CN113321241A - High-valence manganese oxide, preparation method thereof and preparation method of nickel manganese sulfate solution - Google Patents
High-valence manganese oxide, preparation method thereof and preparation method of nickel manganese sulfate solution Download PDFInfo
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Abstract
The invention relates to the technical field of hydrometallurgy, in particular to a high-valence manganese oxide and a preparation method thereof, and a preparation method of a nickel-manganese sulfate solution. The preparation method of the high valence manganese oxide comprises the following steps: adding an oxidant and a neutralizing agent into the copper-zinc-calcium-removed copper-manganese chloride solution to perform manganese oxidation precipitation reaction, and performing solid-liquid separation to obtain a high-valence manganese oxide; wherein the higher manganese oxide comprises: trimanganese tetroxide, manganese dioxide, basic manganese sulfate and manganese hydroxide; the pH value of the copper chloride manganese solution after copper, zinc and calcium removal is 3.0-5.0; in the process of carrying out manganese oxidation precipitation reaction, the pH value of the solution system is 7.0-10.5. The preparation method is simple and easy to implement, mild in operation condition and high in manganese yield, the reusable high-valence manganese oxide is prepared by taking the copper-manganese chloride solution as a raw material, the investment cost of the extracting agent is reduced, and meanwhile, a large amount of oxidant is obtained on the premise of keeping the original operation cost.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a high-valence manganese oxide and a preparation method thereof, and a preparation method of a nickel-manganese sulfate solution, and more particularly relates to a treatment process of a copper-manganese chloride solution in a cobalt metallurgy process, and a process for preparing battery-grade nickel sulfate for a ternary precursor by dissolving nickel powder.
Background
With the rapid development of the ternary nickel-cobalt-manganese-lithium battery, in order to obtain a stable raw material source, many companies for producing ternary precursors adopt a mode of purchasing raw materials and preparing the raw materials by themselves aiming at nickel sulfate and cobalt sulfate which are high in price and short in supply. The nickel sulfate is prepared by adding sulfuric acid and dissolving with hydrogen peroxide, wherein the nickel sulfate is usually prepared by taking nickel powder or nickel beans as raw materials.
In the process of preparing nickel sulfate by dissolving nickel powder, the nickel powder and sulfuric acid have poor reactivity, so that the sulfuric acid is difficult to completely consume during the reaction, the acidity of the nickel sulfate solution after the reaction is high, and the reaction is difficult to continue at the acidity of 0.1-0.9N. In the prior art, hydrogen peroxide is added when the reaction acidity reaches 0.1-0.9N, and the nickel powder is promoted to be dissolved by using the oxidative nickel oxide powder of the hydrogen peroxide, so that a nickel sulfate solution with low acidity (pH of 2-3) is obtained. However, in the process of using hydrogen peroxide to dissolve nickel powder, the reaction temperature is usually 70 to 90 ℃, so hydrogen peroxide is easy to volatilize and decompose, which increases the amount of hydrogen peroxide and increases the cost. In addition, a large amount of hydrogen gas is generated in the reaction process of the nickel powder and the sulfuric acid, which easily causes a safety problem. Therefore, an oxidant which does not introduce impurities and is low in price is found to replace hydrogen peroxide, and the process has excellent prospect.
In addition, in the process of preparing cobalt sulfate from the cobalt hydroxide intermediate product, the P507 extraction agent cannot separate calcium, so that the P204 extraction process needs to be preset for calcium removal. Since calcium sulfate is slightly soluble, hydrochloric acid is often used for washing in the washing stage, which results in the production of copper manganese chloride liquor. The common treatment scheme of the copper chloride manganese solution is that impurities such as copper, zinc, calcium and the like in the copper chloride manganese solution are removed by a chemical method, and then a manganese sulfate back-extraction solution is obtained by a P507 extraction process, so that the recovery of manganese resources is realized. Manganese is an element with multiple valence states, and manganese oxide with a higher valence state is insoluble in water in most cases, so that manganese in the copper chloride manganese solution can be oxidized into high-valence manganese oxide by using air, so that the manganese is separated from the solution and recovered. Meanwhile, the obtained high-valence manganese oxide can be used as an oxidant in the nickel powder dissolving process, and the high-valence manganese oxide is finally converted into manganese sulfate in the process. The nickel sulfate solution is converted to a nickel manganese sulfate solution. However, for the preparation of the ternary precursor, the preparation of the ternary precursor is not affected only by controlling the proportion in the final nickel-manganese solution and the content of other impurity elements.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of high valence manganese oxide, which is simple and easy to implement, mild in operation condition and high in manganese yield, and the reusable high valence manganese oxide is prepared by taking copper manganese chloride liquid as a raw material, so that the investment cost of an extracting agent is reduced, and meanwhile, a large amount of oxidant is obtained on the premise of keeping the original operation cost.
