A method for preparing polymeric ferric aluminum chloride with iron and aluminum residues in a waste battery recycling process

Abstract

The application provides a method for preparing polymeric ferric aluminum chloride from iron and aluminum residues in a waste battery recycling process, which comprises the following steps: subjecting a waste lithium ion battery to alkali dissolution to obtain aluminum-containing material and powder; mixing the aluminum-containing material with a hydrolysis agent to perform a hydrolysis reaction and obtain aluminum hydroxide; subjecting the powder to acid leaching, then adding iron powder to perform a displacement reaction to obtain copper precipitate and copper-removed leaching solution, and then adjusting the pH value of the copper-removed leaching solution to obtain iron-removed leaching solution and iron-vanadium residue; subjecting the iron residue to chlorination roasting to obtain a chloride, then performing acid leaching to obtain an acid leaching solution, and then adding an extraction agent to obtain an iron-containing extraction solution and a nickel-cobalt-manganese-containing raffinate; and mixing the aluminum hydroxide with the iron-containing solution to obtain the polymeric ferric aluminum chloride. The method can not only realize the recovery of high-value metals, but also realize the resource utilization of iron and aluminum residues, and the polymeric ferric aluminum chloride is prepared, which has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solid waste resource recycling and utilization, and particularly relates to a method for preparing polymeric ferric aluminum chloride from iron and aluminum residues in a waste battery recycling process. BACKGROUND

[0002] With the improvement and maturity of new energy vehicle technology in China, the sales of lithium ion battery power vehicles in China continue to rise. Limited by the service life of power batteries, the number of scrapped power batteries has been increasing since 2020. The scrapped power batteries are generally recycled by a wet method, but iron and aluminum residues are generated in the recycling process, causing resource waste.

[0003] Composite aluminum iron is a new type of high-efficiency coagulant prepared by adding elemental iron ions or ferric oxide and other iron-containing compounds to coagulate and hydrolyze. It has obvious advantages in improving the form of aluminum ions and iron ions. The liquid product of composite aluminum iron is a brown or red-brown transparent body without precipitation. The solid product is a brown-red powder or crystalline grain, which is easily dissolved in water. Especially in the treatment of high-turbidity water and low-turbidity water, the treatment effect is more obvious. It can be used for drinking water, industrial water and industrial wastewater, and domestic sewage treatment. In addition to the decrease of residual turbidity and color, the coagulation effect also has the advantages of fast flocculation, high adsorption performance, good filtration and dewatering performance of sludge, especially in the treatment of high-turbidity water, low temperature and low turbidity, the treatment effect is better than that of alum, polymeric ferric sulfate and ferric chloride.

[0004] Therefore, it is urgent to provide a method for preparing composite iron and aluminum from iron and aluminum residues generated in the recycling process of scrapped batteries, so as to not only realize the recycling of high-value metals, but also realize the resource utilization of iron and aluminum residues. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a method for preparing polymeric ferric aluminum chloride from iron and aluminum residues in the recycling process of waste batteries. The method provided by the present application not only realizes the recycling of high-value metals, thereby converting into battery materials, but also realizes the resource utilization of iron and aluminum residues, thereby preparing polymeric ferric aluminum chloride which can be used as a high-performance coagulant. Moreover, the method is simple in process, high in recovery efficiency, and has a broad application prospect.

[0006] To achieve the purpose of the present application, the following technical solutions are adopted:

[0007] In a first aspect, the present application provides a method for preparing polymeric ferric aluminum chloride from iron and aluminum residues in the recycling process of waste batteries, which comprises the following steps:

[0008] (1) the waste lithium ion battery is subjected to alkali dissolution to obtain an aluminum-containing material and a powder, then the aluminum-containing material and a hydrolysis agent are mixed to perform a hydrolysis reaction to obtain aluminum hydroxide;

[0009] (2) the powder is subjected to acid leaching, then iron powder is added to perform a displacement reaction to obtain copper precipitate and a copper-removed leaching solution, then the pH value of the copper-removed leaching solution is adjusted to obtain an iron-removed leaching solution and iron sulfide residue;

[0010] (3) the iron sulfide residue is subjected to chlorination roasting to obtain a chloride, then acid leaching is performed to obtain an acid leaching solution, then an extractant is added to obtain an iron-containing raffinate and a nickel-cobalt-manganese-containing extraction solution;

[0011] (4) the aluminum hydroxide and the iron-containing raffinate are mixed to react to obtain the polyaluminum ferric chloride.

