A process for recovering manganese from a crude feed material

Abstract

The application discloses a method for recovering manganese from crude raw materials, and belongs to the technical field of manganese recovery and treatment in battery materials. The method comprises the following steps: oxidizing and roasting the crude raw materials to be treated to obtain roasted materials; wherein the crude raw materials contain at least one of nickel hydroxide and cobalt hydroxide, and manganese hydroxide; preparing slurry from the roasted materials to obtain slurry; performing normal pressure leaching on the slurry under acidic conditions until the pH value of the leaching solution obtained by normal pressure leaching is 4-6, and then performing solid-liquid separation to obtain the first leaching solution and the first leaching residue containing manganese dioxide; performing high-pressure oxygen leaching on the first leaching residue under acidic conditions to remove most of the residual nickel and / or cobalt in the first leaching residue, and then performing solid-liquid separation to obtain the second leaching solution and the second leaching residue mainly containing manganese dioxide. The method is simple in operation, low in cost, and can recover manganese from crude raw materials at a high yield.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of manganese recovery treatment in battery materials, in particular to a method for recovering manganese from crude raw materials. BACKGROUND

[0002] In the crude nickel-cobalt hydroxide raw material, the mass ratio of total mass of nickel and cobalt to mass of manganese is about 7:1 to 14:1. The existing technology smelts nickel-cobalt hydroxide by generally adopting impurity removal by leaching, 204 impurity extraction, 507 cobalt-magnesium extraction, nickel sulfate evaporation process, and C272 manganese recovery production line. Part of the manganese is back-extracted with calcium, copper and other impurities during 204 impurity extraction, and needs to be purified by C272 extraction and de-coppering to meet the requirements of battery-grade manganese sulfate. The remaining manganese-calcium mixed solution is generally back-extracted by hydrochloric acid to avoid pipe blockage due to high calcium content, and needs to be treated by precipitation and other treatments. The cost of the entire process is more than 20,000 yuan per ton of metal manganese, while the market price of 1 ton of battery-grade manganese sulfate is about 15,000 yuan.

[0003] In view of this, the present application is proposed. SUMMARY

[0004] The present application aims to provide a method for recovering manganese from crude raw materials to solve or improve the above technical problems.

[0005] The present application can be achieved as follows:

[0006] The present application provides a method for recovering manganese from crude raw materials, comprising the following steps:

[0007] Oxidizing and roasting the crude raw material to be treated to convert the manganese hydroxide contained in the crude raw material into manganese dioxide, to obtain a roasting material; wherein the crude raw material contains at least one of nickel hydroxide and cobalt hydroxide and manganese hydroxide;

[0008] Preparing a slurry from the roasting material;

[0009] Carrying out atmospheric leaching of the slurry at a pH value of 4-6, followed by solid-liquid separation, to obtain a first leaching solution and a first leaching residue containing manganese dioxide;

[0010] Carrying out high-pressure oxygen leaching of the first leaching residue under acidic conditions to remove most of the residual nickel and / or cobalt in the first leaching residue, followed by solid-liquid separation, to obtain a second leaching solution and a second leaching residue mainly containing manganese dioxide.

[0011] In an optional embodiment, the temperature of the oxidizing and roasting is 200-500°C, and / or the time of the oxidizing and roasting is 2-4h.

[0012] In an optional embodiment, the oxidizing roasting is performed in an oxidizing atmosphere.

[0013] In an optional embodiment, the oxidizing atmosphere is provided by oxygen or oxygen-rich gas.

[0014] In an optional embodiment, the oxygen content in the oxygen-rich gas is 20wt% to 99.95wt%.

[0015] In an optional embodiment, the solid content of the slurry is 10wt% to 40wt%.

[0016] In an optional embodiment, the temperature of the atmospheric leaching is 40°C to 100°C, and / or the time of the atmospheric leaching is 1.5h to 4h.

[0017] In an optional embodiment, the pH value of the atmospheric leaching process is controlled by adding inorganic acid to the slurry.

[0018] In an optional embodiment, the atmospheric leaching process is further added with an oxidizing agent to make Fe 2+ in the slurry completely converted into Fe 3+ .

[0019] In an optional embodiment, the oxidizing agent includes at least one of hydrogen peroxide and sodium persulfate.