The second purpose of the invention is to provide high valence manganese oxide, which has low raw material cost for preparation, strong oxidizability, can be used as an oxidant and can be used for preparing nickel manganese sulfate.
The third purpose of the invention is to provide a preparation method of nickel manganese sulfate solution, which can promote the dissolution of nickel, reduce the generation of hydrogen and ensure safer method. In addition, the high-valence manganese oxide is used for replacing hydrogen peroxide, so that the problems of high volatility, easy decomposition, large using amount and high cost existing in the condition of using hydrogen peroxide as an oxidant can be avoided.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the preparation method of the high-valence manganese oxide comprises the following steps:
adding an oxidant and a neutralizing agent into the copper-zinc-calcium-removed copper-manganese chloride solution to perform manganese oxidation precipitation reaction, and performing solid-liquid separation to obtain a high-valence manganese oxide;
wherein the higher manganese oxide comprises: trimanganese tetroxide, manganese dioxide, basic manganese sulfate and manganese hydroxide;
the pH value of the copper chloride manganese solution after copper, zinc and calcium removal is 3.0-5.0;
in the process of carrying out manganese oxidation precipitation reaction, the pH value of the solution system is 7.0-10.5.
The preparation method of the high-valence manganese oxide provided by the invention takes copper-manganese chloride solution as a raw material, firstly reacts with continuously added oxidant under an alkaline condition, and continuously adds alkali liquor to neutralize acid released in the high-valence manganese precipitation process so as to control the reaction pH to be maintained between 7 and 10.5 and convert bivalent manganese ions into trimanganese tetroxide, and the yield of manganese in the step can reach 70 to 99 percent.
Preferably, a strong oxidant can be used for further oxidizing the high-valence manganese oxide, and/or alkali is used for carrying out precipitation reaction on the manganese ions left in the filtrate after solid-liquid separation. This further increases the yield of manganese to 99%.
In addition, the preparation method is simple and feasible, mild in condition and wide in reaction condition, manganese is oxidized by air to be converted into high-valence manganese oxide, the cost is low, and meanwhile Mn is2+The recovery rate is higher.
In the process of preparing the cobalt sulfate, a P204 extraction procedure is required to remove calcium, and because calcium sulfate is a slightly soluble substance, hydrochloric acid is usually adopted for washing in a washing section, and a copper manganese chloride solution is generated in the step. The main component of the copper chloride manganese solution is manganese chloride, and impurities such as copper ions, zinc ions, calcium ions and the like also exist in the copper chloride manganese solution.
The main components of the copper chloride manganese solution without removing copper, zinc and calcium provided by the invention comprise: manganese chloride, copper chloride, zinc chloride and calcium chloride; wherein, the content of manganese element is 50-100g/L, the content of zinc element is 0-10g/L, the content of copper element is 0-15g/L, and the content of calcium element is 0-10 g/L; the other impurity elements are cobalt, magnesium and aluminum which are all less than 1 g/L.
Preferably, the pH value of the copper chloride manganese solution after copper, zinc and calcium removal is 4.0-4.9.
Preferably, in the process of carrying out the manganese oxidation precipitation reaction, the pH value of the solution system is 7.5-8.5.
Preferably, the neutralizing agent comprises at least one of aqueous ammonia, sodium hydroxide solution and potassium hydroxide solution, more preferably sodium hydroxide solution.
