution feed pipe are provided, and a mixer is provided at the top of the mixture feed pipe. The furnace is equipped with a compressed air inlet and an inlet for supplying the liquid to be iron-removed, and the maturation reactor is equipped with an automatic stone powder supply device. The mixer is provided with a chopstick-shaped mixing tank with a large upper part and a small lower part. The mixing tank is fitted with an electric heater on the bottom surface, and the compressed air inlet is located at the top of the mixing tank. The iron removing liquid supply port is provided on the bottom of the pump so that the iron removing liquid is in contact with the compressed air from the side. The diameter of the outlet at the bottom of the mixing tank is 1 / 100th of the diameter of the bottom of the mixing tank. The mixing tank is 1 / 2 the diameter of the tank, and the outlet at the bottom of the mixing tank is connected to the mixing supply pipe. The height of the mixing tank is 30% of the total height of the mixer. The bottom end of the mixing supply pipe is 35 cm away from the bottom of the iron removal reactor, and the outlet of the mixing supply pipe The mixing direction of the mixer is tangent to the mixing direction of the first mixer. The feed pipe of the mixer and the carbonate solution feed pipe are tangent to each other. The aspect ratio of the iron removal reactor is 1.5 to 2.0:1. 1 The agitator consists of two parts: a motor and a stirring paddle. The stirring paddle is a cross-shaped two-layer agitator. The maximum diameter of the stirring blade is 1 / 3 of the diameter of the iron removal reactor, and the stirring pad at the bottom The blades of the stirring blade are 60-70 cm away from the bottom of the reactor, and the two blades on the top and bottom are The carbonate solution supply pipe is located 35 cm from the bottom of the iron removal reactor. m apart, and the direction of the outlet of the carbonate solution supply pipe is in contact with the stirring direction of the first stirrer. The inner cylinder of the iron removal reactor is configured in a cylindrical shape with open upper and lower parts, and is fixed to the inner wall of the iron removal reactor by a connecting plate. The diameter of the inner cylinder is 70% to 80% of the diameter of the iron removal reactor. The second stirrer consists of two parts: a motor and a stirring paddle. The stirring paddle uses cross-shaped double-layer stirring blades. The diameter of the stirring blades is 1 / 3 of the diameter of the aging reactor. The blades of the lowermost stirring paddle are 60 to 70 cm away from the bottom of the reactor, and the interval between the two stirring blades above and below is 80 to 100 cm. Embodiments of the present invention

[0053] To understand the present invention more clearly, the following will further describe the present invention with reference to FIGS. 1 to 3 and examples. will be further described.

