Phase analysis methods for manganese in ores

Abstract

This application provides a method for phase analysis of manganese in ores, belonging to the field of phase analysis of ores. The method involves weighing an ore sample and sequentially leaching it with silver nitrate solution to separate the manganese sulfate phase; then leaching it with aluminum nitrate solution under heating, adding a mixed solution of isoamyl alcohol and isoamyl acetate as a first inhibitor to separate the manganese carbonate phase; followed by stepwise leaching with sulfurous acid solution and hydroxylamine sulfate-sulfuric acid solution, adding a mixed solution of n-butanol and ethyl acetate as a second inhibitor to separate the manganese oxide phase; and finally, the remaining residue is digested by ashing to obtain the silicate phase. The manganese content of each phase digest is determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). This application rationally selects various possible forms of manganese in the ore and scientifically selects the leaching agent for each phase, ensuring that the leaching agent of the previous phase does not leach manganese from the subsequent phases, thus guaranteeing accurate determination of each phase.

Description

Technical Field

[0001] This invention relates to the field of phase analysis technology in ores, and specifically to a method for phase analysis of manganese in ores. Background Technology

[0002] Manganese ore is an important raw material in metallurgy, chemical industry, and battery materials. The main forms of manganese in ore include manganese carbonate, manganese oxide, manganese sulfate, and manganese silicate. The chemical behavior of manganese varies significantly among these different phases, resulting in different leaching properties, migration and transformation patterns, and economic values ​​during beneficiation and smelting processes. Therefore, establishing accurate and comprehensive manganese phase analysis methods is of great significance for process mineralogical research, beneficiation and smelting process development, and comprehensive resource evaluation of manganese ore.

[0003] Currently, common methods for manganese phase analysis are mainly based on the principle of selective leaching-chemical determination. This involves utilizing the differences in the solubility of different manganese minerals in a specific leaching agent to separate each phase through stepwise leaching, followed by quantitative determination. However, existing manganese phase analysis methods suffer from the following technical drawbacks: incomplete phase classification leads to distorted analytical results, thus affecting ore beneficiation evaluation and smelting process design; poor selectivity and severe cross-contamination cause interference between the determination results of different phases; outdated analytical methods make it difficult to analyze batch samples; and poor universality limits applicability to all types of ore samples, restricting the methods' broad applicability.

[0004] In view of this, it is necessary to design a phase analysis method for manganese in ore to solve the above problems. Summary of the Invention

[0005] In view of the technical problems existing in the background art, this application provides a phase analysis method for manganese in ore, which aims to solve the technical problems of incomplete phase classification, serious cross-phase interference between different phases, low analysis efficiency and poor universality in existing manganese phase analysis methods.

[0006] This application provides a method for phase analysis of manganese in ore, comprising the following steps: S1. Determination of manganese in sulfur-manganese ore: Weigh the ore sample, add silver nitrate solution as the leaching agent, shake to leach, filter and separate to obtain the first filtrate and the first filter residue; after digestion, the manganese content of the first filtrate is determined by inductively coupled plasma atomic emission spectrometry. S2. Determination of manganese in manganese carbonate: The first filter residue obtained in step S1 was added to aluminum nitrate solution as an extractant, heated and leached, and a first inhibitor was added during the leaching process. After filtration and separation, a second filtrate and a second filter residue were obtained. After digestion, the manganese content of the second filtrate was determined by inductively coupled plasma atomic emission spectrometry. The first inhibitor was a mixed solution of isoamyl alcohol and isoamyl acetate. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2 was sequentially leached and digested using sulfurous acid solution and hydroxylamine sulfate-sulfuric acid solution as leaching agents, and a second inhibitor was added during the leaching process. After treatment, a third filter residue was obtained. The digestion solutions were combined, and the manganese content was determined by inductively coupled plasma atomic emission spectrometry. The second inhibitor was a mixed solution of n-butanol and ethyl acetate. S4. Determination of manganese in silicates: The third filter residue obtained in step S3 was subjected to ashing and digestion in sequence, and the manganese content was determined by inductively coupled plasma atomic emission spectrometry.

[0007] As a further improvement of this application, in step S1, the concentration of the silver nitrate solution is 4~6 g / L, the shaking leaching time is 20~30 minutes, and the shaking frequency is 40~60 times / minute.

[0008] As a further improvement of this application, in step S2, the concentration of the aluminum nitrate solution is 20~30g / L, and the heating leaching temperature is 160~180℃.

[0009] As a further improvement of this application, the volume ratio of isoamyl alcohol to isoamyl acetate in the first inhibitor is (3~5):1.

[0010] As a further improvement of this application, in step S3, the mass fraction of the sulfurous acid solution is 1~3%; the concentration of hydroxylamine sulfate in the sulfuric acid-sulfuric acid solution is 25~35g / L, and the volume fraction of sulfuric acid is 0.5~1.5%.

[0011] As a further improvement to this application, the volume ratio of n-butanol to ethyl acetate in the second inhibitor is (0.8~1.2):1.