When ammonia is selected as the alkali solution, the ammonia is responsible for Mn2+Has stronger complexing ability and can cause Mn2+Incomplete precipitation of Mn2+The recovery rate is low, and the Mn can be increased only by increasing the pH of the reaction system2+However, the impurities such as calcium and magnesium are likely to enter the high-valence manganese oxide by increasing the reaction pH. Therefore, the neutralizing agent is more preferably a sodium hydroxide solution.
Preferably, the molar concentration of the hydroxide ions in the neutralizing agent is 3-12 mol/L, more preferably 6-10 mol/L, including but not limited to any one of the points of 4mol/L, 5mol/L, 7mol/L, 8mol/L, 9mol/L, 11mol/L or a range between any two.
Preferably, in the manganese oxidation precipitation reaction, the temperature of the solution system is 40 to 95 ℃, more preferably 60 to 80 ℃, including but not limited to any one of 45 ℃, 50 ℃, 55 ℃, 65 ℃, 70 ℃, 75 ℃, 85 ℃ and 90 ℃ or a range between any two.
Preferably, the oxidant comprises at least one of air, oxygen, potassium permanganate, potassium perchlorate, and ammonium persulfate, more preferably air.
Preferably, the preparation method of the higher manganese oxide comprises the following steps: continuously introducing air into the copper-zinc-calcium-removed copper-manganese chloride solution, continuously adding ammonia water to enable the pH value of the mixed solution system to be 7.5-8.5, carrying out manganese oxidation precipitation reaction, and after the reaction is finished, adding a potassium permanganate solution into the mixed solution to react with the residual Mn2+Further recovering, and then carrying out solid-liquid separation to obtain the high-valence manganese oxide.
Air is introduced into the alkaline copper-manganese chloride solution, and the reaction principle is as follows:
Mn2++OH-＝＝Mn(OH)2；
6Mn(OH)2+O2＝＝2Mn3O4+6H2O。
preferably, the time of the oxidation precipitation reaction is 8-30 h, more preferably 10-24 h, including but not limited to any one of 9h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h and 23h or a range between any two.
Preferably, the copper and zinc removing treatment of the copper and manganese chloride solution specifically comprises the following steps: and mixing the copper-manganese chloride solution with sulfide, and after reaction, carrying out solid-liquid separation to obtain a copper-manganese chloride mixed solution without copper and zinc.
In the mixing process, the pH value of the solution system is 2.5-5.0.
Preferably, the sulphide comprises at least one of manganese sulphide, sodium sulphide, ammonium sulphide and hydrogen sulphide, more preferably sodium sulphide and/or ammonium sulphide.
And sulfide is added into the copper-manganese chloride solution, so that copper ions and zinc ions in the copper-manganese chloride solution can be converted into copper sulfide and zinc sulfide precipitates, and then the copper sulfide and the zinc sulfide precipitates are removed.
Preferably, the copper chloride manganese solution is subjected to calcium removal treatment, and the method specifically comprises the following steps: and mixing the copper and zinc-removed copper and manganese chloride mixed solution with sulfate, and after reaction, carrying out solid-liquid separation to obtain a preliminary calcium-removed copper and manganese chloride mixed solution.
The step mainly utilizes CaSO4Low solubility in water, Ca2+Converted to calcium sulfate precipitate and removed.
Preferably, the sulfate salt comprises at least one of sodium sulfate, ammonium sulfate, and potassium sulfate, more preferably sodium sulfate and/or ammonium sulfate.
Preferably, the calcium removal treatment further comprises: and mixing the preliminary calcium-removal copper-manganese chloride mixed solution with a fluoride, and after reaction, carrying out solid-liquid separation to obtain the copper-zinc-calcium-removal copper-manganese chloride mixed solution. The step is a deep calcium removal process. The preliminary calcium removal copper-manganese chloride mixed solution reacts with fluoride to generate calcium fluoride precipitate, and calcium impurities can be completely removed after solid-liquid separation.
Preferably, the fluoride comprises at least one of sodium fluoride, ammonium fluoride and manganese fluoride.
In some specific embodiments, the primary calcium-removing copper-manganese chloride mixed solution can be selected as a raw material to react with the oxidant, and the copper-manganese chloride mixed solution with copper, zinc and calcium removed can also be selected as a raw material to react with the oxidant.