[0054] Example 1 In an iron removal device for a nickel-cobalt-manganese sulfate solution, an iron removal reactor 2 and an aging reactor 9 are provided. A first stirrer 3 is provided in the iron removal reactor 2, and a second stirrer 7 is provided in the aging reactor 9. The iron removal reactor 2 and the aging reactor 9 are connected via an overflow port connecting pipe 5. An inner cylinder 5 of the iron removal reactor is provided in the iron removal reactor 2. A mixing supply pipe 12 and a carbonate solution supply pipe 4 are provided between the iron removal reactor 2 and the intervening layer of the inner cylinder 5 of the iron removal reactor. A mixer 1 of a preheating device is provided at the top of the mixing supply pipe 1 2. A compressed air inlet 11 and an iron removal target liquid supply port 10 are provided on the mixer 1. A stone powder automatic supply device 8 is provided on the aging reactor 9. The mixer 1 is provided with a mixing tank 15 having a funnel-shaped structure that narrows from top to bottom. Since the above-mentioned compressed air inlet 11 is provided at the top of the mixing tank 15, compressed air is directly injected from the top, and the iron removal target liquid supply port 10 is arranged such that the iron removal target liquid is tangent to the compressed air from the side. object liquid supply port 10 is provided such that the iron removal target liquid is tangent to the compressed air from the side. The mixer 1 is provided with a mixing tank 15 having a funnel-shaped structure that narrows from top to bottom. Since the above-mentioned compressed air inlet 11 is provided at the top of the mixing tank 15, compressed air is directly injected from the top, and the iron removal target liquid supply port 10 is arranged such that the iron removal target liquid is tangent to the compressed air from the side. The above-mentioned compressed air inlet 11 is provided at the top of the mixing tank 15, so that compressed air is directly injected from the top, and the iron removal target liquid supply port 10 is arranged such that the iron removal target liquid is tangent to the compressed air from the side. directly injected, and the iron removal target liquid supply port 10 is arranged such that the iron removal target liquid is tangent to the compressed air from the side. is provided on the side of the mixing tank 15, and the diameter of the outlet at the bottom of the mixing tank 15 is 1 / 2 of the diameter of the bottom of the mixing tank, so that compressed air and the liquid to be deironed enter the deironing reactor 2 as a microbubble-like jet flow. An electric heating part 16 is provided on the lower surface of the mixing tank 15, and the outlet at the bottom of the mixing tank 15 is connected to the mixing supply pipe 12, and the mixing supply pipe 12 penetrates through the electric heating part 16. The mixing tank 15 occupies 25% to 35% of the total length of the mixer 1. and thus, compressed air and the liquid to be deironed enter the deironing reactor 2 as a microbubble-like jet flow. An electric heating part 16 is provided on the lower surface of the mixing tank 15, and the outlet at the bottom of the mixing tank 15 is connected to the mixing supply pipe 12, and the mixing supply pipe 12 penetrates through the electric heating part 16. An electric heating part 16 is provided on the lower surface of the mixing tank 15, and the outlet at the bottom of the mixing tank 15 is connected to the mixing supply pipe 12, and the mixing supply pipe 12 penetrates through the electric heating part 16. The mixing tank 15 occupies 25% to 35% of the total length of the mixer 1.

[0055] In Example 1, since the structure of the equipment is simple, the manufacturing cost is low, and continuous production is possible, the stopping time in the middle is omitted, the production efficiency is greatly improved, and the production capacity is also improved accordingly. In Example 1, since the structure of the equipment is simple, the manufacturing cost is low, and continuous production is possible, the stopping time in the middle is omitted, the production efficiency is greatly improved, and the production capacity is also improved accordingly. In Example 1, since the structure of the equipment is simple, the manufacturing cost is low, and continuous production is possible, the stopping time in the middle is omitted, the production efficiency is greatly improved, and the production capacity is also improved accordingly.