[0012] As a further improvement of this application, in step S4, the ashing temperature is 650~750℃.

[0013] As a further improvement of this application, the particle size of the ore sample is less than 0.075 mm.

[0014] As a further improvement of this application, a mixed acid solution is used for digestion, wherein the mixed acid solution is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, and perchloric acid; after digestion, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%.

[0015] As a further improvement to this application, a total manganese determination step is also included: weigh another ore sample, perform total digestion using a mixed acid solution, and determine the total manganese content using inductively coupled plasma atomic emission spectrometry.

[0016] The beneficial effects of this application are as follows: This application provides a method for phase analysis of manganese in ore, comprising: weighing an ore sample, sequentially leaching it with silver nitrate solution to separate the manganese sulfate phase, leaching it with aluminum nitrate solution under heating, adding a mixed solution of isoamyl alcohol and isoamyl acetate as a first inhibitor to separate the manganese carbonate phase, then performing stepwise leaching with sulfurous acid solution and hydroxylamine sulfate-sulfuric acid solution, adding a mixed solution of n-butanol and ethyl acetate as a second inhibitor to separate the manganese oxide phase, and obtaining the silicate phase after ashing and digestion of the remaining residue; determining the manganese content of each phase digestion solution using inductively coupled plasma atomic emission spectrometry. This application rationally selects various possible forms of manganese in the ore and scientifically selects the leaching agent for each phase, ensuring that the leaching agent of the previous phase will not leach manganese from the subsequent phases, thus ensuring accurate determination of each phase.

[0017] This application improves the classification system of manganese phases by adding the determination of the sulfur-manganese mineral phase, overcoming the defect of incomplete phase determination in existing methods. In the leaching process of manganese carbonate and manganese oxides, a mixed inhibitor of isoamyl alcohol and isoamyl acetate and a mixed inhibitor of n-butanol and ethyl acetate are added respectively, which effectively suppresses interphase crosstalk and significantly improves the selectivity of each phase determination. The stepwise leaching of manganese oxides using sulfurous acid and hydroxylamine sulfate-sulfuric acid ensures that manganese oxides with different solubility characteristics can be fully extracted.

[0018] The process described in this application is simple to operate and suitable for batch processing. When combined with inductively coupled plasma atomic emission spectrometry, it enables rapid, accurate, and universally applicable manganese phase analysis. The sum of the determination results of each phase is in high agreement with the total manganese determination value.

[0019] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Detailed Implementation

[0020] The embodiments of the technical solution of this application are described in detail below. The following embodiments are only used to illustrate the technical solution of this application more clearly, and are therefore only examples, and should not be used to limit the scope of protection of this application.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are intended to cover non-exclusive inclusion.

[0022] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0023] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0024] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more (including two sets), and "multiple pieces" refers to two or more (including two pieces).

[0025] Existing manganese phase analysis methods typically separate manganese into three phases: manganese carbonate, manganese oxide, and manganese silicate. However, these methods have several shortcomings: First, the phase classification is incomplete, failing to include manganese sulfate ore in the analysis, leading to distorted results. Second, leaching selectivity is poor, with severe cross-contamination between phases. Third, the methods often employ water bath heating and volumetric methods, resulting in low efficiency and difficulty in batch processing. Fourth, the methods lack universality and are not applicable to different types of manganese ores. These problems limit the accuracy and reliability of manganese phase analysis and urgently require improvement.

[0026] To address the technical problems of incomplete phase classification, severe crosstalk between different phases, low analytical efficiency, and poor universality in existing manganese phase analysis methods, this application provides a phase analysis method for manganese in ores. By rationally selecting various possible forms of manganese in the ore and selectively choosing leaching agents and inhibitors, the method achieves the technical effects of complete phase classification, effective suppression of crosstalk between phases, improved selectivity and accuracy of phase determination, and simple operation with strong universality.