Preferably, the product obtained by sequentially reacting the preliminary calcium-removing copper-manganese chloride mixed solution with an oxidant and an oxidant is a high-valence manganese oxide subjected to preliminary calcium removal.
Preferably, the product obtained by sequentially reacting the copper-zinc-calcium-removed copper-manganese chloride mixed solution with an oxidant and an oxidant is a high-valence manganese oxide subjected to deep calcium removal.
In some embodiments, if the prepared high-valence manganese oxide is used in the front-end process of nickel powder dissolution, and the requirement on calcium content is high due to the high-valence manganese oxide usage amount, the high-valence manganese oxide with deep calcium removal can be used as the oxidant.
If the prepared high-valence manganese oxide is used for the process of replacing hydrogen peroxide at the tail end of the nickel powder dissolution, the high-valence manganese oxide with less consumption has loose requirements on the calcium content, and the high-valence manganese oxide subjected to preliminary calcium removal can be used as an oxidant, and the high-valence manganese oxide subjected to deep calcium removal can be used as the oxidant.
The high-valence manganese oxide provided by the invention is prepared by the preparation method.
The high-valence manganese oxide provided by the invention has stronger oxidizability, can be used as an oxidant, and can be used for preparing nickel manganese sulfate.
The preparation method of the nickel sulfate manganese solution provided by the invention comprises the following steps: and mixing the high-valence manganese oxide prepared by the preparation method or the high-valence manganese oxide with sulfuric acid and metallic nickel, and reacting to obtain the nickel-manganese sulfate solution.
The preparation principle of the nickel sulfate manganese solution is as follows:
Mn3O4+Ni+4H2SO4＝＝NiSO4+3MnSO4+4H2O；
MnO2+Ni+2H2SO4＝＝NiSO4+MnSO4+2H2O；
Mn(OH)2+H2SO4＝＝MnSO4+H2O；
Mn2(OH)2SO4+H2SO4＝＝MnSO4+2H2O；
Ni+H2SO4＝＝NiSO4+H2↑。
in the prior art, a large amount of hydrogen is generated during the reaction of nickel and sulfuric acid, so that the safety problem is easy to generate. The preparation method provided by the invention can reduce the generation of hydrogen and radically reduce the occurrence of safety problems.
Wherein the nickel sulfate manganese solution mainly comprises nickel sulfate and manganese sulfate.
According to the preparation method of the nickel sulfate manganese solution, provided by the invention, the high-valence manganese oxide is used as an oxidant, so that the dissolution of metal nickel is promoted, and the cost of a hydrogen peroxide oxidant is greatly reduced; in addition, the preparation method provided by the invention can reduce hydrogen generated by the reaction of nickel and sulfuric acid, so as to relieve the safety problem caused by too fast generation of hydrogen.
Preferably, the preparation method specifically comprises the following steps:
(a) adding high-valence manganese oxide into a mixed solution containing metal nickel and sulfuric acid, then adding metal nickel into the mixed solution, and reacting until the molar concentration of hydrogen ions in the solution is 0.1-0.9 mol/L to obtain a nickel-manganese sulfate solution with high acidity; and/or the presence of a gas in the gas,
(b) adding high-valence manganese oxide into the nickel sulfate manganese solution with high acidity obtained in the step (a), reacting until the pH value of the solution is 2-3, and after solid-liquid separation, respectively obtaining the nickel sulfate manganese solution with low acidity and the nickel powder which is not completely reacted.
Wherein, the nickel powder which is not completely reacted can be recycled.
In the reaction process, because the reaction performance of the nickel powder and the sulfuric acid is poor, the sulfuric acid is difficult to completely consume in the reaction, so that the acidity of the prepared nickel sulfate solution or nickel manganese sulfate solution is high, and the subsequent use is not facilitated. According to the invention, the high-valence manganese oxide is added into the solution, and the high-valence manganese oxide can oxidize nickel powder to promote reaction, so that the pH value of the nickel sulfate manganese solution is increased to reach a qualified value.
Preferably, in the step (a), the molar concentration of the hydrogen ions in the mixed solution is 1-6 mol/L, and preferably 4-5 mol/L.