[0056] Example 2 In the iron removal device for nickel-cobalt-manganese sulfate solution, an iron removal reactor 2 and an aging reactor 9 are provided, and the aspect ratio of the iron removal reactor 2 is 1:1. A first stirrer 3 is provided in the iron removal reactor 2. The first stirrer 3 consists of two parts, a motor and a stirring paddle. The stirring paddle uses a cross-shaped double-layer stirring blade, and the diameter of the stirring blade is 1 / 3 of the diameter of the iron removal reactor 2. The blades of the lowermost stirring paddle are 50 cm away from the bottom of the reactor, and the interval between the upper and lower two stirring blades is 50 cm. A second stirrer 7 is provided in the aging reactor 9. The second stirrer 7 consists of two parts, a motor and a stirring paddle. The motor is fixed to the bracket 18, and the stirring paddle uses a cross-shaped double-layer stirring blade. The diameter of the stirring blade is 1 / 3 of the diameter of the aging reactor 9. The blades of the lowermost stirring paddle are 50 cm away from the bottom of the reactor, and the interval between the upper and lower two stirring blades is 50 cm. The iron removal reactor 2 and the aging In the iron removal device for nickel-cobalt-manganese sulfate solution, an iron removal reactor 2 and an aging reactor 9 are provided, and the aspect ratio of the iron removal reactor 2 is 1:1. A first stirrer 3 is provided in the iron removal reactor 2. The first stirrer 3 consists of two parts, a motor and a stirring paddle. The stirring paddle uses a cross-shaped double-layer stirring blade, and the diameter of the stirring blade is 1 / 3 of the diameter of the iron removal reactor 2. The blades of the lowermost stirring paddle are 50 cm away from the bottom of the reactor, and the interval between the upper and lower two stirring blades is 50 cm. A second stirrer 7 is provided in the aging reactor 9. The second stirrer 7 consists of two parts, a motor and a stirring paddle. The motor is fixed to the bracket 18, and the stirring paddle uses a cross-shaped double-layer stirring blade, and the diameter of the stirring blade is 1 / 3 of the diameter of the aging reactor 9. The blades of the lowermost stirring paddle are 50 cm away from the bottom of the reactor, and the interval between the upper and lower two stirring blades is 50 cm. The iron removal reactor 2 and the aging The forming reactor 9 is connected via an overflow port connecting pipe 5, and an iron removal reactor inner cylinder 5 is provided in the iron removal reactor 2. The iron removal reaction The inner cylinder of the reactor is provided. The iron removal reactor inner cylinder 5 is configured in a cylindrical shape with open upper and lower parts, and is fixed to the inner wall of the iron removal reactor 2 by a connection plate 17. The diameter of the inner cylinder is 70% of the diameter of the iron removal reactor 2. A mixing supply pipe 1 2 and a carbonate solution supply pipe 4 are provided between the iron removal reactor 2 and the intervening layer of the iron removal reactor inner cylinder 5. The mixer supply pipe 12 and the carbonate solution supply pipe 4 are symmetrically provided. The bottom end of the mixing supply pipe 12 is 30 cm away from the bottom surface of the iron removal reactor 2, and the direction of the outlet of the mixing supply pipe 12 is in contact with the stirring direction of the first stirrer 3. The carbonate solution supply pipe 4 is 30 cm away from the bottom surface of the iron removal reactor 2, and the direction of the outlet of the carbonate solution supply pipe 4 is in contact with the stirring direction of the first stirrer 3. A mixer 1 of a preheating device is provided at the top of the mixing supply pipe 12. The mixer 1 is provided with a compressed air inlet 11 and an iron removal target liquid supply port 10. A stone powder automatic supply device 8 is provided in the aging reactor 9. The stone powder automatic supply device 8 is automatically controlled by an electromagnetic valve, and automatically supplies by controlling the supply speed and supply amount through input. Stone powder In the automatic supply device 8, the supply is controlled by a pneumatic knife gate valve manufactured by Shanghai Beisi Special Automation Technology Co., Ltd., and the model of the gate valve is QZ41-50CPV24-DXZ43.

[0057] In the second embodiment, by operating the iron removal reactor and the aging reactor in cooperation, the continuity of iron removal is realized. The structure of the equipment is simple, the manufacturing cost is low, and continuous production by a continuous method is possible. The intermediate stop time is omitted, the production efficiency is greatly improved, and the production capacity is also improved accordingly.