[0027] This application provides a method for phase analysis of manganese in ore, comprising the following steps: S1. Determination of manganese in sulfur-manganese ore: Weigh the ore sample, add silver nitrate solution as the leaching agent, shake to leach, filter and separate to obtain the first filtrate and the first filter residue; after digestion, the manganese content of the first filtrate is determined by inductively coupled plasma atomic emission spectrometry. Specifically, weigh 0.1000g~0.2000g of ore sample with a particle size of less than 0.075mm, add 45~55mL of silver nitrate solution, shake to leach, filter to separate, and obtain the first filtrate and the first filter residue; after heating and concentrating the first filtrate, digest it with a mixed acid solution containing hydrochloric acid, nitric acid and perchloric acid; S2. Determination of manganese in manganese carbonate: The first filter residue obtained in step S1 was added to aluminum nitrate solution as an extractant, heated and leached, and a first inhibitor was added during the leaching process. After filtration and separation, a second filtrate and a second filter residue were obtained. After digestion, the manganese content of the second filtrate was determined by inductively coupled plasma atomic emission spectrometry. The first inhibitor was a mixed solution of isoamyl alcohol and isoamyl acetate. Specifically, 45-55 mL of aluminum nitrate solution is added to the first filter residue, and the mixture is heated at 160-180°C for 10 min. Then, the first inhibitor is added, and the mixture is heated and leached. The residue is then filtered to obtain the second filtrate and the second filter residue. The second filtrate is concentrated by heating and then digested using a mixed acid solution containing hydrochloric acid, nitric acid, and perchloric acid. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2 was sequentially leached and digested using sulfurous acid solution and hydroxylamine sulfate-sulfuric acid solution as leaching agents, and a second inhibitor was added during the leaching process. After treatment, a third filter residue was obtained. The digestion solutions were combined, and the manganese content was determined by inductively coupled plasma atomic emission spectrometry. The second inhibitor was a mixed solution of n-butanol and ethyl acetate. Specifically, the amount of sulfurous acid solution added is 20-30 mL, and the amount of hydroxylamine sulfate-sulfuric acid solution added is 45-55 mL; after both leachings, a mixed acid solution containing hydrochloric acid, nitric acid, and perchloric acid is used for digestion. S4. Determination of manganese in silicates: The third filter residue obtained in step S3 was successively ashed and digested, and the manganese content was determined by inductively coupled plasma atomic emission spectrometry.

[0028] Specifically, after ashing, a mixed acid solution containing hydrochloric acid, nitric acid, hydrofluoric acid, and perchloric acid is used for digestion.

[0029] In the technical solution of this application embodiment, the different solubility selectivity of different manganese minerals in a specific leaching agent is utilized to achieve the separation of each phase through stepwise leaching. Among them, silver nitrate selectively leaches manganese sulfate, aluminum nitrate leaches manganese carbonate and isoamyl alcohol / isoamyl acetate is used to inhibit the dissolution of manganese oxides, sulfurous acid and hydroxylamine sulfate stepwise leach manganese oxides and n-butanol / ethyl acetate is used to inhibit the dissolution of manganese silicate. The residue is ashing and digested to obtain manganese in silicate. The leachate of each phase is digested and then measured by inductively coupled plasma optical emission spectrometry (ICP-OES), thereby achieving accurate quantitative analysis of each phase of manganese.

[0030] Furthermore, in some embodiments, in step S1, the concentration of the silver nitrate solution is 4~6 g / L, the shaking leaching time is 20~30 minutes, and the shaking frequency is 40~60 times / minute.

[0031] In the technical solution of this application embodiment, silver nitrate is used as an oxidizing leaching agent to oxidize sulfur ions in manganese ore to elemental sulfur or sulfate ions, while manganese is leached as Mn. 2+ The form is released into the solution; by controlling the concentration of silver nitrate, the shaking time and frequency, selective and complete leaching of manganese sulfide can be achieved under mild conditions, while avoiding the dissolution of other manganese minerals, thereby ensuring the accuracy and selectivity of manganese sulfide phase determination.

[0032] Furthermore, in some embodiments, in step S2, the concentration of the aluminum nitrate solution is 20-30 g / L, and the leaching temperature is 160-180°C. The volume ratio of isoamyl alcohol to isoamyl acetate in the first inhibitor is (3-5):1.

[0033] In the technical solution of this application embodiment, aluminum nitrate solution undergoes a metathesis reaction with manganese carbonate under heating conditions, converting the manganese in the manganese carbonate into Mn. 2+ Selective leaching is employed; simultaneously, a mixed solution of isoamyl alcohol and isoamyl acetate is added as a first inhibitor. This inhibitor effectively suppresses the dissolution of manganese oxides during the leaching process through adsorption or interfacial interactions, thereby reducing interphase crosstalk and ensuring the accuracy of the manganese carbonate phase determination results. If the isoamyl alcohol content is insufficient, a complete and dense adsorption film cannot be formed on the surface of manganese oxides, and the leaching agent will directly contact and dissolve some manganese oxides, leading to an overestimation of the manganese carbonate phase determination results. If the isoamyl alcohol content is excessive, the excess isoamyl alcohol may not only adsorb onto the surface of manganese oxides but also onto the surface of the target manganese carbonate mineral, hindering the effective contact between aluminum nitrate and manganese carbonate, resulting in incomplete leaching of manganese carbonate and an underestimation of the determination results. Specifically, the amount of the first inhibitor added is 1-3 mL, and the total leaching time is 30-60 minutes.

[0034] Further, in some embodiments, in step S3, the mass fraction of the sulfurous acid solution is 1-3%; the concentration of hydroxylamine sulfate in the hydroxylamine-sulfuric acid solution is 25-35 g / L, and the volume fraction of sulfuric acid is 0.5-1.5%. The volume ratio of n-butanol to ethyl acetate in the second inhibitor is (0.8-1.2):1.