[0020] In an optional embodiment, the ratio of the molar mass of nickel and cobalt in the crude raw material to the molar mass of the oxidizing agent is 100:1 to 100:5.

[0021] In an optional embodiment, the mass concentration of the hydrogen peroxide is 7.8wt% to 27.5wt%.

[0022] In an optional embodiment, the temperature of the high-pressure oxygen leaching is 120°C to 220°C; and / or the oxygen partial pressure of the high-pressure oxygen leaching is 0.3MPa to 0.5MPa; and / or the time of the high-pressure oxygen leaching is 2h to 6h.

[0023] In an optional embodiment, the oxygen atmosphere used in the high-pressure oxygen leaching process is an oxygen atmosphere provided by pure oxygen.

[0024] In an optional embodiment, the high-pressure oxygen leaching process is performed in the presence of an acid.

[0025] In an optional embodiment, the acid used in the high-pressure oxygen leaching process is an inorganic acid.

[0026] In an optional embodiment, the acid used in the high-pressure oxygen leaching process includes at least one of sulfuric acid and hydrochloric acid.

[0027] In an optional embodiment, the acid solution is added to the container containing the first leaching residue and pure oxygen is introduced to perform high-pressure oxygen leaching, wherein the initial acidity of the acid solution is 50-100 g / L.

[0028] In an optional embodiment, the second leaching solution is subjected to copper removal treatment to obtain a copper-removed solution and a copper product.

[0029] In an optional embodiment, the copper-removed solution is recycled to the roasting material slurry-making process.

[0030] The beneficial effects of the present application include:

[0031] The present application can convert manganese hydroxide in the crude raw material into manganese dioxide by oxidizing roasting of the crude raw material to obtain a roasting material; can separate a first leaching residue containing manganese dioxide by atmospheric leaching of the slurry obtained by slurry-making of the roasting material under acidic conditions; and can separate a second leaching residue mainly containing manganese dioxide by high-pressure oxygen leaching of the first leaching residue under acidic conditions.

[0032] The method for recovering manganese from the crude raw material provided by the present application has a short process flow, simple operation, low cost, small manganese leaching amount, and can efficiently recover a manganese product with high purity by precipitating manganese in the residue, thereby providing a new feasible way for recovery and utilization of manganese in the crude raw material. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced as follows. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. Other related drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0034] Figure 1 The process flow chart of the method for recovering manganese from the crude raw material in the embodiment 1 of the present application;

[0035] Figure 2 The XRD pattern of the crude nickel-cobalt hydroxide in the embodiment 6 of the present application;

[0036] Figure 3 The XRD pattern of the roasting material in the embodiment 6 of the present application;

[0037] Figure 4 The XRD pattern of the second leaching residue in the embodiment 6 of the present application. DETAILED DESCRIPTION

[0038] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. If specific conditions are not indicated in the embodiments, the conventional conditions or the conditions suggested by the manufacturers are adopted. If the manufacturers of the reagents or instruments are not indicated, the conventional products that can be purchased in the market are adopted.

[0039] The method for recovering manganese from crude raw materials provided by the present application will be described in detail below.

[0040] The present application provides a method for recovering manganese from crude raw materials, comprising the following steps:

[0041] S1: oxidizing roasting the crude raw material to be treated, so that the manganese hydroxide contained in the crude raw material is converted into manganese dioxide, to obtain a roasting material; wherein the crude raw material contains at least one of nickel hydroxide and cobalt hydroxide and manganese hydroxide.

[0042] In some embodiments, the crude raw material can be crude nickel hydroxide, which mainly contains nickel hydroxide and additionally contains a small amount of manganese hydroxide and other components. In some embodiments, the crude raw material can be crude cobalt hydroxide, which mainly contains cobalt hydroxide and additionally contains a small amount of manganese hydroxide and other components. In some other embodiments, the crude raw material can be crude nickel-cobalt hydroxide, which mainly contains nickel hydroxide and cobalt hydroxide and additionally contains a small amount of manganese hydroxide and other components.

[0043] The aforementioned "mainly" and "small amount" are relative concepts, and the present application does not limit the specific content range thereof, that is, as long as the content of nickel hydroxide and / or cobalt hydroxide is higher than that of manganese hydroxide, the manganese hydroxide can be considered as a "small amount" of component, and the nickel hydroxide and / or cobalt hydroxide can be considered as a "main" component.