Preferably, in the step (a), the molar ratio of the metallic nickel to the sulfuric acid in the mixed solution is 1-3: 1.
Preferably, in the step (a), the sum of the amount of the substance of the manganese element in the higher manganese oxide and the amount of the substance of the metallic nickel to be added subsequently and the like and the amount of the substance of the sulfuric acid in the mixed solution.
Preferably, in the step (a), the molar ratio of the manganese element in the high-valence manganese oxide to the sulfuric acid in the mixed solution is 0.1-0.3: 1.
Preferably, in step (a), the molar ratio of manganese element to metallic nickel in the higher oxides of manganese ranges from 1:5 to 1:1, more preferably from 1:5 to 3:5, during said addition of metallic nickel thereto.
In the step (b), the molar ratio of the manganese element in the high-valence manganese oxide to the sulfuric acid in the solution is 0.4-0.5: 1.
Preferably, in step (a) and/or step (b), the temperature of the solution system is 50 to 100 ℃, more preferably 90 to 95 ℃, including but not limited to the point value of any one of 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 95 ℃ or 98 ℃ or the range value between any two.
The nickel powder and the sulfuric acid react to generate a large amount of hydrogen, and if the nickel powder and the sulfuric acid are thrown into the reactor once too much, safety problems are easy to occur, so that the feeding speed needs to be controlled to control the generation rate of the hydrogen.
The reaction can be promoted to proceed toward the positive direction by using the above temperature range.
Preferably, in the step (b), after the nickel manganese sulfate solution is obtained, iron removal and copper removal steps are further included.
Wherein, iron impurity and copper impurity all derive from nickel powder or equipment corruption, and along with the reaction goes on, copper impurity and iron impurity easily take place to enrich, pile up, produce the condition that exceeds standard, consequently need carry out the operation of deironing and decoppering.
Preferably, the solid-liquid separation comprises filtration and/or centrifugation.
Preferably, the method for removing iron comprises a jarosite method and the method for removing copper comprises a nickel displacement copper removal method.
The nickel-cobalt-manganese sulfate solution provided by the invention can be used for preparing a nickel-cobalt-manganese ternary material, and specifically, cobalt sulfate is added into the nickel-manganese sulfate solution, the proportion of each raw material is adjusted to obtain a ternary precursor feed liquid, and the ternary precursor feed liquid reacts with a complexing agent and a precipitating agent to obtain the nickel-cobalt-manganese ternary material. The method recycles the waste liquid to prepare the nickel manganese sulfate solution, and does not influence the application of the original nickel sulfate solution in the direction of the ternary precursor.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the high-valence manganese oxide provided by the invention takes the copper-manganese chloride solution as a raw material, and reacts with an oxidant under specific conditions, so that manganese can be oxidized into the high-valence manganese oxide and precipitated and separated out.
(2) Compared with pure battery grade trimanganese tetroxide, the preparation method provided by the invention has lower requirements on the original solution and the physical and chemical properties of the product such as purity, appearance and the like, so that NaOH instead of ammonia water can be used as alkali for reaction, or strong oxidant is used for recovering residual manganese and the like, and higher manganese yield is obtained by sacrificing the appearance, the purity and the like.
(3) The main component of the high-valence manganese oxide provided by the invention comprises trimanganese tetroxide, the high-valence manganese oxide has stronger oxidizability, can be used as an oxidant, has low raw material cost, and is beneficial to further popularization and use.
(4) The preparation method of the nickel sulfate manganese solution provided by the invention is safer, and can reduce the generation of hydrogen while promoting the dissolution of nickel; in addition, the high-valence manganese oxide is used as an oxidant to replace the traditional hydrogen peroxide, so that the cost is greatly reduced.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The main components of the copper chloride manganese solution without removing copper, zinc and calcium provided in the following embodiments of the invention comprise: manganese chloride, copper chloride, zinc chloride and calcium chloride; wherein, the content of manganese element is 50-100g/L, the content of zinc element is 0-10g/L, the content of copper element is 0-15g/L, and the content of calcium element is 0-10 g/L; the other impurity elements are cobalt element, magnesium element and aluminum element, and the content is less than 1 g/L.