[0035] In the technical solution of this application embodiment, the reducing property of sulfurous acid is first used to remove Mn from high-valence manganese oxides. 4+ Restored to Mn 2+The manganese oxides are leached, and then further reduced and dissolved with a hydroxylamine-sulfuric acid solution to achieve stepwise complete extraction. Simultaneously, a mixture of n-butanol and ethyl acetate is added as a second inhibitor to suppress the dissolution of manganese in silicates through interfacial protection, effectively preventing cross-contamination and ensuring the selectivity and accuracy of manganese oxide phase determination. If the proportion of n-butanol is too low, the polarity and interfacial activity of the mixed solvent are insufficient, making it difficult to form an effective protective film on the silicate mineral surface. This causes the hydroxylamine-sulfuric acid solution to dissolve some manganese in the silicate lattice during the leaching process, resulting in an overestimation of the manganese oxide phase and an underestimation of the silicate phase. Conversely, if the proportion of n-butanol is too high, the hydrophobicity of the mixed solvent is too strong, excessively inhibiting the dissolution of manganese in silicates, leading to an underestimation of the silicate phase and compromising the accuracy of phase distribution. Specifically, the amount of the second inhibitor added is 0.5–1 mL. When using sulfurous acid extractant for the first extraction, the shaking time is 10-40 minutes and the shaking frequency is 150-200 times / minute; when using hydroxylamine sulfate extractant for the second extraction, the heating temperature is 150-200℃ and the heating time is 10-40 minutes.

[0036] Furthermore, in some embodiments, the ashing temperature in step S4 is 650~750°C.

[0037] In the technical solution of this application embodiment, the filter residue remaining after filtration in step S3, together with the filter paper, is ashed at 650~750°C. This can completely remove cellulose and residual organic inhibitors from the filter paper, while keeping the silicate mineral structure stable and avoiding unnecessary phase transitions or manganese volatilization losses at high temperatures. The residue after ashing is digested with mixed acid, which can completely release the manganese in the silicate lattice into the solution, thereby accurately determining the manganese content in the silicate phase.

[0038] Furthermore, in some embodiments, the particle size of the ore sample is less than 0.075 mm.

[0039] In the technical solution of this application embodiment, grinding the ore sample to a particle size of less than 0.075 mm can fully destroy the mineral aggregate, causing the individual manganese mineral particles to dissociate, thereby increasing the specific surface area and ensuring that the leaching agent and the target mineral are in full contact during the subsequent step-by-step leaching process, so as to achieve selective, rapid and complete leaching of each phase.

[0040] Furthermore, in some embodiments, a mixed acid solution is used for digestion, wherein the mixed acid solution is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, and perchloric acid; after digestion, hydrochloric acid is added for leaching, and the acidity is controlled to be 15-20%.

[0041] In the technical solution of this application embodiment, a mixed acid consisting of one or more of hydrochloric acid, nitric acid, hydrofluoric acid, and perchloric acid is used to digest the sample. By utilizing the synergistic effect of each acid, all forms of manganese in each phase of the leachate or residue are fully converted into soluble Mn. 2+ After digestion, hydrochloric acid is added to adjust and control the acidity at 15-20%. This acidity range ensures that Mn... 2+ It exists stably in solution, preventing hydrolysis and precipitation, and meets the optimal injection acidity requirements of inductively coupled plasma atomic emission spectrometry, thus obtaining accurate and stable measurement results.

[0042] Furthermore, in some embodiments, the method further includes a total manganese determination step: weighing another ore sample, performing total digestion with a mixed acid solution, and determining the total manganese content using inductively coupled plasma atomic emission spectrometry.

[0043] In the technical solution of this application embodiment, the total manganese value is compared and verified with the sum of the manganese contents of each phase. If the deviation is within the allowable range, it proves that the phases are completely separated during the stepwise leaching process, with no cross-contamination or leakage. At the same time, it confirms the accuracy and reliability of the phase separation measurement results, providing a self-consistent verification basis for the effectiveness of the method. The mass of the ore sample is consistent with the amount weighed in step S1.

[0044] Specifically, the concentration of manganese in each phase is calculated using the following formula: ; In the formula, W(Mn) is the mass fraction of manganese in each phase; C represents the concentration of the sample measured; C0 represents the blank determination concentration; V is the constant volume of the sample; d represents the dilution factor of the sample; m represents the sample mass.