[0044] In the present application, the oxidizing roasting can be carried out in a rotary kiln, a steel belt furnace or other roasting equipment.

[0045] The temperature of the oxidizing roasting can be 200℃-500℃, such as 200℃, 250℃, 300℃, 350℃, 400℃, 450℃ or 500℃, etc., or other arbitrary values within the range of 200℃-500℃.

[0046] If the temperature of the oxidizing roasting is lower than 200℃, the manganese hydroxide cannot be effectively converted into manganese dioxide; if the temperature of the oxidizing roasting is higher than 500℃, the processing cost will be greatly increased.

[0047] The time of the oxidizing roasting can be 2h-4h, such as 2h, 2.5h, 3h, 3.5h or 4h, etc., or other arbitrary values within the range of 2h-4h.

[0048] Similarly, if the oxidizing roasting time is shorter than 2h, the manganese hydroxide cannot be effectively converted into manganese dioxide; if the oxidizing roasting time is longer than 4h, the processing cost will be greatly increased.

[0049] By performing the oxidizing roasting under the above conditions, the manganese hydroxide in the crude raw material can be converted into manganese dioxide, and the corresponding reaction equation is as follows: 2Mn(OH)2+O2=2MnO2+H2O. In the process, the nickel hydroxide and the cobalt hydroxide are still in the form of hydroxides and will not be converted into the corresponding oxides.

[0050] In the present application, the oxidizing roasting is performed in an oxidizing atmosphere.

[0051] The above oxidizing atmosphere can be provided by oxygen or oxygen-enriched gas, etc. Among them, the oxygen content in the oxygen-enriched gas can be 20wt%~99.95wt%, such as 20wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, 95wt% or 99.95wt%, etc. When the oxygen content in the oxygen-enriched gas is about 21wt%, the oxygen-enriched gas can be considered as air.

[0052] S2: The roasting material is subjected to slurry preparation to obtain a slurry.

[0053] In the present application, the solid content of the slurry can be 10wt%~40wt%, such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%, etc., or any other value within the range of 10wt%~40wt%.

[0054] By roughly controlling the solid content of the slurry within the above range, the subsequent operation is facilitated.

[0055] S3: The slurry is subjected to atmospheric leaching under the condition that the pH value is 4~6, followed by solid-liquid separation to obtain a first leaching liquid and a first leaching residue containing manganese dioxide.

[0056] The atmospheric leaching process can be performed in a reaction kettle.

[0057] In the present application, the temperature of the atmospheric leaching can be 40℃~100℃, such as 40℃, 50℃, 60℃, 70℃, 80℃, 90℃ or 100℃, etc., or any other value within the range of 40℃~100℃.

[0058] The time of the atmospheric leaching can be 1.5h~4h, such as 1.5h, 2h, 2.5h, 3h, 3.5h or 4h, etc., or any other value within the range of 1.5h~4h.

[0059] By way of illustration, the pH value of the atmospheric leaching process can be controlled by adding inorganic acid to the slurry. Accordingly, the time of atmospheric leaching is the reaction time after the acid is added. The amount of acid added is determined by the pH value of the mixture of the slurry and the acid being 4-6 (e.g. 4, 4.5, 5, 5.5 or 6).

[0060] Illustratively, the inorganic acid can include at least one of sulfuric acid and hydrochloric acid.

[0061] In the present application, no reducing agent is added during the atmospheric leaching process, and in some embodiments, an oxidizing agent can be added to the atmospheric leaching process to convert Fe 2+ in the slurry to Fe 3+ in the slurry. The oxidizing agent can include at least one of hydrogen peroxide and sodium persulfate. The concentration of the hydrogen peroxide can be, for example, 7.8wt%-27.5wt%.

[0062] By way of illustration, the ratio of the molar mass of nickel and cobalt in the crude raw material to the molar mass of the oxidizing agent can be 100:1-100:5, such as 100:1, 100:2, 100:3, 100:4 or 100:5, etc.

[0063] After the atmospheric leaching described above, the elements such as iron, aluminum and copper that can be contained in the slurry can be precipitated into the first leaching residue after solid-liquid separation (e.g. filtration), while the elements such as nickel and cobalt in the slurry remain in the first leaching solution.

[0064] The first leaching solution described above can be further subjected to processes such as extraction and deep impurity removal to obtain a battery-grade nickel product or a cobalt product or a nickel-cobalt product.

