CN118619351A - A method for preparing manganese tetraoxide from impure manganese liquid - Google Patents

Abstract

The invention discloses a method for preparing manganese tetraoxide from manganese-containing liquid. The specific implementation process is: after removing copper, zinc, calcium and magnesium metals from manganese-containing liquid produced by nickel-cobalt hydrometallurgy in steps with additives, the manganese liquid and the additives are quantitatively proportioned; at the same time, the configured manganese liquid and alkali solution are continuously introduced into the synthesis kettle, and oxidation synthesis is performed under certain reaction conditions. The invention can use the manganese-containing solution produced by hydrometallurgical extraction as a raw material, and the obtained manganese tetraoxide is nearly spherical and has high purity, meeting the index requirements of battery-grade materials.

Description

A method for preparing manganese tetraoxide from impure manganese liquid

Technical Field

The invention belongs to the technical field of battery material preparation, and in particular relates to a method for preparing manganese tetraoxide by using impure manganese-containing liquid.

Background Art

With the development of industrial technology, nickel cobalt is widely used in the fields of catalysts, aerospace, alloy materials, electronic battery materials, etc., and the demand is increasing day by day. In recent years, with the rise of the battery recycling industry, nickel-cobalt hydrometallurgy has become the focus of non-ferrous metal resource recovery. Manganese is the most common and highest content impurity element in nickel-cobalt hydrometallurgy. In production, it is often discharged from the system in the form of manganese carbonate slag or manganese sulfate solution. The added value of the product is low and the application range is narrow.

There are many methods for preparing manganese tetraoxide, but due to factors such as raw material cost, process conditions, product quality, etc., they only remain at the laboratory level and many methods cannot be industrialized. At present, the common production processes at home and abroad include metal manganese method, manganese salt method, manganese carbonate method and high-priced manganese oxide method.

The metal manganese method is to crush electrolytic manganese flakes into a suspension, add a certain amount of catalyst, and then introduce air, and then make it through processes such as stirring, washing, filter pressing, and drying. At present, most companies use the metal manganese method to prepare manganese tetraoxide. This method is simple to operate and has a high manganese recovery rate, but the cost of the raw material electrolytic manganese flakes is high. Limited by the price of raw materials, it lacks market competitiveness and has poor risk resistance.

Air oxidation is a wet method for preparing manganese tetraoxide. Air is used as an oxidant. A certain concentration of ammonia water is added dropwise to a manganese sulfate solution to obtain manganese hydroxide. The product of manganese tetraoxide is obtained by pressurizing and passing oxygen. This method has a long reaction time and low production efficiency.

Summary of the invention

In view of the above problems, the object of the present invention is to provide a method for preparing manganese tetraoxide from a manganese-containing liquid.

The specific technical solutions are as follows:

A method for preparing manganese tetraoxide from a manganese-containing liquid comprises the following steps:

S1: Using the manganese-containing liquid produced by nickel-cobalt hydrometallurgy as raw material, adjusting the pH of the manganese-containing liquid to 4.0-5.0 with alkali solution, adding additive A, stirring and reacting for 2-3 hours, and then separating the solid and liquid;

S2: Continue to adjust the pH of the impure manganese solution in step S1 to 5.0-6.0 with alkali solution, raise the temperature to 70-80° C., add additive B, stir and react for 2-3 hours, and separate the solid and liquid;

S3: Adding additive C and additive D to the solution treated in step S2, and stirring and mixing for 0.5-1 hour;

S4: adding deionized water as the base liquid to the synthesis reactor, adjusting the pH of the base liquid to 8.5-9.0 with alkali solution, continuously introducing the prepared manganese-containing solution and alkali solution of step S3, controlling the reaction temperature to 40-60° C., maintaining the pH at 8.5-9.5, continuing the reaction under air introduction until the particle size distribution of manganese tetraoxide in the slurry meets the requirements, stopping the reaction and aging for 1-2 hours, and performing solid-liquid separation;

S5: washing and drying the solid phase obtained in step S4 to obtain a spherical manganese tetraoxide product;

Additive A is at least one of sodium sulfide and manganese sulfide, additive B is powdered sodium fluoride, additive C is at least one of ammonium chloride, ammonium sulfate, ammonium nitrate and ammonia monohydrate, and additive D is EDTA.