[0058] Example 3 ​​​​​​​​In an iron removal device for a nickel-cobalt-manganese sulfate solution, an iron removal reactor 2 and an aging reactor 9 are provided, and the aspect ratio of the iron removal reactor 2 is 2.5:1. Inside the iron removal reactor 2 a first stirrer 3 is provided, and the first stirrer 3 consists of two parts, a motor and a stirring paddle , and the stirring paddle uses a cross-shaped two-layer stirring blade. The diameter of the stirring blade is 1 / 3 of the diameter of the iron removal reactor 2, and the blade of the lowermost stirring paddle is 80 cm away from the bottom of the reactor, and the distance between the two stirring blades above and below is 115 cm. A second stirrer 7 is provided in the aging reactor 9 . The second stirrer 7 consists of two parts, a motor and a stirring paddle. The motor is fixed to the bracket 1 8, and the stirring paddle uses a cross-shaped two-layer stirring blade. The diameter of the stirring blade is 1 / 3 of the diameter of the aging reactor 9 , and the blade of the stirring paddle in the lowermost layer is 80 cm away from the bottom of the reactor, and the distance between the two stirring blades above and below is 115 cm. The iron removal reactor 2 and the aging reactor 9 are connected through an overflow port connecting pipe 5. An inner cylinder 5 of the iron removal reactor is provided in the iron removal reactor 2 . The inner cylinder 5 of the iron removal reactor is configured in a cylindrical shape with an open upper and lower part, and is fixed to the inner wall of the iron removal reactor 2 by a continuous plate 17 , and the diameter of the inner cylinder is 80% of the diameter of the iron removal reactor 2 . A mixing supply pipe 12 and a carbonate solution supply pipe 4 are provided between the iron removal reactor 2 and the intervening layer of the inner cylinder 5 of the iron removal reactor. The mixer supply pipe 12 and the carbonate solution supply pipe 4 are provided symmetrically . The bottom end of the mixing supply pipe 12 is 40 cm away from the bottom surface of the iron removal reactor 2 , and the direction of the outlet of the mixing supply pipe 12 is in contact with the stirring direction of the first stirrer 3. The carbonate solution supply pipe 4 flows 40 cm from the bottom surface of the iron removal reactor 2, and the direction of the outlet of the carbonate solution supply pipe 4 is in contact with the stirring direction of the first stirrer 3. At the top of the mixing supply pipe 12, a mixer of a preheating device is provided at the top of the mixing supply pipe 12. -1 is provided, and the mixer 1 is provided with a compressed air inlet 11 and a liquid to be deironed supply port 10. An automatic stone powder supply device 8 is provided for the aging reactor 9. The automatic stone powder supply device 8 is controlled automatically by a solenoid valve and automatically supplies by controlling the supply speed and supply amount through the input. In the automatic stone powder supply device 8, the supply is controlled by a pneumatic knife gate valve manufactured by Shanghai Beisi Special Automation Technology Co., Ltd. and the model of the gate valve is QZ41-50CPV24-DXZ43.

[0059] In this Example 3, by operating the deironing reactor and the aging reactor in cooperation, the continuity of deironing is realized, the structure of the equipment is simple, the manufacturing cost is low, and continuous production by the continuous method is possible. Among them, the intermediate stop time is omitted, the production efficiency is greatly improved, and the production capacity is also improved accordingly.

[0060] Example 4 A method for continuously removing iron ions at low temperature in a nickel cobalt manganese sulfate solution using an iron removal device for nickel cobalt manganese sulfate solution includes the following steps. a. The components of the nickel cobalt manganese sulfate solution to be deironed are Fe: 1.15 g / L, Co: 26.03 g / L, Mn: 5.41 g / L, Ni: 7.35 g / L. b. 124 g / L of manganese carbonate slurry was prepared and kept warm at 45 °C. c. Both the deironing reactor 2 and the aging reactor 9 have a diameter of 3 m, a height of 4 m, and an effective volume of 24.72 cubic meters. d. While starting the mixer 1, the solution to be deironed, compressed air, and manganese carbonate slurry were injected. The flow rate of the solution to be deironed is 10.5 m / h, and the compressed air is 21 m / h. e. The temperature of the mixer is 45 3 / h, and 3 ℃, the internal temperature of the reactor is 45℃, and the pH value of the reaction is controlled at 3.05. f. When the iron removal reactor 2 is filled and the content inside flows into the aging reactor 9, the stone powder automatic feeder 8 is started, and the amount of stone powder added per hour is set to 5 kg. g. When the aging reactor 9 is filled, the filtration device is started for filtration. At this time, the iron removal device balances, enabling continuous material discharge and realizing continuous production. h. After analyzing and detecting the components of the solution after iron removal, the results are as follows: Fe: 0.0055 g / L, Co: 25.99 g / L, Mn: 11.13 g / L, Ni: 7.05 g / L.