[0065] In some embodiments, the first leaching residue can be recycled for multiple atmospheric leaching and then subjected to high-pressure oxygen leaching to improve the enrichment effect of manganese and reduce the content of nickel and cobalt in the residue.

[0066] In this way, the requirement that the content of impurities such as iron, aluminum and copper be <2ppm can be met in the process of extracting nickel and cobalt without the need for impurity removal.

[0067] S4: The first leaching residue is subjected to high-pressure oxygen leaching under acidic conditions to remove most of the residual nickel and / or cobalt in the first leaching residue, followed by solid-liquid separation to obtain a second leaching solution and a second leaching residue mainly composed of manganese dioxide.

[0068] The process can be carried out in an autoclave.

[0069] In the present application, the temperature of the high-pressure oxygen leaching can be 120°C-220°C, such as 120°C, 140°C, 160°C, 180°C, 200°C or 220°C, etc., or any other value within the range of 120°C-220°C.

[0070] The oxygen partial pressure of the high-pressure oxygen leaching can be 0.3 MPa to 0.5 MPa, such as 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, or 0.5 MPa, or any other value within the range of 0.3 MPa to 0.5 MPa. It can be understood that the high-pressure oxygen leaching is carried out under the condition of 0.3 MPa to 0.5 MPa higher than the normal pressure.

[0071] If the oxygen partial pressure of the high-pressure oxygen leaching is too low, the oxidation effect will be poor; if the oxygen partial pressure of the high-pressure oxygen leaching is too high, the risk of spontaneous combustion will easily occur.

[0072] The time of the high-pressure oxygen leaching can be 2 h to 6 h, such as 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, or 6 h, or any other value within the range of 2 h to 6 h.

[0073] The oxygen atmosphere used in the high-pressure oxygen leaching process is an oxygen atmosphere provided by pure oxygen.

[0074] The high-pressure oxygen leaching process is carried out in the presence of an acid, and the acid used in the process is an inorganic acid, which can include at least one of sulfuric acid and hydrochloric acid.

[0075] In some embodiments, an acid solution can be added to the autoclave containing the first leaching residue, and pure oxygen is introduced to carry out high-pressure oxygen leaching. For reference, the initial acidity of the acid solution can be 50 g / L to 100 g / L, such as 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, or 100 g / L. Taking sulfuric acid as an example, the initial concentration of the acid solution can be understood as containing 50 g to 100 g of sulfuric acid per liter of acid solution.

[0076] Through high-pressure oxygen leaching, the residual nickel and cobalt elements in the first leaching residue can be leached into the second leaching solution, while the manganese in the first leaching residue is enriched in the second leaching residue, thereby facilitating the increase of the manganese content in the second leaching residue and the reduction of the nickel and / or cobalt content in the second leaching residue. If the crude raw material contains iron and aluminum, Fe 3+ is hydrolyzed to diiron trioxide, and Al 3+ is hydrolyzed to aluminum trioxide, which is left in the second leaching residue together with manganese dioxide.

[0077] In some embodiments, if the crude raw material contains copper, the second leaching solution can be subjected to copper removal treatment to obtain a copper-removed solution and a copper product. The copper-removed solution can be recycled to the roasting material pulping process.

[0078] In some embodiments, the second leaching residue can be washed to further wash away the free cobalt and / or nickel remaining in the second leaching residue, to improve the purity of manganese in the residue, so that the obtained manganese dioxide product can reach the standard of manganese concentrate.

[0079] In some embodiments, the second leaching residue can be recycled for multiple high-pressure oxygen leaching, and then washed, to improve the enrichment effect of manganese.

[0080] In some embodiments, the washing residue water after washing the leaching residue can also be returned to the roasting material slurry process for recycling.

[0081] In summary, the method for recovering manganese from crude raw materials provided by the present application has a short process flow, simple operation, low cost, and can efficiently recover a high-purity manganese product, thereby providing a new feasible way for the recovery and utilization of manganese in crude raw materials.

[0082] The features and performances of the present application are further described in detail below in combination with examples.