Example 1
The preparation method of the high-valence manganese oxide provided by the embodiment comprises the following steps:
(a) adjusting the pH value of the copper and manganese chloride raw material liquid to 2.0, adding 34g of sodium sulfide into 2L of the copper and manganese chloride raw material liquid, continuously stirring, reacting for 1 hour, and carrying out solid-liquid separation to obtain a liquid without copper and zinc and sulfide slag; under the condition of continuous stirring, adjusting the pH value of the solution after copper and zinc removal to be 4.0, continuously adding ammonium sulfate into the solution after copper and zinc removal, detecting the content of calcium in the solution until the content of calcium is less than 0.5g/L, and carrying out solid-liquid separation to obtain copper and zinc removal and preliminary calcium removal copper and manganese chloride solution and calcium slag.
The components of the copper chloride manganese raw material solution and the components of the copper zinc removal and preliminary calcium removal copper chloride manganese solution are shown in the following table 1:
TABLE 1 comparison of the composition of copper manganese chloride feed solution with copper zinc removal and preliminary calcium removal copper manganese chloride solution
(b) Adding NaOH solution into the copper and zinc removal and preliminary calcium removal copper and manganese chloride solution at 70 ℃, adjusting the pH to 7, continuously introducing air into the solution to serve as an oxidant, slowly and continuously adding the NaOH solution (the concentration of hydroxide ions is 6mol/L, the volume is 0.5L, and the using amount is 2 times of the amount of manganese elements), controlling the pH of a reaction system to be 7.5, adjusting the pH to 8.5 after 9 hours of reaction, stirring for 10min, and performing solid-liquid separation to obtain high-valence manganese oxide (no drying operation is needed during use).
The high-valence manganese oxide was washed and dried, and weighed 237.15g, calculated from the amount of manganese in the slag and the manganese solution before reaction, the yield of manganese in the preparation step of the high-valence manganese oxide was 99.26%, and the analysis of the components of the high-valence manganese oxide is shown in table 2 below.
TABLE 2 compositional analysis of higher oxides of manganese
| Element(s) | Mn | Ca | Mg | Al | Cu | Zn | Co |
| High manganese oxide (%) | 70.12 | 0.032 | 0.0012 | 0.0005 | 0.0002 | 0.0003 | 0.0005 |
The preparation method of the nickel manganese sulfate solution provided by the embodiment comprises the following steps:
adding 14g of the prepared high-valence manganese oxide into 2L of nickel sulfate solution containing 400g of nickel powder and 0.5mol/L of hydrogen ions, continuously stirring at 95 ℃, reacting until the solution is clear, and obtaining the nickel-manganese sulfate solution with low acidity, wherein the pH value of the nickel-manganese sulfate solution is 3.0, the concentration of calcium element is 0.0036g/L, most of calcium comes from the high-valence manganese oxide, and the concentration meets the standard of calcium content in the battery-grade nickel sulfate solution. The composition of the initial nickel sulfate solution and the resulting nickel manganese sulfate solution are shown in table 3 below.
TABLE 3 compositional analysis of the initial nickel sulfate solution and the resulting nickel manganese sulfate solution
| Element(s) | Ni | Mn | Cu | Zn | Ca | Al | Mg |
| Copper manganese liquid (g/L) | 102.68 | 0.0005 | 0.0004 | 0.0003 | 0.0013 | 0.0005 | 0.0005 |
| Preliminary calcium removal (g/L) | 104.68 | 4.89 | 0.0004 | 0.0004 | 0.0036 | 0.0006 | 0.0007 |
Example 2
The preparation method of the high-valence manganese oxide provided by the embodiment comprises the following steps:
(a) adjusting the pH value of the copper and manganese chloride raw material liquid to 2.5, adding 35g of ammonium sulfide into 2L of the copper and manganese chloride raw material liquid, continuously stirring, reacting for 2 hours, and carrying out solid-liquid separation to obtain a liquid without copper and zinc and a sulfide slag; under the condition of continuous stirring, adjusting the pH value of the solution after copper and zinc removal to be 5.0, continuously adding sodium sulfate into the solution after copper and zinc removal, detecting the content of calcium in the solution until the content of calcium is less than 0.5g/L, and carrying out solid-liquid separation to obtain copper and zinc removal and preliminary calcium removal copper and manganese chloride solution and calcium slag;
then, at the temperature of 95 ℃, 5.2g of sodium fluoride (3 times of the theoretical dosage of calcium and magnesium in the reaction) is added into the obtained copper and zinc removal and preliminary calcium and copper and manganese removal chloride liquid, the mixture is continuously stirred and reacted for 1 hour, and after solid-liquid separation, the copper and manganese chloride liquid with deep calcium and magnesium removal is obtained, and the components of the copper and manganese chloride liquid are shown in the following table 4.