[0012] The method provided by the application can not only realize recovery of high-value metals, thereby fully utilizing and converting into battery materials, but also realize resource utilization of iron and aluminum residues to prepare polyaluminum ferric chloride which can be used as a high-performance coagulant. Moreover, the method has simple process, high recovery efficiency and wide application prospect.

[0013] In the application, aluminum in the waste lithium ion battery is preferentially removed, which can effectively improve the purity of the pole piece powder and is conducive to full-process recovery of high-purity metals for synthesis of positive electrode precursors. In addition, the removed aluminum can be converted into aluminum hydroxide as an intermediate product, which can not only be used as an Al source for polyaluminum ferric chloride, but also improve the pH value of the solution during mixing with the iron-containing raffinate.

[0014] In the application, chlorination roasting can convert the iron sulfide residue into soluble nickel-cobalt-manganese salt and iron salt.

[0015] In the application, the iron-removed leaching solution and the extraction solution can be mixed for recovery to prepare positive electrode precursor materials.

[0016] As a preferred technical solution of the application, the alkali solution used in the process of alkali dissolution in step (1) includes sodium hydroxide solution.

[0017] It should be noted that the mass fraction of the alkali solution is not limited in the application, for example, it can be 10% or the like.

[0018] Preferably, the temperature of alkali dissolution in step (1) is 60-80℃, for example, it can be 60℃, 65℃, 70℃, 75℃ or 80℃ or the like, and the time of alkali dissolution is 90-150min, for example, it can be 90min, 100min, 110min, 120min, 130min, 140min or 150min or the like.

[0019] In the present application, the alkali solution at 60-80℃ for 90-150min helps to convert the aluminum-containing material into precipitates.

[0020] Preferably, the hydrolysis agent in step (1) comprises dilute sulfuric acid and / or dilute sulfurous acid.

[0021] It should be noted that the chemical formula of dilute sulfuric acid is H2SO4; the chemical formula of dilute sulfurous acid is H2SO3, and the CAS number is 7782-99-2.

[0022] Preferably, the concentration of the dilute sulfuric acid is 50-100g / L, for example, it can be 50g / L, 60g / L, 70g / L, 80g / L, 90g / L or 100g / L, etc.

[0023] In the present application, the addition of dilute sulfuric acid to the aluminum-containing material can convert NaAlO2 into Al(OH)3. For example, the following reaction can occur:

[0024] 2NaAlO2+H2SO4+2H2O==Na2SO4+2Al(OH)3.

[0025] Preferably, the temperature of the hydrolysis reaction in step (1) is 50-90℃, for example, it can be 50℃, 60℃, 70℃, 80℃ or 90℃, etc.

[0026] Preferably, the molar ratio of the aluminum-containing material to the hydrolysis agent in step (1) is 1:(0.01-0.08), for example, it can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07 or 1:0.08, etc., preferably stoichiometric ratio.

[0027] It should be noted that stoichiometric ratio means that the aluminum-containing material and the hydrolysis agent react according to the reaction equation, and the reaction is complete.

[0028] As a preferred technical solution of the present application, the acid solution in the process of acid leaching in step (2) comprises sulfuric acid.

[0029] Preferably, the concentration of the acid solution in the process of acid leaching in step (2) is 300-350g / L, for example, it can be 300g / L, 310g / L, 320g / L, 330g / L, 340g / L or 350g / L, etc.

[0030] In the present application, the concentration of the acid solution is 300-350g / L, which is beneficial to the efficient leaching of the powder material. The higher the concentration of hydrogen ions within a certain range, the faster the reaction proceeds.

[0031] Preferably, the temperature of the acid leaching in step (2) is 80-90℃, for example, it can be 80℃, 82℃, 84℃, 86℃, 88℃ or 90℃, etc., and the acid leaching time is 240-360min, for example, it can be 240min, 260min, 280min, 300min, 320min, 340min or 360min, etc.