[0083] Example 1

[0084] This example provides a method for recovering manganese from crude raw materials, please refer to Figure 1 , which comprises the following steps:

[0085] S1: oxidizing roasting the crude nickel-cobalt hydroxide to be treated in a rotary kiln, the temperature of the oxidizing roasting is 200℃, the time of the oxidizing roasting is 3h, and the oxidizing atmosphere of the oxidizing roasting is provided by air. Through the oxidizing roasting treatment, the manganese hydroxide contained in the crude raw material is converted into manganese dioxide, to obtain a roasting material.

[0086] Among them, the crude nickel-cobalt hydroxide mainly contains Ni and Co, and further contains Mn, Al, Ca, Cr, Cu, Fe, Zn and Mg, etc., and part of the elemental composition is shown in Table 1.

[0087] Table 1: Part of the elemental content of the crude nickel-cobalt hydroxide (dry basis, wt%)

[0088] Ni Co Mn Ca Fe Cr Cu Zn Mg Al 40.2238 2.8676 7.074 0.065 0.1789 0.0025 0.0337 0.4154 2.01 0.0567

[0089] S2: slurry the roasting material with water to obtain a slurry with a solid content of 30wt%.

[0090] S3: pass the slurry into a reaction kettle, add sulfuric acid until the pH value of the mixed solution of the slurry and sulfuric acid is 5, add hydrogen peroxide with a concentration of 27.5wt%, the molar mass ratio of nickel and cobalt in the crude raw material to the molar mass of the oxidizing agent is 100:3, and the normal pressure leaching is carried out at 60℃ for 2h, followed by filtration, to obtain a first leaching liquid and a first leaching residue containing manganese dioxide.

[0091] The first leaching solution is used for extraction and deep impurity removal.

[0092] S4: The first leaching residue is put into an autoclave, and a sulfuric acid solution with an initial acidity of 75 g / L is added and pure oxygen is introduced. High-pressure oxygen leaching is carried out at a temperature of 160°C and an oxygen partial pressure of 0.4 MPa for 3 hours, and then filtration is performed to obtain a second leaching solution and a second leaching residue mainly composed of manganese dioxide.

[0093] The mass percentages of the contents of some elements in the second leaching residue obtained in this step and the contents of some elements in the second leaching solution in the total amount of the element contained in the crude cobalt hydroxide are shown in Table 2.

[0094] Table 2 Element statistical results

[0095]

[0096] S5: The second leaching solution is subjected to copper removal treatment to obtain a copper-removed solution and a copper product. The copper-removed solution can be recycled to the roasting material slurry process.

[0097] S6: The second leaching residue is washed (water washing, 3 times) to obtain a manganese concentrate. The residue washing water can also be recycled to the roasting material slurry process.

[0098] Example 2

[0099] The difference between this example and Example 1 is that in the S1 step, the oxidizing atmosphere of the oxidation roasting is provided by pure oxygen.

[0100] The mass percentages of the contents of some elements in the second leaching residue obtained in the S4 step of this example and the contents of some elements in the second leaching solution in the total amount of the element contained in the crude cobalt hydroxide are shown in Table 3.

[0101] Table 3 Element statistical results

[0102]

[0103] Example 3

[0104] The difference between this example and Example 1 is that in the S1 step, the temperature of the oxidation roasting is 500°C.

[0105] The mass percentages of the contents of some elements in the second leaching residue obtained in the S4 step of this example and the contents of some elements in the second leaching solution in the total amount of the element contained in the crude cobalt hydroxide are shown in Table 4.

[0106] Table 4 Element statistical results

[0107]

[0108] Example 4

[0109] The difference between this example and Example 1 is that no oxidizing agent is used in the S3 step.

[0110] The mass percentages of the contents of some elements in the second leaching residue obtained in the S4 step of this example and the contents of some elements in the second leaching solution relative to the total contents of the elements in the crude cobalt hydroxide are shown in Table 5.

[0111] Table 5 Element statistics

[0112]

[0113] Example 5

[0114] This example provides a method for recovering manganese from a crude raw material, comprising the following steps:

[0115] S1: oxidizing roasting the crude nickel hydroxide to be treated in a rotary kiln, the oxidizing roasting temperature is 300°C, the oxidizing roasting time is 4h, and the oxidizing atmosphere of the oxidizing roasting is provided by an oxygen-enriched gas with an oxygen content of 59wt%. Through the oxidizing roasting treatment, the manganese hydroxide contained in the crude nickel hydroxide is converted into manganese dioxide, and a roasted material is obtained.