TABLE 4 composition analysis of deep calcium and magnesium-depleted copper manganese chloride liquids
(b) Adding NaOH solution into the copper and zinc removal and preliminary calcium removal copper and manganese chloride solution at 80 ℃, adjusting the pH to 10, continuously introducing air into the solution to serve as an oxidant, slowly and continuously adding the NaOH solution (the concentration of hydroxide ions is 10mol/L, the volume is 0.3L, and the using amount is 2 times of the amount of manganese elements), controlling the pH of a reaction system to be 8.5, after reacting for 15 hours, adjusting the pH to 9, stirring for 15 minutes, and after solid-liquid separation, obtaining high-valence manganese oxide (drying operation is not needed during use). The compositional analysis of the higher manganese oxide is shown in Table 5 below.
TABLE 5 compositional analysis of higher manganese oxides
| Element(s) | Mn | Ca | Mg | Al | Cu | Zn | Co |
| High manganese oxide (%) | 70.35 | 0.0016 | 0.0011 | 0.0005 | 0.0002 | 0.0003 | 0.0005 |
The preparation method of the nickel manganese sulfate solution provided by the embodiment comprises the following steps:
adding 80g of the prepared high-valence manganese oxide into 2L of sulfuric acid solution containing 400g of nickel powder and 4mol/L of hydrogen ion concentration, continuously stirring at 90 ℃, slowly and continuously adding 175g of nickel powder in the reaction process, reducing the hydrogen ion concentration in the solution to 0.5mol/L after reacting for 15h, and carrying out solid-liquid separation to obtain the nickel-manganese sulfate solution with high acidity. The composition of the nickel manganese sulfate solution is shown in table 6 below.
TABLE 6 composition analysis of nickel manganese sulfate solution
Example 3
The preparation method of higher manganese oxide provided in this example is substantially the same as that of example 1, except that in step (b), the NaOH solution is replaced with ammonia water, the amount of ammonia water used is 0.5L, and the concentration of ammonia water is 6 mol/L.
The high-valence manganese oxide obtained in the example was washed, dried, and weighed 188.45g, and the yield of manganese in the preparation process of the high-valence manganese oxide was 79.96%, calculated from the amount of manganese in the slag and the manganese solution before the reaction, and the analysis of the components of the high-valence manganese oxide is shown in table 7 below.
TABLE 7 analysis of higher manganese oxides
| Element(s) | Mn | Ca | Mg | Al | Cu | Zn | Co |
| High manganese oxide (%) | 71.09 | 0.031 | 0.0013 | 0.0004 | 0.0003 | 0.0004 | 0.0002 |
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. The preparation method of the high-valence manganese oxide is characterized by comprising the following steps of:
adding an oxidant and a neutralizing agent into the copper-zinc-calcium-removed copper-manganese chloride solution to perform manganese oxidation precipitation reaction, and performing solid-liquid separation to obtain a high-valence manganese oxide;
wherein the higher manganese oxide comprises: trimanganese tetroxide, manganese dioxide, basic manganese sulfate and manganese hydroxide;
the pH value of the copper chloride manganese solution after copper, zinc and calcium removal is 3.0-5.0;
in the process of carrying out manganese oxidation precipitation reaction, the pH value of the solution system is 7.0-10.5.