[0045] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0046] Example 1 This embodiment provides a method for phase analysis of manganese in ore, including the following steps: S1. Determination of manganese in manganese ore: Manganese ore samples were crushed, ground, and sieved to obtain samples with a particle size less than 0.075 mm. The samples were dried at 105℃ to constant weight. 0.1 g of the ore sample was weighed into a 150 mL Erlenmeyer flask, and 50 mL of a 5 g / L silver nitrate solution was added as the extraction solvent. The flask was shaken horizontally for 25 minutes at a frequency of 50 times / minute. After shaking, the sample was filtered using a single layer of quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 100 mL to obtain the first filtrate and the first filter residue. The first filtrate was placed on a hot plate and heated... Concentrate the solution to 20 mL using a heat-concentrated solution, ensuring the watch glass is covered to prevent it from drying out. Add 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid to the concentrate, and heat to 280 °C for digestion. After digestion, adjust the acidity to 15-20% with hydrochloric acid, transfer to a 100 mL volumetric flask, dilute to volume with deionized water, and mix well. Determine the manganese concentration in the solution using ICP-OES. The measured value is 0.50 μg / mL, obtained from the standard working curve. Simultaneously, a reagent blank is measured, with a blank value of 0.05 μg / mL. The calculated mass fraction of manganese in the manganese ore is 0.045%. S2. Determination of manganese in manganese carbonate: Transfer the first filter residue obtained in step S1, along with the filter paper, to a 150 mL Erlenmeyer flask. Add 50 mL of 25 g / L aluminum nitrate solution as the extraction solvent. Cover with a watch glass and heat on a 170 °C hot plate for 10 minutes. Then add 3 mL of the first inhibitor (isoamyl alcohol to isoamyl acetate volume ratio 4:1) and continue heating for leaching for 40 minutes. After cooling to room temperature, filter using double-layer quantitative filter paper. Wash the Erlenmeyer flask and filter residue with deionized water, collect the filtrate, and dilute to 250 mL. The second filtrate and the second filter residue were obtained. The second filtrate was heated on a hot plate and concentrated to 20 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added, and the mixture was heated to 280 °C for digestion. After digestion, the acidity was adjusted to 15-20% with hydrochloric acid, and the solution was transferred to a 100 mL volumetric flask and diluted to volume. The concentration of manganese in the solution was determined by ICP-OES. The manganese concentration was found to be 0.78 μg / mL from the working curve, and the blank value was 0.03 μg / mL. The mass fraction of manganese in manganese carbonate was calculated to be 0.075%. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2, along with the filter paper, was placed in a 150 mL Erlenmeyer flask. 25 mL of 2% sulfurous acid solution and 1 mL of the second inhibitor (n-butanol to ethyl acetate volume ratio 1:1) were added. The flask was placed on a horizontal shaker and shaken at 180 times / minute for 25 minutes. The mixture was filtered using double-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 50 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the filtrate. The mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The acidity was adjusted to 15-20%. The filtrate was then stored for later use. The filtered residue, along with the filter paper, was transferred to another 150 mL Erlenmeyer flask. 50 mL of hydroxylamine sulfate-sulfuric acid solution (hydroxylamine sulfate concentration 30 g / L, sulfuric acid volume fraction 1%) was added. The flask was heated on a 170 °C hot plate for 10 minutes. 1 mL of the second inhibitor was added, and the leaching process continued for 50 minutes. The mixture was cooled to room temperature and filtered using a single-layer quantitative filter paper. The Erlenmeyer flask and residue were washed with deionized water. The filtrate was collected and brought to a final volume of 250 mL. The filtrate was then concentrated on a hot plate until sulfuric acid fumes were just generated. After slightly cooling, 2 mL of hydrogen peroxide was added, and the flask was immediately returned to the hot plate. Hydrogen peroxide was added in two batches of 2 mL each, and the mixture was heated again after the bubbles disappeared. Sulfuric acid fumes were produced. The beaker was removed and allowed to cool slightly. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added. The mixture was heated to 280°C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The two leaching solutions were combined and the acidity was adjusted to 15-20% with hydrochloric acid. The solution was then transferred to a 100 mL volumetric flask and brought to volume. Due to the high manganese content, 5.00 mL of the solution was accurately pipetted into another 100 mL volumetric flask, diluted with deionized water, and shaken well. ICP-OES analysis showed that the manganese concentration in the diluted solution was 3.53 μg / mL, and the blank value was 0.02 μg / mL. The calculated mass fraction of manganese in the manganese oxide was 7.02%. S4. Determination of manganese in silicates: The filter residue obtained in step S3, along with the filter paper, was placed in a 100 mL corundum crucible and heated to 700 °C in a muffle furnace for ashing. After ashing, 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid were added to the crucible, and the mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching, with the acidity controlled at 15-20%. The solution was transferred to a 100 mL volumetric flask and diluted to volume, then shaken well. The manganese concentration in the solution was determined by ICP-OES to be 0.58 μg / mL, with a blank value of 0.01 μg / mL. The calculated mass fraction of manganese in the silicates was 0.057%. S5. Weigh 0.1g of the same sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid, and heat on a hot plate to 280℃ for digestion. After digestion, add hydrochloric acid to adjust the acidity to 15-20%, and transfer to a 100mL volumetric flask and make up to volume. Accurately pipette 5.00mL of the solution into another 100mL volumetric flask, dilute to volume, and shake well. ICP-OES analysis showed that the manganese concentration in the diluted solution was 3.61μg / mL, the blank value was 0.01μg / mL, and the total manganese content was calculated to be 7.20%.