[0116] The crude nickel hydroxide mainly contains Ni, and further contains Co, Mn, Al, Ca, Cr, Cu, Fe and Mg, etc., and the compositions of some elements are shown in Table 6.

[0117] Table 6 Contents of some elements in the crude nickel hydroxide (dry basis, wt%)

[0118] Ni Co Mn Al Ca Cr Cu Fe Mg 40.1322 2.7345 7.003 0.06 0.1342 0.0025 0.0287 0.4232 1.98

[0119] S2: slurry the roasted material with water to obtain a slurry with a solid content of 10wt%.

[0120] S3: pass the slurry into a reaction kettle, add sulfuric acid until the pH value of the mixture of the slurry and hydrochloric acid is 4, add hydrogen peroxide with a concentration of 7.8wt%, the ratio of the molar mass of nickel and cobalt in the crude raw material to the molar mass of the oxidizing agent is 100:1, and the slurry is leached at 40°C under normal pressure for 2.5h, followed by filtration to obtain a first leaching solution and a first leaching residue containing manganese dioxide.

[0121] The above first leaching solution is used for processes such as extraction and deep impurity removal.

[0122] S4: pass the first leaching residue into an autoclave, add an aqueous sulfuric acid solution with an initial acidity of 50g / L and pass in pure oxygen, and perform high-pressure oxygen leaching at a temperature of 120°C and an oxygen partial pressure of 0.3MPa for 4h, followed by filtration to obtain a second leaching solution and a second leaching residue mainly containing manganese dioxide.

[0123] The mass percentage of the content of some elements in the second leaching residue and the content of some elements in the second leaching solution in the total content of the elements in the crude cobalt hydroxide is shown in Table 7.

[0124] Table 7 Element statistics

[0125]

[0126] S5: The second leaching solution is subjected to copper removal treatment to obtain a copper-removed solution and a copper product. The copper-removed solution can be recycled to the roasting material slurry process.

[0127] S6: The second leaching residue is washed (water washing, washing 2 times) to obtain a manganese concentrate. The washing water can also be recycled to the roasting material slurry process.

[0128] Example 6

[0129] The present embodiment provides a method for recovering manganese from a crude raw material, comprising the following steps:

[0130] S1: The crude cobalt hydroxide to be treated is subjected to oxidative roasting in a steel belt furnace, the temperature of the oxidative roasting is 400°C, the time of the oxidative roasting is 2h, and the oxidizing atmosphere of the oxidative roasting is provided by an oxygen-rich gas with an oxygen content of 80wt%. Through the oxidative roasting treatment, the manganese hydroxide contained in the crude cobalt hydroxide is converted into manganese dioxide to obtain a roasting material. The XRD pattern of the crude nickel-cobalt hydroxide is shown in Figure 2 .

[0131] The crude cobalt hydroxide mainly contains Co, and further contains Ni, Mn, Al, Ca, Cr, Cu, Fe and Mg, etc., and the composition of some elements is shown in Table 8.

[0132] Table 8 Partial element content of crude cobalt hydroxide (dry basis, wt%)

[0133] Co Ni Mn Al Ca Cr Cu Fe Mg 39.0421 2.6673 7.1207 0.062 0.1298 0.0022 0.0319 0.3892 2.0142

[0134] S2: The roasting material is added with water to obtain a slurry with a solid content of 40wt%.

[0135] S3: The slurry is introduced into a reaction kettle, sulfuric acid is added until the pH value of the mixture of the slurry and sulfuric acid is 6, hydrogen peroxide with a concentration of 27.5wt% is added, the molar mass ratio of nickel and cobalt in the crude raw material to the molar mass of the oxidizing agent is 100:5, and the slurry is subjected to atmospheric pressure leaching at 100°C for 1.5h, followed by filtration to obtain a first leaching solution and a first leaching residue containing manganese dioxide.

[0136] The XRD patterns of the above roasting material and the first leaching residue are shown inFigure 3 As shown.

[0137] The first leaching solution is used for the processes of extraction and deep impurity removal.

[0138] S4: The first leaching residue is put into an autoclave, an aqueous solution of sulfuric acid with an initial acidity of 100 g / L is added, and pure oxygen is introduced, and high-pressure oxygen leaching is carried out at a temperature of 220 ℃ and an oxygen partial pressure of 0.5 MPa for 2 h, followed by filtration to obtain a second leaching solution and a second leaching residue mainly composed of manganese dioxide.