[0032] In the present application, the acid leaching is carried out at 80-90℃ for 240-360min, which helps to accelerate the collision of hydrogen ions with the material and speed up the reaction, so that the reaction is sufficient.

[0033] As a preferred technical solution of the present application, the amount of iron powder added in step (2) is 1.1-1.2 times the theoretical amount, for example, it can be 1.1 times, 1.12 times, 1.14 times, 1.16 times, 1.18 times or 1.2 times, etc.

[0034] In the present application, the amount of iron powder added is 1.1-1.2 times the theoretical amount, which helps to fully realize copper replacement and prevent the presence of residual copper.

[0035] In the present application, the theoretical amount refers to the amount of iron powder required to replace all the copper.

[0036] Preferably, after adjusting the pH value of the copper removal leaching solution in step (2), the pH value of the copper removal leaching solution is 3.8-4.5, for example, it can be 3.8, 4, 4.2 or 4.5, etc.

[0037] In the present application, adjusting the pH value of the copper removal leaching solution to 3.8-4.5 helps to remove iron elements in the copper removal leaching solution.

[0038] As a preferred technical solution of the present application, the specific steps of chloridizing roasting in step (3) include:

[0039] Mixing the jarosite residue and the chlorinating agent and roasting.

[0040] In the present application, since adjusting the pH value of the copper removal leaching solution will cause high-value metals to be removed along with the iron elements, the removed high-value metals can be converted into soluble chlorides through chloridizing roasting, so as to facilitate subsequent recycling.

[0041] Preferably, the chlorinating agent includes ammonium chloride and / or hydrochloric acid.

[0042] In the present application, ammonium chloride and other substances can be used as chlorinating agents to fully perform chloridizing reduction roasting.

[0043] Preferably, the mass ratio of the jarosite residue to the chlorinating agent is 1:(1-3), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, etc.

[0044] In the present application, if the mass ratio of the jarosite residue and the chlorinating agent is too small, the utilization rate of the chlorinating agent can be insufficient, the residues of the reactants exist, and the reaction is affected; if the mass ratio of the jarosite residue and the chlorinating agent is too large, the reaction is insufficient, and the jarosite residue cannot be completely converted.

[0045] Preferably, the temperature of the roasting is 300-500℃, for example, it can be 300℃, 350℃, 400℃, 450℃ or 500℃, etc., and the time of the roasting is 180-240min, for example, it can be 180min, 200min, 220min or 240min, etc.

[0046] In the present application, if the temperature of the roasting is too low, the reaction is insufficient; if the temperature of the roasting is too high, the energy consumption is large, which is not conducive to reducing the cost.

[0047] As a preferred technical solution of the present application, the acid solution in the process of the acid leaching of step (3) includes any one or a combination of at least two of sulfuric acid, sulfurous acid or hydrochloric acid.

[0048] Preferably, the concentration of the acid solution in the process of the acid leaching of step (3) is 60-120g / L, for example, it can be 60g / L, 80g / L, 100g / L or 120g / L, etc.

[0049] Preferably, the extractant of step (3) includes a phosphorus-based extractant.

[0050] The present application adopts a phosphorus-based extractant, which can separate high-value metals and iron elements.

[0051] Preferably, the phosphorus-based extractant includes P204 and / or P507.

[0052] It should be noted that the Chinese name of P204 is di(2-ethylhexyl) phosphate, and the Chinese name of P507 is 2-ethylhexyl phosphoric acid.

[0053] Preferably, the volume-mass ratio of the acid leaching solution and the extractant of step (3) is 1mL:(1-3)mg, for example, it can be 1mL:1mg, 1mL:2mg or 1mL:3mg, etc.

[0054] In the present application, the volume-mass ratio of the acid leaching solution and the extractant is 1mL:(1-3)mg, which can realize sufficient separation of high-value metals and iron elements.

[0055] As a preferred technical solution of the present application, the mixing of step (4) is accompanied by stirring.

[0056] In the present application, the purpose of stirring is to accelerate the reaction.

[0057] Preferably, the stirring rate in step (4) is 300-800 rpm, for example, it can be 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm or 800 rpm, etc.

[0058] In the present application, the stirring is carried out at 300-800 rpm, so that the stirring can be carried out sufficiently and the reaction can be realized.