[0061] In Example 4 of the present invention, according to the conventional solution iron removal technology, the problem of requiring high temperature conditions of 85℃ or higher to remove iron is solved, and iron can be removed from the solution at a low temperature of 45℃. As a result of iron removal from the solution, the iron removal rate reaches

[0062] Example 5 A method for continuously removing iron ions at low temperature from a nickel cobalt manganese sulfate solution using an iron removal device for nickel cobalt manganese sulfate solution includes the following steps. a. The components of the iron removal target solution (nickel cobalt manganese sulfate solution) are Fe: 5.22 g / L, Co: 16.03 g / L, Mn: 3.47 g / L, Ni: 3.35 g / L. b. A 127 g / L nickel carbonate slurry is prepared and kept warm at 45℃. c. Both the iron removal reactor 2 and the aging reactor 9 are 3 m in diameter, 4 m in height, and have an effective volume of 24.72 cubic meters. d. While starting the mixer, the iron removal target solution, compressed air, and manganese carbonate slurry are injected. The 3 flow rate of the iron removal target solution is 9.9 m 3 / h, and the compressed air is 31 m The temperature is 5°C, the internal temperature of the reactor is 45°C, and the pH value of the reaction is controlled at 3.11. f. Iron removal reactor 2 When it is full and the internal material flows into the aging reactor 9, the stone powder automatic feeding device 8 is started, and the amount of stone powder added per hour is set to 4.6 kg. g. When the aging reactor 9 is full, the filtration device is started for filtration. At this time, the iron removal device balances and continuous material discharge becomes possible, realizing continuous production. h. Analyze and detect the components of the solution after iron removal, and the results show that Fe: 0.0025 g / L, Co: 15.98 g / L, Mn: 3.13 g / L, Ni: 9.05 g / L.

[0063] Example 5 According to the conventional solution iron removal technology, high temperature conditions of 85°C or higher are required to remove iron, solving the problem and enabling iron removal from the solution at a low temperature of 45°C. For a solution with a high iron content of 5.22 g / L, the iron removal rate reaches 99.95% after iron removal. In this method, even when the iron content is high, iron ions can be sufficiently removed without adding an additional oxidizing agent, reducing the production cost.

[0064] Example 6 A method for continuously removing iron ions at low temperature from a nickel cobalt manganese sulfate solution using an iron removal device for nickel cobalt manganese sulfate solution includes the following steps. a. The components of the iron removal target solution (nickel cobalt manganese sulfate solution) are Fe: 0.77 g / L, Co: 22.03 g / L, Mn: 1.47 g / L, Ni: 4.31 g / L. b. Prepare a 121 g / L cobalt carbonate slurry and keep it warm at 45°C. c. The iron removal reactor 2 and the aging reactor 9 are both 3 m in diameter, 4 m high, and have an effective volume of 24.72 cubic meters. d. Start the mixer 1 ​​​​While agitating, an iron-removing target solution, compressed air, and a slurry of manganese carbonate were injected. The iron-removing target liquid flow rate was 12.7 m 3 / h, and the compressed air was 30 m 3 / h. e. The temperature of the mixer was 4 5 °C, the internal temperature of the reactor was 45 °C, and the pH value of the reaction was controlled at 3.13. f. When the iron-removing reactor 2 was filled and flowed into the aging reactor 9, the stone powder automatic feeder 8 was started, and the stone powder addition amount per hour was set to 5.2 kg. g. When the aging reactor 9 was filled, the filtration device was started and filtration was performed. At this time, the iron-removing device balanced and continuous material discharge became possible and continuous production was realized. h. As a result of analyzing and detecting the components of the solution after iron removal , Fe: 0.0023 g / L, Co: 25.98 g / L, Mn: 1.19 g / L, Ni: 4.05 g / L.