Furthermore, the metal impurities contained in the manganese-containing liquid produced by the nickel-cobalt hydrometallurgy in step S1 include manganese, copper, zinc, calcium and magnesium, and the manganese concentration is 60-90 g/l.

Furthermore, the alkali solution in steps S1 to S4 is 200-400 g/l sodium hydroxide solution.

Furthermore, the reaction pressure in step S4 is 0.01-0.05 MPa, and the air introduction rate is 100-200 m ³ /h.

Furthermore, the amount of additive A added in step S1 is in a ratio of 1 to 1.05:1 to the amount of copper and zinc contained in the impure manganese-containing liquid, and additive A is added at a rate of 0.2 to 0.5 kg/s.

Furthermore, the amount of additive B added in step S2 is in a ratio of 1.05 to 1.1:1 to the amount of calcium and magnesium contained in the impure manganese-containing liquid, and additive B is added at a rate of 0.2 to 0.5 kg/s.

Furthermore, the amounts of additive C and additive D added in step S3 are 0.06-0.1% and 0.08-0.12% of the total mass of the solution, respectively.

Furthermore, in step S4, the flow rate of the impure manganese solution is 400-800 L/h, and the flow rate of the alkali solution is 100-400 L/h.

Furthermore, the specific operation process of step S5 is to wash and filter the manganese tetraoxide with deionized water for 2 to 3 times, and then dry it at a temperature of 140 to 160° C. until the moisture content is less than 0.3%.

Furthermore, the prepared spherical trimanganese tetraoxide product has a manganese content of ≥70wt%, 4μm≤D ₅₀ ≤10μm, a tap density of ≥2.3g/cm ³ , and a specific surface area of ≤0.7m ² /g.

The beneficial effects of the present invention are:

1) The present invention uses liquid alkali instead of ammonia water, thereby improving the operating environment;

2) The present invention uses impure manganese liquid produced in hydrometallurgy as raw material, reduces the content of impurities such as Cu, Zn, Ca, Mg, etc. after purification, meets the index requirements of battery-grade materials, realizes the resource recovery of manganese, has a simple process route, and is easy to control conditions, and has industrial application value.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a process flow chart of the present invention.

DETAILED DESCRIPTION

In order to make the technical problems, technical solutions and advantages to be solved by the present invention more clear, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

Unless otherwise defined, all professional terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

Manganese tetraoxide was prepared from manganese-containing liquid produced by nickel-cobalt hydrometallurgy. The manganese-containing liquid came from a smelting enterprise in Huludao. The manganese content was 82.69 g/l, the copper content was 0.12 g/l, the zinc content was 1.09 g/l, the calcium content was 1.98 g/l, and the magnesium content was 0.003 g/l. It was prepared using the process shown in Figure 1.

Example 1

S1: Add 200g/l of liquid caustic soda to the impure manganese solution to adjust the pH to 4.5, then add sodium sulfide at a rate of 0.2kg/s, the ratio of the amount of sodium sulfide added to the sum of the amounts of copper and zinc in the solution is 1.05:1, stir and react for 3 hours, filter to obtain a filtrate and a filter residue, the filtrate contains 81.34g/l of Mn, 1.96g/l of Ca, 0.003g/l of Mg, and the contents of Cu and Zn are both less than 1ppm;

S2: Add 200 g/l of liquid caustic soda to the filtrate obtained in S1 to adjust the pH to 5.5, and introduce steam to raise the temperature to 80°C, then add sodium fluoride at a rate of 0.2 kg/s, the ratio of the amount of sodium fluoride added to the sum of the amounts of calcium and magnesium in the solution is 1.1:1, stir and react for 3 hours, filter to obtain a filtrate and a filter residue, the filtrate contains Mn 81.19 g/l, and contains Ca and Mg less than 10 ppm;