2. The preparation method according to claim 1, wherein the pH of the copper-manganese chloride solution after copper, zinc and calcium removal is 4.0-4.9;
preferably, in the process of carrying out the manganese oxidation precipitation reaction, the pH value of a solution system is 7.5-8.5;
preferably, the neutralizing agent comprises at least one of ammonia, sodium hydroxide solution and potassium hydroxide solution, more preferably sodium hydroxide solution;
preferably, the molar concentration of hydroxide ions in the neutralizing agent is 3-12 mol/L, and more preferably 6-10 mol/L;
preferably, in the process of carrying out the manganese oxidation precipitation reaction, the temperature of the solution system is 40-95 ℃, and more preferably 60-80 ℃.
3. The production method according to claim 1, wherein the oxidizing agent comprises at least one of air, oxygen, potassium permanganate, potassium perchlorate, and ammonium persulfate, more preferably air;
preferably, the time of the oxidation precipitation reaction is 8-30 h, and more preferably 10-24 h.
4. The preparation method according to claim 1, wherein the copper and zinc removal treatment is carried out on the copper and manganese chloride solution, and specifically comprises the following steps: mixing the copper-manganese chloride solution with sulfide, and after reaction, carrying out solid-liquid separation to obtain a copper-manganese chloride mixed solution after copper and zinc removal;
preferably, the sulphide comprises at least one of manganese sulphide, sodium sulphide, ammonium sulphide and hydrogen sulphide, more preferably sodium sulphide and/or ammonium sulphide.
5. The preparation method according to claim 4, wherein the copper-manganese chloride solution is subjected to calcium removal treatment, and specifically comprises the following steps: mixing the copper and zinc-removed copper and manganese chloride mixed solution with sulfate, and after reaction, carrying out solid-liquid separation to obtain a preliminary calcium-removed copper and manganese chloride mixed solution;
preferably, the sulfate salt comprises at least one of sodium sulfate, ammonium sulfate, and potassium sulfate, more preferably sodium sulfate and/or ammonium sulfate.
6. The method of claim 5, wherein the decalcifying treatment further comprises: mixing the preliminary calcium-removal copper-manganese chloride mixed solution with a fluoride, and after reaction, carrying out solid-liquid separation to obtain a copper-zinc-calcium-removal copper-manganese chloride mixed solution;
preferably, the fluoride comprises at least one of sodium fluoride, ammonium fluoride and manganese fluoride.
7. High valence manganese oxide prepared by the method of any one of claims 1 to 6.
8. The preparation method of the nickel sulfate manganese solution is characterized by comprising the following steps: mixing the high-valence manganese oxide prepared by the preparation method of any one of claims 1 to 6 or the high-valence manganese oxide of claim 7 with sulfuric acid and metallic nickel, and reacting to obtain the nickel-manganese sulfate solution.
9. The method according to claim 8, comprising the steps of:
(a) adding high-valence manganese oxide into a mixed solution containing metal nickel and sulfuric acid, then adding metal nickel into the mixed solution, and reacting until the molar concentration of hydrogen ions in the solution is 0.1-0.9 mol/L to obtain a nickel-manganese sulfate solution with high acidity; and/or the presence of a gas in the gas,
(b) adding high-valence manganese oxide into the nickel sulfate manganese solution with high acidity obtained in the step (a), reacting until the pH value of the solution is 2-3, and after solid-liquid separation, respectively obtaining the nickel sulfate manganese solution with low acidity and the nickel powder which is not completely reacted.
10. The method according to claim 9, wherein in the step (a), the molar concentration of hydrogen ions in the mixed solution is 1 to 6mol/L, preferably 4 to 5 mol/L;
preferably, in the step (a), the molar ratio of the metallic nickel to the sulfuric acid in the mixed solution is 1-3: 1;
preferably, in step (a) and/or step (b), the temperature of the solution system is 50 to 100 ℃, more preferably 90 to 95 ℃.
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Non-Patent Citations (2)
| Title |
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| NIHAN KAYA ET AL.: "Catalytic air oxidation of manganese in synthetic waters", 《CENTRAL EUROPEAN JOURNAL OF CHEMISTRY》 * |
| P. PHATAI ET AL.: "Removal of manganese ions from synthetic ground water by oxidation using KMnO4 and the characterization of produced MnO2 particles", 《WATER SCIENCE & TECHNOLOGY—WST》 * |
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