[0065] In Example 6, according to the conventional solution iron-removing technology, the problem that high-temperature conditions of 85 °C or higher are required to remove iron was solved, and iron could be removed from the solution at a low temperature of 45 °C. As a result of removing iron from a solution with a high iron content of 0.77 g / L, the iron removal rate reached 99.70%. This method can also be applied when the iron content is not high, and the continuity of the process is not affected.

[0066] Example 7 A method for continuously removing iron ions at low temperature in a nickel-cobalt-manganese sulfate solution using an iron-removing device for nickel-cobalt-manganese sulfate solution includes the following steps. a. The components of the iron-removing target liquid (nickel-cobalt-manganese sulfate solution) are Fe: 3.04 g / L, Co: 35.03 g / L, Mn: 1.47 g / L, Ni: 14.31 g / L. b. 146 g / L of sodium carbonate A thorium slurry was prepared and kept warm at 45°C. c. The iron removal reactor 2 and the aging reactor 9 are both 3 m in diameter, 4 m in height, and have an effective volume of 24.72 cubic meters. d. While starting the mixer , an iron removal target solution, compressed air, and a slurry of manganese carbonate were injected. The flow rate of the iron removal target solution is 11.3 m 3 / h, and the compressed air is 30 m 3 / h. e. The temperature of the mixer is 45°C, the internal temperature of the reactor is 45°C, and the pH value of the reaction is controlled at 3.15. f. When the iron removal reactor 2 is filled and the contents inside flow into the aging reactor 9, the stone powder automatic feeder 8 is started , and the amount of stone powder added per hour is set to 4.7 kg. g. When the aging reactor 9 is filled, the filtration device is started to perform filtration. The iron removal device is balanced, enabling continuous material discharge , and continuous production is realized. h. As a result of analyzing and detecting the components of the solution after iron removal, it was found that Fe: 0.0043 g / L, Co: 34.88 g / L, Mn: 1.13 g / L, Ni: 14.05 g / L. In Example 7 of the present invention, according to the conventional solution iron removal technology, the problem of requiring high temperature conditions of 85°C or higher to remove iron is solved, and iron can be removed from the solution at a low temperature of 45°C. As a result of iron removal from the solution, the iron removal rate reaches 99.86%. By using the aging technology with calcium in this process, the slag has excellent filterability, and iron ions do not remain in the solution,

[0067] nor does it affect the concentration of iron ions in the solution.

[0068] The above are only preferred embodiments of the present invention and do not limit the present invention. Those skilled in the art

[0068] can make various changes and modifications to the present invention. Without departing from the spirit and principle of the present invention , All modifications, equivalent substitutions, improvements, etc. made without departing from the scope of the present invention are included in the patent scope of the present invention shall be

Industrial Applicability

[0069] The present invention is applicable to industrial production, and can remove iron from nickel-cobalt manganese sulfate solution at a low temperature of 40 to 45 °C, and the iron removal rate is 99.5% or more ​

Claims

1. An iron removal device for nickel cobalt manganese sulfate solution, which is provided with an iron removal reactor and an aging reactor, a first stirrer is provided in the iron removal reactor, a second stirrer is provided in the aging reactor, and the iron removal reactor and the aging reactor are connected through an overflow port connecting pipe, an iron removal reactor inner cylinder is provided in the iron removal reactor, a mixing supply pipe and a carbonate solution supply pipe are provided between the iron removal reactor and the intervening layer of the iron removal reactor inner cylinder, a mixer is provided at the top of the mixing supply pipe, a compressed air inlet and an iron removal target liquid supply port are provided on the mixer, and an automatic supply device for stone powder mainly composed of calcium carbonate is provided in the aging reactor. The iron removal device for nickel cobalt manganese sulfate solution is characterized in that.

2. The mixer is provided with a mixing tank having a spatula-shaped structure with a large upper part and a small lower part, an electric heating part is provided on the lower surface of the mixing tank, the compressed air inlet is provided at the top of the mixing tank, the iron removal target liquid supply port is provided on the side surface of the mixing tank, the diameter of the outlet at the bottom of the mixing tank is 1 / 2 of the diameter of the bottom of the mixing tank, the outlet at the bottom of the mixing tank is connected to the mixing supply pipe, and the mixing supply pipe penetrates through the electric heating part. The iron removal device for nickel cobalt manganese sulfate solution according to claim 1, characterized in that.