S3: adding ammonium chloride and EDTA to the filtrate obtained in S2, wherein the mass of ammonium chloride added is 0.08% of the mass of the manganese solution, and the mass of EDTA added is 0.1% of the mass of the manganese solution, and stirring is performed for 0.5 hours for later use;

S4: Add a small amount of deionized water to the bottom of the synthesis reactor, add 200g/l of liquid caustic soda to adjust the pH to 9.0, then add the manganese solution prepared in S3 and 200g/l of liquid caustic soda at the same time, during which 0.02MPa of air is introduced, the manganese solution introduction flow rate is 400L/h, the initial liquid caustic soda introduction flow rate is 200L/h, the pH is set to 8.8-9.2, and the liquid caustic soda flow rate is automatically adjusted by pH, the air introduction flow rate is ^150m3 /h, the feeding is stopped after 24 hours of reaction, the reaction is aged for 2 hours, and the filtrate and filter residue are obtained by filtration;

S5: The filter residue obtained in S4 was washed and filtered three times with deionized water, and flash dried at 140° C. until the moisture content was less than 0.25%, to obtain trimanganese tetraoxide, the particle size distribution of which is shown in Table 1.

The test results show that the manganese content is 70.96%, the tap density is 2.44 g/cm ³ , the specific surface area is 0.41 m ² /g, and the particle size D50 is 8.029 μm.

Table 1 Summary of particle size distribution of manganese tetraoxide prepared in Example 1

Particle size/μm Range/% accumulation/% Particle size/μm Range/% accumulation/% 0.684-0.753 0.00 0.00 4.682-5.154 2.53 6.91 0.753-0.829 0.01 0.01 5.154-5.674 4.15 11.06 0.829-0.913 0.03 0.04 5.674-6.247 7.47 18.53 0.913-1.004 0.11 0.15 6.247-6.878 10.54 29.07 1.004-1.106 0.07 0.22 6.878-7.572 12.52 41.59 1.106-1.218 0.02 0.24 7.572-8.336 13.51 55.10 1.219-1.341 0.00 0.24 8.336-9.178 13.05 68.15 1.341-1.476 0.00 0.24 9.178-10.10 10.82 78.67 1.476-1.625 0.00 0.24 10.10-11.12 8.37 87.04 1.625-1.789 0.00 0.24 11.12-12.24 6.13 93.17 1.789-1.970 0.00 0.24 12.24-13.48 3.99 97.16 1.970-2.169 0.01 0.25 13.48-14.84 1.82 98.98 2.169-2.388 0.02 0.27 14.84-16.34 0.70 99.68 2.388-2.629 0.12 0.39 16.34-17.98 0.26 99.94 2.629-2.894 0.21 0.60 17.98-19.80 0.03 100.00 2.894-3.187 0.31 0.91 19.80-21.80 0.00 100.00 3.187-3.508 0.43 1.34 21.80-24.00 0.00 100.00 3.508-3.862 0.61 1.95 24.00-26.43 0.00 100.00 3.862-4.252 0.92 2.87 26.43-29.10 0.00 100.00 4.252-4.682 1.51 4.38 29.10-32.03 0.00 100.00

Example 2

The other operation steps are the same as those in Example 1, with the main difference being that in step S4 the pH automatic control range in the synthesis reactor is set to 8.5 to 8.9. The particle size distribution of the obtained trimanganese tetraoxide is shown in Table 2.

The test results show that the manganese content is 70.96%, the tap density is 2.44 g/cm ³ , the specific surface area is 0.41 m ² /g, and the particle size D50 is 8.029 μm.