[0139] The mass percentages of the contents of some elements in the second leaching residue obtained in this step and the contents of some elements in the second leaching solution in the total amount of the element contained in the crude cobalt hydroxide are shown in Table 9, and the XRD spectrum of the second leaching residue is shown in Figure 4 As shown.

[0140] Table 9 Element Statistics

[0141]

[0142] S5: The second leaching solution is subjected to copper removal treatment to obtain a copper-removed solution and a copper product. The copper-removed solution can be recycled to the roasting material slurry process.

[0143] S6: The second leaching residue is washed (water washing, washing 1 time) to obtain a manganese concentrate. The residue washing water can also be recycled to the roasting material slurry process.

[0144] Comparative Example 1

[0145] The difference between this comparative example and Example 1 is that the crude nickel-cobalt hydroxide is not subjected to the S1 step, and the treatment starts directly from the S2 step.

[0146] The mass percentages of the contents of some elements in the second leaching residue obtained by high-pressure oxygen leaching in this comparative example and the contents of some elements in the second leaching solution in the total amount of the element contained in the crude cobalt hydroxide are shown in Table 10.

[0147] Table 10 Element Statistics

[0148]

[0149] Comparative Example 2

[0150] The difference between this comparative example and Example 1 is that in the S1 step, the roasting is carried out in an oxygen-free atmosphere.

[0151] The mass percentages of the contents of some elements in the second leaching residue obtained by high-pressure oxygen leaching in this comparative example and the contents of some elements in the second leaching solution in the total amount of the element contained in the crude cobalt hydroxide are shown in Table 11.

[0152] Element statistics results of Table 11

[0153]

[0154] Comparative Example 3

[0155] The difference between this comparative example and Example 1 is that the temperature of the oxidative roasting in step S1 is 180°C.

[0156] The mass percentages of the contents of some elements in the second leaching residue obtained by high-pressure oxygen leaching of this comparative example and the contents of some elements in the second leaching solution account for the total amount of the element contained in the crude cobalt hydroxide are shown in Table 12.

[0157] Element statistics results of Table 12

[0158]

[0159] Comparative Example 4

[0160] The difference between this comparative example and Example 1 is that the oxygen atmosphere in step S4 is provided by air.

[0161] The mass percentages of the contents of some elements in the second leaching residue obtained by high-pressure oxygen leaching of this comparative example and the contents of some elements in the second leaching solution account for the total amount of the element contained in the crude cobalt hydroxide are shown in Table 13.

[0162] Element statistics results of Table 13

[0163]

[0164] Comparative Example 5

[0165] The difference between this comparative example and Example 1 is that the high-pressure leaching in step S4 is carried out in an oxygen-free environment.

[0166] The mass percentages of the contents of some elements in the second leaching residue obtained by high-pressure oxygen leaching of this comparative example and the contents of some elements in the second leaching solution account for the total amount of the element contained in the crude cobalt hydroxide are shown in Table 14.

[0167] Element statistics results of Table 14

[0168]

[0169] Comparative Example 6

[0170] The difference between this comparative example and Example 1 is that the initial acidity of the acid solution in step S4 is 40 g / L.

[0171] The content of some elements in the second leaching residue obtained by high-pressure oxygen leaching of the present comparative example and the content of some elements in the second leaching solution account for the total amount of the element contained in the crude cobalt hydroxide in mass percentage as shown in Table 15.

[0172] Table 15 Element statistical results

[0173]

[0174] Comparative example 7

[0175] The difference between the present comparative example and example 1 is that in the S4 step, the initial acidity of the acid solution is 120 g / L.

[0176] The content of some elements in the second leaching residue obtained by high-pressure oxygen leaching of the present comparative example and the content of some elements in the second leaching solution account for the total amount of the element contained in the crude cobalt hydroxide in mass percentage as shown in Table 16.

[0177] Table 16 Element statistical results

[0178]

[0179] As can be seen from the comparison of examples 1-3 and comparative example 1, the leaching rate of manganese corresponding to the process without oxidation roasting is about 57%, while the leaching rate of manganese corresponding to the process with oxidation roasting is < 15%, which greatly reduces the leaching rate of manganese.