[0059] Preferably, the mixing time in step (4) is 3-5 h, for example, it can be 3 h, 4 h or 5 h, etc.

[0060] As a preferred technical solution of the present application, a stabilizer is further added during the mixing in step (4).

[0061] In the present application, the stabilizer functions to slow down the reaction, maintain the chemical equilibrium and reduce the surface tension.

[0062] Preferably, the stabilizer comprises sodium orthophosphate and / or sodium metaphosphate.

[0063] In the present application, the sodium orthophosphate and / or sodium metaphosphate as the stabilizer can be reacted sufficiently to generate the specified product.

[0064] As a preferred technical solution of the present application, the reaction temperature in step (4) is 60-90℃, for example, it can be 60℃, 70℃, 80℃ or 90℃, etc., and the reaction time is 12-24 h, for example, it can be 12 h, 18 h or 24 h, etc.

[0065] In the present application, if the reaction temperature is too low, the reaction speed is slow and the reaction is insufficient; if the reaction temperature is too high, the energy consumption is too large.

[0066] As a preferred technical solution of the present application, the method comprises the following steps:

[0067] (I) crushing the waste ternary lithium ion battery, then adding an alkaline solution with a mass fraction of 5-15% to carry out a dissolution reaction at 60-80℃ for 90-150 min to obtain an aluminum-containing material and a ternary powder;

[0068] (II) mixing the aluminum-containing material and a hydrolysis agent according to a molar ratio of 1:(0.01-0.08) to carry out a hydrolysis reaction at 50-90℃ to obtain aluminum hydroxide;

[0069] (III) mixing the ternary powder and an acid solution with a concentration of 300-350 g / L to carry out acid leaching, the acid leaching temperature is 80-90℃, the acid leaching time is 240-360 min, then adding iron powder to carry out a displacement reaction to obtain copper precipitate and copper-removed leaching solution;

[0070] The adding amount of the iron powder is 1.1-1.2 times of the theoretical amount;

[0071] (IV) adjusting the pH value of the copper-removed leaching solution to 3.8-4.5 to obtain an iron-removed leaching solution and iron precipitate;

[0072] (V) crushing and screening the iron precipitate, and then adding a chlorinating agent to perform chlorination roasting to obtain a chloride;

[0073] The mass ratio of the iron precipitate to the chlorinating agent is 1:(1-3), the temperature of the chlorination roasting is 300-500 DEG C, and the time of the chlorination roasting is 180-240 min;

[0074] (VI) performing acid leaching on the chloride to obtain an acid leaching solution, and then adding an extraction agent to obtain an iron-containing raffinate and a nickel-cobalt-manganese-containing extraction solution;

[0075] The volume-to-mass ratio of the acid leaching solution to the extraction agent is 1 mL:(1-3) mg;

[0076] (VII) stirring and mixing the aluminum hydroxide, the iron-containing raffinate and a stabilizer at a speed of 300-800 rpm for 3-5 h, and then reacting to obtain the polyaluminum ferric chloride;

[0077] The temperature of the reaction is 60-90 DEG C, and the time of the reaction is 12-24 h.

[0078] The numerical range in the present application not only includes the point values listed above, but also includes any point values between the above numerical ranges which are not listed, and the specific point values included in the range are not listed in the present application due to the limitation of the length and the consideration of simplicity.

[0079] Compared with the prior art, the present application has the following beneficial effects:

[0080] The method provided by the present application can not only realize the recovery of high-value metals, thereby fully utilizing and converting into battery materials, but also realize the resource utilization of iron and aluminum slag to prepare polyaluminum ferric chloride which can be used as a high-performance coagulant. Moreover, the method has simple process, high recovery efficiency and wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0081] Figure 1 The process flow chart for preparing polyaluminum ferric chloride is provided for example 1 in the present application.

[0082] Figure 2 The scanning electron microscope image of the polyaluminum ferric chloride prepared in example 1 in the present application at a low magnification.