Table 2 Summary of particle size distribution of manganese tetraoxide prepared in Example 2

Particle size/μm Range/% accumulation/% Particle size/μm Range/% accumulation/% 0.684-0.753 0.11 1.79 4.682-5.154 8.41 70.52 0.753-0.829 0.03 1.82 5.154-5.674 7.76 78.28 0.829-0.913 0.00 1.82 5.674-6.247 6.28 84.56 0.913-1.004 0.00 1.82 6.247-6.878 4.97 89.53 1.004-1.106 0.02 1.84 6.878-7.572 3.82 93.35 1.106-1.218 0.11 1.95 7.572-8.336 2.74 96.09 1.219-1.341 0.20 2.15 8.336-9.178 1.77 97.86 1.341-1.476 0.30 2.45 9.178-10.10 0.97 98.83 1.476-1.625 0.48 2.93 10.10-11.12 0.60 99.43 1.625-1.789 0.73 3.66 11.12-12.24 0.34 99.77 1.789-1.970 1.17 4.83 12.24-13.48 0.17 99.94 1.970-2.169 1.81 6.64 13.48-14.84 0.05 99.99 2.169-2.388 2.76 9.40 14.84-16.34 0.01 100.00 2.388-2.629 4.44 13.84 16.34-17.98 0.00 100.00 2.629-2.894 5.86 19.70 17.98-19.80 0.00 100.00 2.894-3.187 7.21 26.91 19.80-21.80 0.00 100.00 3.187-3.508 8.31 35.22 21.80-24.00 0.00 100.00 3.508-3.862 9.02 44.24 24.00-26.43 0.00 100.00 3.862-4.252 9.02 53.26 26.43-29.10 0.00 100.00 4.252-4.682 8.85 62.11 29.10-32.03 0.00 100.00

Example 3

The other operation steps are the same as those in Example 1, with the main difference being that in step S4 the pH automatic control range in the synthesis reactor is set to 9.1-9.5. The particle size distribution of the obtained trimanganese tetraoxide is shown in Table 3.

The test results show that the manganese content is 70.88%, the tap density is 2.50 g/cm ³ , the specific surface area is 0.45 m ² /g, and the particle size D50 is 6.78 μm.

Table 3 Summary of particle size distribution of manganese tetraoxide prepared in Example 3

Particle size/μm Range/% accumulation/% Particle size/μm Range/% accumulation/% 0.684-0.753 0.19 2.95 4.682-5.154 6.19 67.38 0.753-0.829 0.07 3.02 5.154-5.674 5.65 73.03 0.829-0.913 0.03 3.05 5.674-6.247 4.71 77.74 0.913-1.004 0.09 3.14 6.247-6.878 4.03 81.77 1.004-1.106 0.19 3.33 6.878-7.572 3.46 85.23 1.106-1.218 0.32 3.65 7.572-8.336 2.92 88.15 1.219-1.341 0.47 4.12 8.336-9.178 2.39 90.54 1.341-1.476 0.67 4.79 9.178-10.10 1.87 92.41 1.476-1.625 1.03 5.82 10.10-11.12 1.60 94.01 1.625-1.789 1.49 7.31 11.12-12.24 1.34 95.35 1.789-1.970 2.07 9.38 12.24-13.48 1.14 96.49 1.970-2.169 2.90 12.18 13.48-14.84 0.90 97.39 2.169-2.388 3.69 15.87 14.84-16.34 0.71 98.10 2.388-2.629 4.89 20.76 16.34-17.98 0.58 98.68 2.629-2.894 5.79 26.55 17.98-19.80 0.46 99.14 2.894-3.187 6.56 33.11 19.80-21.80 0.35 99.49 3.187-3.508 7.11 40.22 21.80-24.00 0.22 99.71 3.508-3.862 7.29 47.51 24.00-26.43 0.15 99.86 3.862-4.252 7.01 54.52 26.43-29.10 0.10 99.96 4.252-4.682 6.67 61.19 29.10-32.03 0.04 100.00

The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims (10)

1. The method for preparing the manganous-manganic oxide by using the hetero-manganese-containing liquid is characterized by comprising the following steps of:

S1, taking a mixed manganese-containing liquid produced by nickel-cobalt hydrometallurgy as a raw material, adjusting the pH value of the mixed manganese-containing liquid to 4.0-5.0 by alkali liquor, adding an additive A, stirring and reacting for 2-3 hours, and then carrying out solid-liquid separation;

S2: continuously adjusting the pH value of the mixed manganese-containing liquid in the step S1 to 5.0-6.0 by using alkali liquor, heating to 70-80 ℃, adding the additive B, stirring and reacting for 2-3 hours, and then carrying out solid-liquid separation;

S3: adding the additive C and the additive D into the solution treated in the step S2, and stirring and mixing for 0.5-1 hour;

s4: adding deionized water as base solution into a synthesis kettle, regulating the pH of the base solution to 8.5-9.0 by using alkali solution, continuously introducing the prepared mixed manganese-containing solution and alkali solution in the step S3, controlling the reaction temperature to 40-60 ℃, keeping the pH at 8.5-9.5, continuously reacting under the condition of introducing air until the granularity distribution of the manganous oxide in the slurry meets the requirement, stopping the reaction, aging for 1-2h, and carrying out solid-liquid separation;

s5: washing and drying the solid phase obtained in the step S4 to obtain a spherical manganous oxide product;

The additive A is at least one of sodium sulfide and manganese sulfide, the additive B is powdery sodium fluoride, the additive C is at least one of ammonium chloride, ammonium sulfate, ammonium nitrate and ammonia monohydrate, and the additive D is EDTA.

2. The method for preparing manganous oxide from a solution containing manganic salt according to claim 1, wherein the metal impurities contained in the solution containing manganous salt produced by hydrometallurgical production of nickel cobalt in the step S1 include manganese, copper, zinc, calcium and magnesium, and the manganese concentration is 60-90g/l.

3. The method for preparing trimanganese tetroxide from a solution containing manganese impurities according to claim 1, wherein the alkaline solution is 200-400 g/l sodium hydroxide solution.

4. The method for preparing manganous oxide by using a solution containing hetero manganese according to claim 1, wherein the reaction pressure in the step S4 is 0.01-0.05 MPa, and the air introducing rate is 100-200 m ³/h.

5. The method for preparing trimanganese tetroxide from a solution containing manganese impurities according to claim 2, wherein the ratio of the amount of additive a added in step S1 to the amount of copper and zinc contained in the solution containing manganese impurities is 1-1.05:1, and additive a is added at a rate of 0.2-0.5 kg/S.

6. The method for preparing trimanganese tetroxide from a solution containing manganese impurities according to claim 5, wherein the ratio of the amount of additive B added in step S2 to the amount of calcium and magnesium contained in the solution containing manganese impurities is 1.05-1.1:1, and additive B is added at a rate of 0.2-0.5 kg/S.

7. The method for preparing manganous-manganic oxide from a solution containing hetero-manganese according to claim 6, wherein the addition amount of the additive C and the additive D in the step S3 is 0.06-0.1% and 0.08-0.12% of the total mass of the solution respectively.

8. The method for preparing trimanganese tetroxide from a solution containing manganese impurities according to claim 7, wherein the flow rate of the solution containing manganese impurities in the step S4 is 400-800L/h, and the flow rate of the alkaline solution is 100-400L/h.

9. The method for preparing trimanganese tetroxide from the heteromanganese-containing solution according to claim 8, wherein the specific operation in step S5 is to wash and filter trimanganese tetroxide 2-3 times with deionized water, and then dry to a moisture content of <0.3% at a temperature of 140-160 ℃.

10. The method for preparing manganous oxide by using the hetero-manganese-containing liquid according to claim 9, wherein the manganese content in the prepared spherical manganous oxide product is more than or equal to 70wt%, D ₅₀ is more than or equal to 4 μm and less than or equal to 10 μm, tap density is more than or equal to 2.3g/cm ³, and specific surface area is less than or equal to 0.7m ²/g.