3. The supply pipe of the mixer and the carbonate solution supply pipe are symmetrically provided. The iron removal device for nickel cobalt manganese sulfate solution according to claim 1, characterized in that.

4. The first stirrer consists of two parts: a motor and a stirring paddle. The stirring paddle uses a cross-shaped two-layer stirring blade. The diameter of the stirring blade is 1 / 3 of the diameter of the iron removal reactor. The blade of the lowermost stirring paddle is 50-80 cm away from the bottom of the iron removal reactor. The interval between the two stirring blades above and below is 50-115 cm. The second stirrer consists of two parts: a motor and a stirring paddle. The stirring paddle uses a cross-shaped two-layer stirring blade. The diameter of the stirring blade is 1 / 3 of the diameter of the aging reactor. The blade of the lowermost stirring paddle is 50-80 cm away from the bottom of the aging reactor. The interval between the two stirring blades above and below is 50-115 cm. The iron removal device for nickel cobalt manganese sulfate solution according to claim 1, characterized in that.

5. The inner cylinder of the iron removal reactor is configured in a cylindrical shape with open upper and lower parts, and is fixed to the inner wall of the iron removal reactor by a connection plate. The diameter of the inner cylinder is 70-80% of the diameter of the iron removal reactor. The iron removal device for nickel-cobalt-manganese sulfate solution according to claim 1, characterized in that.

6. A method for continuously removing iron ions at low temperature in a nickel-cobalt-manganese sulfate solution using an iron removal device for nickel-cobalt-manganese sulfate solution, comprising: Preparing a carbonate, that is, first, step a of preparing a carbonate solution or slurry with a carbonate concentration of 120-240 g / L and a temperature controlled at 40-45 °C; Injecting the solution to be deironed, that is, step b of putting the nickel-cobalt-manganese sulfate solution to be deironed and compressed air into the iron removal reactor by a mixer with a preheating device; Injecting the carbonate solution, that is, while injecting the nickel-cobalt-manganese sulfate solution to be deironed, adding the prepared carbonate solution or slurry into the iron removal reactor and controlling the pH value during the reaction between 2.5 and 3.

5. Step c; Stirring and reacting, that is, when injecting the solution to be deironed and the carbonate solution, stirring while injecting, controlling the temperature between 40 and 45 °C during that time, and when the reactor is filled, flowing the reaction slurry into the aging reactor. Step d; Adding stone powder mainly composed of calcium carbonate, that is, after putting the reaction slurry into the aging reactor, stirring, and then adding stone powder mainly composed of calcium carbonate by an automatic feeding device. Step e; Filtering the solution, that is, when the aging reactor is filled, filtering the solution to obtain iron slag as a filter slag and a nickel-cobalt-manganese sulfate solution after iron removal as a filtrate. Step f; Including, a low-temperature continuous removal method characterized in that.

7. In the step of injecting the solution to be deironed, the flow rate of the solution is calculated according to the formula: flow velocity = volume V of the reactor (cubic meters / (2-5.5 hours)) based on the volume of the reactor, and the flow rate of the compressed air is The method for continuously removing iron ions at low temperature in a nickel-cobalt-manganese sulfate solution using the iron removal device for nickel-cobalt-manganese sulfate solution according to claim 6, characterized in that it is 2-8 times the flow rate of the solution to be deironed.

8. A method for continuously removing iron ions at low temperature from a nickel-cobalt-manganese sulfate solution, using the iron removal device for nickel-cobalt-manganese sulfate solution according to claim 6, wherein the addition amount of stone powder mainly composed of calcium carbonate is 0.05 to 0.5 kg / cubic meter of solution.

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