[0083] Figure 3 The scanning electron microscope image of the polyaluminum ferric chloride prepared in example 1 in the present application at a high magnification. DETAILED DESCRIPTION

[0084] The technical solutions of the present application are further illustrated by the following specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0085] Example 1

[0086] The present embodiment provides a method for preparing polymeric ferric aluminum chloride from iron and aluminum residues in a waste battery recycling process, and a process flow chart of the preparation of polymeric ferric aluminum chloride is shown as follows Figure 1 The method comprises the following steps:

[0087] (I) crushing waste ternary lithium ion batteries to a particle size D50 of 500 nm, then adding a sodium hydroxide solution with a mass fraction of 10% to perform alkali dissolution at 80°C for 90 min to obtain aluminum-containing material NaAlO2 and ternary powder;

[0088] (II) mixing the aluminum-containing material and H2SO4 according to the stoichiometric ratio to perform hydrolysis reaction at 80°C to obtain aluminum hydroxide;

[0089] (III) mixing the ternary powder and a sulfuric acid solution with a concentration of 300 g / L to perform acid leaching, the temperature of the acid leaching is 80°C, the time of the acid leaching is 240 min, then adding iron powder to perform displacement reaction at 80°C to obtain copper precipitate and copper-removed leaching solution containing Ni, Co and Mn elements;

[0090] wherein the amount of iron powder added is 1.1 times the theoretical amount;

[0091] (IV) adjusting the pH value of the copper-removed leaching solution to 4.1 to obtain iron-removed leaching solution and iron pyrite residue;

[0092] (V) crushing and sieving the iron pyrite residue, then adding ammonium chloride to perform chlorination roasting to obtain chlorides;

[0093] wherein the mass ratio of iron pyrite residue and ammonium chloride is 1:1.1, the temperature of chlorination roasting is 300°C, and the time of chlorination roasting is 180 min;

[0094] (VI) mixing the chlorides and an acid solution with a concentration of 80 g / L to perform acid leaching to obtain an acid leaching solution, then adding an extractant to obtain an iron-containing raffinate and a nickel-cobalt-manganese-containing extract;

[0095] wherein the extractant is P204, and the volume-to-mass ratio of the acid leaching solution and the extractant is 1 mL:1.05 g;

[0096] (Ⅶ) stirring and mixing the aluminum hydroxide, the iron-containing raffinate and the stabilizer at a speed of 300 rpm for 3 h, and then reacting under a nitrogen atmosphere to obtain the polymeric ferric aluminum chloride;

[0097] wherein the stabilizer is sodium orthophosphate, the reaction temperature is 90°C, and the reaction time is 12 h.

[0098] Figure 2 and Figure 3 respectively show scanning electron microscope images of the polymeric ferric aluminum chloride prepared in this embodiment at different magnifications, and Figure 2 and Figure 3 It can be seen that the polymeric ferric aluminum chloride has a good structure, more cavities and a large surface area.

[0099] Example 2

[0100] This embodiment provides a method for preparing polymeric ferric aluminum chloride from iron-aluminum slag in a waste battery recycling process, the method comprising the following steps:

[0101] (I) crushing a waste ternary lithium ion battery to a particle size D50 of 500 nm, and then adding a sodium hydroxide solution with a mass fraction of 10% to perform a dissolution reaction at 60°C for 120 min to obtain an aluminum-containing material NaAlO2 and a ternary powder;

[0102] (II) mixing the aluminum-containing material and H2SO4 according to a stoichiometric ratio, and performing a hydrolysis reaction at 60°C to obtain aluminum hydroxide;

[0103] (III) mixing the ternary powder and a sulfuric acid solution with a concentration of 320 g / L to perform acid leaching, the acid leaching temperature being 85°C and the acid leaching time being 300 min, and then adding iron powder to perform a displacement reaction at 80°C to obtain copper precipitate and a copper-removed leaching solution containing Ni, Co and Mn elements;

[0104] wherein the amount of iron powder added is 1.15 times the theoretical amount;

[0105] (IV) adjusting the pH value of the copper-removed leaching solution to 2.5 to obtain a iron-removed leaching solution and a jarosite residue;

[0106] (V) crushing and sieving the jarosite residue, and then adding ammonium chloride to perform chlorination roasting to obtain a chloride;

[0107] wherein the mass ratio of the jarosite residue to ammonium chloride is 1:3, the chlorination roasting temperature is 400°C, and the chlorination roasting time is 200 min;

[0108] (VI) mixing the chloride and an acid solution with a concentration of 80 g / L to perform acid leaching to obtain an acid leaching solution, and then adding an extractant to obtain an iron-containing raffinate and a nickel-cobalt-manganese-containing extraction solution;

[0109] The extraction agent is P507, and the volume-mass ratio of the acid leaching solution and the extraction agent is 1 mL:3 mg.