[0180] As can be seen from the results of the above examples and comparative examples, the method provided by the present application can reduce the leaching rate of manganese, obtain a manganese product with higher yield, and thus achieve the purpose of effectively recovering manganese from crude raw materials.

[0181] In summary, the method for recovering manganese from crude raw materials provided by the present application has a short process flow, simple operation, low cost, and less manganese leaching amount, and can efficiently recover a high-purity manganese product by precipitating manganese in the slag, which can meet the requirements of manganese concentrate and be sold as a product, and no solid waste or hazardous waste is produced during the entire leaching process, which is not only environmentally friendly and safe, but also beneficial to improving profits, and provides a new feasible way for the recovery and utilization of manganese in crude raw materials.

[0182] The above only describes preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method of recovering manganese from a crude feed material, characterised in that, The method comprises the following steps: oxidizing roasting a crude raw material to be treated to convert manganese hydroxide contained in the crude raw material into manganese dioxide, to obtain a roasting material; wherein the crude raw material contains at least one of nickel hydroxide and cobalt hydroxide, and manganese hydroxide; slurry preparation of the roasting material to obtain a slurry; atmospheric leaching of the slurry at a pH value of 4-6, followed by solid-liquid separation, to obtain a first leaching solution and a first leaching residue containing manganese dioxide; high-pressure oxygen leaching of the first leaching residue under acidic conditions to remove most of the residual nickel and / or cobalt in the first leaching residue, followed by solid-liquid separation, to obtain a second leaching solution and a second leaching residue mainly containing manganese dioxide.

2. The method of claim 1, wherein, The temperature of the oxidizing roasting is 200-500°C, and / or the time of the oxidizing roasting is 2-4 hours.

3. The method according to claim 1 or 2, characterized in that, The oxidizing roasting is performed in an oxidizing atmosphere.

4. The method of claim 3, wherein, The oxidizing atmosphere is provided by oxygen or oxygen-rich gas.

5. The method of claim 4, wherein, The oxygen content in the oxygen-rich gas is 20-99.95 wt%.

6. The method of claim 1, wherein, The solid content of the slurry is 10-40 wt%.

7. The method of claim 1, wherein, The temperature of the atmospheric leaching is 40-100°C, and / or the time of the atmospheric leaching is 1.5-4 hours.

8. The method of claim 1, wherein, The pH value of the atmospheric leaching process is controlled by adding inorganic acid to the slurry.

9. The method of claim 8, wherein, The inorganic acid comprises at least one of sulfuric acid and hydrochloric acid.

10. The method of claim 7, wherein, The atmospheric leaching process is also supplemented with an oxidizing agent to oxidize Fe 2+ to Fe 3+ in the slurry.

11. The method of claim 10, wherein, The oxidizing agent comprises at least one of hydrogen peroxide and sodium persulfate.

12. The method of claim 11, wherein, The ratio of the molar mass of nickel and cobalt in the crude raw material to the molar mass of the oxidizing agent is 100:1-100:

5.

13. The method of claim 11, wherein, The mass concentration of the hydrogen peroxide is 7.8-27.5 wt%.

14. The method of claim 1, wherein, The temperature of the high-pressure oxygen leaching is 120-220°C; and / or the oxygen partial pressure of the high-pressure oxygen leaching is 0.3-0.5 MPa; and / or the time of the high-pressure oxygen leaching is 2-6 hours.

15. The method of claim 14, wherein, The oxygen atmosphere used in the high-pressure oxygen leaching process is provided by pure oxygen.

16. The method of claim 14, wherein, The high-pressure oxygen leaching process is performed in the presence of an acid.

17. The method of claim 16, wherein, The acid used in the high-pressure oxygen leaching process is an inorganic acid.

18. The method of claim 17, wherein, The acid used in the high-pressure oxygen leaching process comprises at least one of sulfuric acid and hydrochloric acid.

19. The method of claim 16, wherein, An acid solution is added to a container containing the first leaching residue, and pure oxygen is introduced to perform high-pressure oxygen leaching, wherein the initial acidity of the acid solution is 50-100 g / L.

20. The method of claim 1, wherein, When the crude raw material also contains copper, the method further comprises: copper removal treatment of the second leaching solution to obtain a copper-removed solution and a copper product.

21. The method of claim 20, wherein, The copper-removed solution is recycled to the roasting material slurry preparation process.

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