[0047] The sum of the manganese content of each phase is: 0.045% + 0.075% + 7.02% + 0.057% = 7.197% ≈ 7.20%, which is in perfect agreement with the total manganese content of 7.20%. This indicates that the method in this embodiment completely separates the phases without cross-contamination or leakage, and the measurement results are accurate and reliable.

[0048] Example 2 This embodiment provides a phase analysis method for manganese in ore, using ores with different manganese contents than in Example 1, and includes the following steps: S1. Determination of manganese in manganese ore: Manganese ore samples were crushed, ground, and sieved to obtain samples with a particle size less than 0.075 mm. The samples were dried at 105℃ to constant weight. 0.2 g of the ore sample was weighed into a 150 mL Erlenmeyer flask, and 50 mL of a 6 g / L silver nitrate solution was added as the extraction solvent. The mixture was shaken horizontally for 20 minutes at a frequency of 40 times / minute. After shaking, the mixture was filtered using a single layer of quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 100 mL to obtain the first filtrate and the first filter residue. The first filtrate was placed on a hot plate and heated... Concentrate the solution to 20 mL using a heat-concentrated solution, ensuring the watch glass is covered to prevent it from drying out. Add 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid to the concentrate, and heat to 280 °C for digestion. After digestion, adjust the acidity to 15-20% with hydrochloric acid, transfer to a 100 mL volumetric flask, dilute to volume with deionized water, and mix well. Determine the manganese concentration in the solution using ICP-OES. The measured value is 0.45 μg / mL, obtained from the standard working curve. Simultaneously, a reagent blank is measured, with a blank value of 0.05 μg / mL. The calculated mass fraction of manganese in the manganese ore is 0.020%. S2. Determination of manganese in manganese carbonate: Transfer the first filter residue obtained in step S1, along with the filter paper, to a 150 mL Erlenmeyer flask. Add 50 mL of 20 g / L aluminum nitrate solution as the extraction solvent. Cover with a watch glass and heat on a 180°C hot plate for 10 minutes. Then add 3 mL of the first inhibitor (isoamyl alcohol to isoamyl acetate volume ratio 4:1) and continue heating for leaching for 40 minutes. After cooling to room temperature, filter using double-layer quantitative filter paper. Wash the Erlenmeyer flask and filter residue with deionized water, collect the filtrate, and dilute to 250 mL. The second filtrate and the second filter residue were obtained. The second filtrate was heated on a hot plate and concentrated to 20 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added, and the mixture was heated to 280 °C for digestion. After digestion, the acidity was adjusted to 15-20% with hydrochloric acid, and the solution was transferred to a 100 mL volumetric flask and diluted to volume. The concentration of manganese in the solution was determined by ICP-OES. The manganese concentration was found to be 1.88 μg / mL from the working curve, and the blank value was 0.03 μg / mL. The mass fraction of manganese in manganese carbonate was calculated to be 0.092%. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2, along with the filter paper, was placed in a 150 mL Erlenmeyer flask. 25 mL of 3% sulfurous acid solution and 1 mL of the second inhibitor (n-butanol to ethyl acetate volume ratio 1:1) were added. The flask was placed on a horizontal shaker and shaken at 180 times / minute for 25 minutes. The mixture was filtered using double-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 50 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the filtrate. The mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The acidity was adjusted to 15-20%. The filtrate was then stored for later use. The filtered residue, along with the filter paper, was transferred to another 150 mL Erlenmeyer flask. 50 mL of hydroxylamine sulfate-sulfuric acid solution (hydroxylamine sulfate concentration 35 g / L, sulfuric acid volume fraction 1%) was added. The flask was heated on a 170 °C hot plate for 10 minutes. 1 mL of the second inhibitor was added, and the leaching process continued for 50 minutes. The mixture was cooled to room temperature and filtered using a single layer of quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and brought to a final volume of 250 mL. The filtrate was then concentrated on a hot plate until sulfuric acid fumes were just generated. After cooling slightly, 2 mL of hydrogen peroxide was added, and the flask was immediately returned to the hot plate for heating. Hydrogen peroxide was added twice, 2 mL each time. After the bubbles disappeared, the mixture was heated again until sulfuric acid fumes were produced. The beaker was removed and allowed to cool slightly. Then, 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added. The mixture was heated to 280°C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The two leaching solutions were combined and the acidity was adjusted to 15-20% with hydrochloric acid. The solution was then transferred to a 100 mL volumetric flask and brought to volume. ICP-OES analysis showed that the manganese concentration in the solution was 1.42 μg / mL, and the blank value was 0.02 μg / mL. The calculated mass fraction of manganese in the manganese oxide was 0.071%. S4. Determination of manganese in silicates: The filter residue obtained in step S3, along with the filter paper, was placed in a 100 mL corundum crucible and heated to 750 °C in a muffle furnace for ashing. After ashing, 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid were added to the crucible, and the mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching, with the acidity controlled at 15-20%. The solution was transferred to a 100 mL volumetric flask and diluted to volume, then shaken well. The manganese concentration in the solution was determined by ICP-OES to be 0.88 μg / mL, with a blank value of 0.02 μg / mL. The calculated mass fraction of manganese in the silicates was 0.043%. S5. Weigh 0.2g of the same sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid, and heat on a hot plate to 280℃ for digestion; after digestion, add hydrochloric acid to adjust the acidity to 15~20%, transfer to a 100mL volumetric flask and make up to volume; by ICP-OES determination, the manganese concentration in the solution was found to be 4.61μg / mL, the blank value was 0.01μg / mL, and the total manganese value was calculated to be 0.23%.