[0110] (Ⅶ) The aluminum hydroxide, the iron-containing raffinate, and the stabilizer are mixed at a stirring speed of 500 rpm for 4 h, and then reacted in a nitrogen atmosphere to obtain the polymeric ferric aluminum chloride.

[0111] The stabilizer is sodium metaphosphate, the reaction temperature is 70°C, and the reaction time is 20 h.

[0112] Example 3

[0113] The present embodiment provides a method for preparing polymeric ferric aluminum chloride from iron-aluminum slag in a waste battery recycling process, the method comprising the following steps:

[0114] (I) The waste ternary lithium ion battery is crushed to a particle size D50 of 500 nm, and then a sodium hydroxide solution with a mass fraction of 10% is added to perform a dissolution reaction at 60°C for 150 min to obtain aluminum-containing material NaAlO2 and ternary powder material;

[0115] (II) The aluminum-containing material and H2SO4 are mixed according to the stoichiometric ratio, and a hydrolysis reaction is performed at 50°C to obtain aluminum hydroxide;

[0116] (III) The ternary powder material and a sulfuric acid solution with a concentration of 350 g / L are mixed to perform acid leaching, the acid leaching temperature is 90°C, the acid leaching time is 360 min, then iron powder is added to perform a displacement reaction at 80°C to obtain copper precipitate and copper-removed leaching solution containing Ni, Co, and Mn elements;

[0117] The amount of iron powder added is 1.2 times the theoretical amount;

[0118] (IV) The pH value of the copper-removed leaching solution is adjusted to 1.5 to obtain iron-removed leaching solution and iron pyrite residue;

[0119] (V) The iron pyrite residue is crushed and sieved, then ammonium chloride is added to perform chlorination roasting to obtain a chloride;

[0120] The mass ratio of the iron pyrite residue and the ammonium chloride is 1:2, the chlorination roasting temperature is 500°C, and the chlorination roasting time is 240 min;

[0121] (VI) The chloride and an acid solution with a concentration of 80 g / L are mixed to perform acid leaching to obtain an acid leaching solution, then an extraction agent is added to obtain an iron-containing raffinate and a nickel-cobalt-manganese-containing extraction solution;

[0122] The extraction agent is P507, the volume-mass ratio of the acid leaching solution and the extraction agent is 1 mL:1 mg;

[0123] (Ⅶ) The aluminum hydroxide, the iron-containing raffinate and the stabilizer are mixed at a stirring speed of 300 rpm for 5 h, and then reacted in a nitrogen atmosphere to obtain the polymeric ferric aluminum chloride;

[0124] The stabilizer is sodium orthophosphate, the reaction temperature is 60℃, and the reaction time is 24 h.

[0125] Example 4

[0126] The difference between this example and Example 1 is that the mass ratio of the jarosite residue and the chlorinating agent in step (V) is 1:5.

[0127] The rest of the methods and parameters remain the same as in Example 1.

[0128] Example 5

[0129] The difference between this example and Example 1 is that the mass ratio of the jarosite residue and the chlorinating agent in step (V) is 1:0.5.

[0130] The rest of the methods and parameters remain the same as in Example 1.

[0131] Example 6

[0132] The difference between this example and Example 1 is that the chlorination roasting temperature in step (V) is 200℃.

[0133] The rest of the methods and parameters remain the same as in Example 1.

[0134] Example 7

[0135] The difference between this example and Example 1 is that the chlorination roasting temperature in step (V) is 600℃.

[0136] The rest of the methods and parameters remain the same as in Example 1.

[0137] Example 8

[0138] The difference between this example and Example 1 is that no stabilizer is added in step (VII).

[0139] The rest of the methods and parameters remain the same as in Example 1.

[0140] Example 9

[0141] The difference between this example and Example 1 is that the reaction temperature in step (VII) is 50℃.

[0142] The rest of the methods and parameters remain the same as in Example 1.

[0143] Example 10

[0144] The difference between this example and Example 1 is that the temperature of the reaction in step (VII) is 100℃.

[0145] The rest of the method and parameters remain the same as Example 1.

[0146] Comparative Example 1

[0147] The difference between this comparative example and Example 1 is that steps (V) and (VI) are not performed.

[0148] The rest of the method and parameters remain the same as Example 1.

[0149] Performance test

[0150] 1) In the method provided in the above examples, the copper leaching solution and the nickel-cobalt-manganese-containing extraction solution obtained are mixed, and the recovery rate of nickel, cobalt and manganese elements in the obtained mixed solution is detected and compared with the copper leaching solution obtained in the above comparative examples.

[0151] 2) The polymeric ferric aluminum chloride prepared in the above examples and comparative examples is used as a coagulant to precipitate impurities in wastewater, and the impurity removal rate is tested to verify the performance of the polymeric ferric aluminum chloride.

[0152] The test results are shown in Table 1.

[0153] Table 1

[0154]

[0155] Analysis:

[0156] From the above table, it can be seen that the method provided by the present application not only realizes the recovery of high-value metals, thereby fully utilizing the conversion into battery materials, but also realizes the resource utilization of iron and aluminum slag, and polymeric ferric aluminum chloride which can be used as a high-performance coagulant is prepared.

[0157] From Example 1 and Examples 4-5, if the mass ratio of jarosite slag to chlorinating agent is too small, i.e. the amount of chlorinating agent added is too much, there will be residual chlorinating agent, which will affect the reaction and result in poor recovery of metals and poor impurity removal performance of polymeric ferric aluminum chloride; if the mass ratio of jarosite slag to chlorinating agent is too large, i.e. the amount of chlorinating agent added is too small, the reaction will be insufficient, and the recovery of metals and the impurity removal performance of polymeric ferric aluminum chloride will be poor.

[0158] From Example 1 and Examples 6-7, if the temperature of chlorination roasting is too low, the reaction will be insufficient, resulting in poor recovery of metals and poor impurity removal performance of polymeric ferric aluminum chloride; if the temperature of chlorination roasting is too high, the energy consumption will increase.

[0159] From Example 1 and Example 8, if no stabilizer is added, the reaction will be incomplete, resulting in poor metal recovery and poor impurity removal performance of the polymeric ferric aluminum chloride.

[0160] From Example 1 and Example 9-10, if the temperature of the reaction in step (VII) is too low, the reaction will be incomplete, resulting in poor metal recovery and poor impurity removal performance of the polymeric ferric aluminum chloride; if the temperature of the reaction in step (VII) is too high, the energy consumption will increase.

[0161] From Example 1 and Comparative Example 1, if steps (V) and (VI) are not performed, the leaching effect will be poor, resulting in poor metal recovery and poor impurity removal performance of the polymeric ferric aluminum chloride.

[0162] The applicant states that the process of the present application is illustrated by the above examples, but the present application is not limited to the above process steps, i.e. it does not mean that the present application must rely on the above process steps to be implemented. It should be understood by those skilled in the art that any improvement on the present application, equivalent replacement of the materials selected by the present application, addition of auxiliary ingredients, selection of specific methods, etc. all fall within the scope of protection and disclosure of the present application.

Claims

1. A method for preparing polymeric ferric aluminum chloride from iron aluminum dregs in a spent battery recycling process, characterized by, The method comprises the following steps: (1) dissolving the waste lithium ion battery with alkali to obtain aluminum-containing material and powder, then mixing the aluminum-containing material with hydrolysis agent to perform hydrolysis reaction to obtain aluminum hydroxide; (2) performing acid leaching on the powder, then adding iron powder to perform displacement reaction to obtain copper precipitate and copper-removed leaching solution, and then adjusting the pH value of the copper-removed leaching solution to obtain iron-removed leaching solution and iron sulfide residue; (3) performing chlorination roasting on the iron sulfide residue to obtain chloride, then performing acid leaching to obtain acid leaching solution, and then adding extraction agent to obtain iron-containing raffinate and extraction solution; (4) mixing the aluminum hydroxide and the iron-containing raffinate to obtain the polyaluminum ferric chloride.