[0049] The sum of the manganese content of each phase is: 0.020% + 0.092% + 0.071% + 0.043% = 0.226% ≈ 0.23%, which is in perfect agreement with the total manganese content of 0.23%. This indicates that the method in this embodiment completely separates each phase without cross-contamination or leakage, and the measurement results are accurate and reliable.

[0050] Example 3 This embodiment provides a phase analysis method for manganese in ore, using ores with different manganese contents than in Example 1, and includes the following steps: S1. Determination of manganese in manganese ore: Manganese ore samples were crushed, ground, and sieved to obtain samples with a particle size less than 0.075 mm. The samples were dried at 105℃ to constant weight. 0.1 g of the ore sample was weighed into a 150 mL Erlenmeyer flask, and 50 mL of a 4 g / L silver nitrate solution was added as the extraction solvent. The flask was shaken horizontally for 30 minutes at a frequency of 60 times / minute. After shaking, the sample was filtered using a single-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 100 mL to obtain the first filtrate and the first filter residue. The filtrate was concentrated to 20 mL on a hot plate, with a watch glass covered to prevent it from drying out. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the concentrate, and the mixture was heated to 280 °C for digestion. After digestion, hydrochloric acid was added to adjust the acidity to 15-20%, and the solution was transferred to a 100 mL volumetric flask. The solution was then diluted to volume with deionized water and shaken well. The concentration of manganese in the solution was determined using ICP-OES. The measured value was 2.56 μg / mL, and the blank value was 0.05 μg / mL. The calculated mass fraction of manganese in the manganese ore was 0.25%. S2. Determination of manganese in manganese carbonate: Transfer the first filter residue obtained in step S1, along with the filter paper, to a 150 mL Erlenmeyer flask. Add 50 mL of 30 g / L aluminum nitrate solution as the extraction solvent. Cover with a watch glass and heat on a 160 °C hot plate for 10 minutes. Then add 3 mL of the first inhibitor (isoamyl alcohol to isoamyl acetate volume ratio 4:1) and continue heating for leaching for 40 minutes. After cooling to room temperature, filter using double-layer quantitative filter paper. Wash the Erlenmeyer flask and filter residue with deionized water, collect the filtrate, and dilute to 25 mL. 0 mL was added to obtain the second filtrate and the second residue. The second filtrate was concentrated to 20 mL on a hot plate, and 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added. The mixture was heated to 280 °C for digestion. After digestion, the acidity was adjusted to 15-20% with hydrochloric acid, and the solution was transferred to a 100 mL volumetric flask and diluted to volume. The concentration of manganese in the solution was determined by ICP-OES, and the manganese concentration was found to be 1.43 μg / mL. The blank value was 0.03 μg / mL, and the mass fraction of manganese in manganese carbonate was calculated to be 0.14%. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2, along with the filter paper, was placed in a 150 mL Erlenmeyer flask. 25 mL of 2% sulfurous acid solution and 1 mL of the second inhibitor (n-butanol to ethyl acetate volume ratio 1:1) were added. The flask was placed on a horizontal shaker and shaken at 180 times / minute for 25 minutes. The mixture was filtered using double-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 50 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the filtrate. The mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The acidity was adjusted to 15-20%. The filtrate was then stored for later use. The filtered residue, along with the filter paper, was transferred to another 150 mL Erlenmeyer flask. 50 mL of hydroxylamine sulfate-sulfuric acid solution (hydroxylamine sulfate concentration 25 g / L, sulfuric acid volume fraction 1%) was added. The flask was heated on a 180°C hot plate for 10 minutes. 1 mL of the second inhibitor was added, and heating continued for another 50 minutes. The mixture was cooled to room temperature and filtered using a single layer of quantitative filter paper. The Erlenmeyer flask and residue were washed with deionized water. The filtrate was collected and brought to a final volume of 250 mL. The filtrate was then concentrated on a hot plate until sulfuric acid fumes were just generated. After cooling slightly, 2 mL of hydrogen peroxide was added, and the flask was immediately returned to the hot plate. Heat the solution, adding 2 mL of hydrogen peroxide in two batches each time. After the bubbles disappear, reheat until sulfuric acid fumes are produced. Remove the beaker, let it cool slightly, and add 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid. Heat the solution on a hot plate to 280°C for digestion. After digestion, add hydrochloric acid for leaching. Combine the two leaching solutions and adjust the acidity to 15-20% with hydrochloric acid. Transfer the solution to a 100 mL volumetric flask and make up to volume. ICP-OES analysis showed that the manganese concentration was 1.44 μg / mL, the blank value was 0.02 μg / mL, and the mass fraction of manganese in the manganese oxide was calculated to be 0.14%. S4. Determination of manganese in silicates: The filter residue obtained in step S3, along with the filter paper, was placed in a 100 mL corundum crucible and heated to 650 °C in a muffle furnace for ashing. After ashing, 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid were added to the crucible, and the mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching, with the acidity controlled at 15-20%. The solution was transferred to a 100 mL volumetric flask and diluted to volume, then shaken well. The manganese concentration in the solution was determined by ICP-OES to be 0.84 μg / mL, with a blank value of 0.02 μg / mL. The calculated mass fraction of manganese in the silicates was 0.082%. S5. Weigh 0.1g of the same sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid, and heat on a hot plate to 280℃ for digestion; after digestion, add hydrochloric acid to adjust the acidity to 15~20%, transfer to a 100mL volumetric flask and make up to volume; by ICP-OES determination, the manganese concentration is 6.11μg / mL, the blank value is 0.01μg / mL, and the total manganese value is calculated to be 0.61%.