2. The method of claim 1, wherein, The temperature of the alkali dissolution in step (1) is 60-80℃, and the time of the alkali dissolution is 90-150min.

3. The method of claim 1, wherein, The hydrolysis agent in step (1) comprises dilute sulfuric acid and / or dilute sulfurous acid.

4. The method of claim 1, wherein, The molar ratio of the aluminum-containing material to the hydrolysis agent in step (1) is 1:(0.01-0.08).

5. The method of claim 4, wherein, The molar ratio of the aluminum-containing material to the hydrolysis agent in step (1) is the stoichiometric ratio.

6. The method of claim 1, wherein, The concentration of the acid solution in the acid leaching in step (2) is 300-350g / L.

7. The method of claim 1, wherein, The temperature of the acid leaching in step (2) is 80-90℃, and the time of the acid leaching is 240-360min.

8. The method of claim 1, wherein, The amount of the iron powder added in step (2) is 1.1-1.2 times of the theoretical amount.

9. The method of claim 1, wherein, After adjusting the pH value of the copper-removed leaching solution in step (2), the pH value of the copper-removed leaching solution is 3.8-4.

5.

10. The method of claim 1, wherein, The specific steps of the chlorination roasting in step (3) comprise: Mixing the iron sulfide residue and chlorination agent to perform roasting.

11. The method of claim 10, wherein, The chlorination agent comprises ammonium chloride and / or hydrochloric acid.

12. The method of claim 10, wherein, The mass ratio of the iron sulfide residue to the chlorination agent is 1:(1-3).

13. The method of claim 10, wherein, The temperature of the roasting is 300-500℃, and the time of the roasting is 180-240min.

14. The method of claim 1, wherein, The extraction agent in step (3) comprises phosphorus-based extraction agent.

15. The method of claim 1, wherein, The volume-mass ratio of the acid leaching solution to the extraction agent in step (3) is 1mL:(1-3)mg.

16. The method of claim 1, wherein, The mixing in step (4) is accompanied by stirring. The stirring rate in step (4) is 300-800rpm.

17. The method of claim 1, wherein, A stabilizing agent is further added in the mixing in step (4). The stabilizing agent comprises sodium orthophosphate and / or sodium metaphosphate.

18. The method of claim 1, wherein, The temperature of the reaction in step (4) is 60-90℃, and the time of the reaction is 12-24h.

19. The method of claim 1, wherein, The method comprises the following steps: (I) crushing the waste ternary lithium ion battery, then adding alkali solution with a mass fraction of 5-15% to perform dissolution reaction at 60-80℃ for 90-150min to obtain aluminum-containing material and ternary powder; (II) mixing the aluminum-containing material with hydrolysis agent according to a molar ratio of 1:(0.01-0.08) to perform hydrolysis reaction at 50-90℃ to obtain aluminum hydroxide; (III) mixing the ternary powder with acid solution with a concentration of 300-350g / L to perform acid leaching at 80-90℃ for 240-360min, then adding iron powder to perform displacement reaction to obtain copper precipitate and copper-removed leaching solution; The amount of iron powder is 1.1-1.2 times of the theoretical amount; (IV) adjusting the pH value of the copper-removed leaching solution to 3.8-4.5 to obtain an iron-removed leaching solution and iron precipitate; (V) crushing and screening the iron precipitate, then adding a chlorinating agent to perform chlorination roasting to obtain a chloride; The mass ratio of the iron precipitate to the chlorinating agent is 1:(1-3), the temperature of the chlorination roasting is 300-500℃, and the time of the chlorination roasting is 180-240 min; (VI) performing acid leaching on the chloride to obtain an acid leaching solution, then adding an extraction agent to obtain an iron-containing raffinate and a nickel-cobalt-manganese-containing extraction solution; The volume-to-mass ratio of the acid leaching solution to the extraction agent is 1 mL:(1-3) mg; (VII) stirring and mixing the aluminum hydroxide, the iron-containing raffinate and a stabilizer at a speed of 300-800 rpm for 3-5 h, and then reacting to obtain the polymeric aluminum ferric chloride; The temperature of the reaction is 60-90℃, and the time of the reaction is 12-24 h.

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