[0051] The sum of the manganese content of each phase is: 0.25% + 0.14% + 0.14% + 0.082% = 0.612% ≈ 0.61%, which is in perfect agreement with the total manganese content of 0.61%. This indicates that the method in this embodiment completely separates the phases without cross-contamination or leakage, and the measurement results are accurate and reliable.

[0052] Example 4 This embodiment provides a phase analysis method for manganese in ore, using ores with different manganese contents than in Example 1, and includes the following steps: S1. Determination of manganese in manganese ore: Manganese ore samples were crushed, ground, and sieved to obtain samples with a particle size less than 0.075 mm. The samples were dried at 105℃ to constant weight. 0.2 g of the ore sample was weighed into a 150 mL Erlenmeyer flask, and 50 mL of a 5 g / L silver nitrate solution was added as the extraction solvent. The flask was shaken horizontally for 25 minutes at a frequency of 50 times / minute. After shaking, the sample was filtered using a single-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 100 mL to obtain the first filtrate and the first filter residue. The first filtrate was placed in an electric heating... The solution was concentrated to 20 mL by heating on a plate, taking care to cover the watch glass to prevent it from drying out. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the concentrate, and the mixture was heated to 280 °C for digestion. After digestion, hydrochloric acid was added to adjust the acidity to 15-20%, and the solution was transferred to a 100 mL volumetric flask. Deionized water was used to make up to volume, and 5 mL was accurately pipetted into the 100 mL volumetric flask. The solution was analyzed using ICP-OES. The measured value was 1.55 μg / mL, and the blank value was 0.05 μg / mL. The calculated mass fraction of manganese in the manganese ore was 1.50%. S2. Determination of manganese in manganese carbonate: Transfer the first filter residue obtained in step S1, along with the filter paper, to a 150 mL Erlenmeyer flask. Add 50 mL of 25 g / L aluminum nitrate solution as the extraction solvent. Cover with a watch glass and heat on a 170°C hot plate for 10 minutes. Then add 3 mL of the first inhibitor (isoamyl alcohol to isoamyl acetate volume ratio 3:1) and continue heating for leaching for 40 minutes. After cooling to room temperature, filter using double-layer quantitative filter paper. Wash the Erlenmeyer flask and filter residue with deionized water, collect the filtrate, and dilute to 2 mL. 50 mL was added to obtain a second filtrate and a second residue. The second filtrate was concentrated to 20 mL by heating on a hot plate. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added, and the mixture was heated to 280 °C for digestion. After digestion, the acidity was adjusted to 15-20% with hydrochloric acid, and the solution was transferred to a 100 mL volumetric flask and diluted to volume. The concentration of manganese in the solution was determined by ICP-OES. The measured value was 6.43 μg / mL, and the blank value was 0.03 μg / mL. The mass fraction of manganese in manganese carbonate was calculated to be 0.32%. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2, along with the filter paper, was placed in a 150 mL Erlenmeyer flask. 25 mL of 2% sulfurous acid solution and 1 mL of the second inhibitor (n-butanol to ethyl acetate volume ratio 1:1) were added. The flask was placed on a horizontal shaker and shaken at 180 times / minute for 25 minutes. The mixture was filtered using double-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 50 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the filtrate. The mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The acidity was adjusted to 15-20%. The filtrate was then stored for later use. The filtered residue, along with the filter paper, was transferred to another 150 mL Erlenmeyer flask. 50 mL of hydroxylamine sulfate-sulfuric acid solution (hydroxylamine sulfate concentration 30 g / L, sulfuric acid volume fraction 1%) was added. The flask was heated on a 170 °C hot plate for 10 minutes. 1 mL of the second inhibitor was added, and the leaching process continued for 50 minutes. The mixture was cooled to room temperature and filtered using a single layer of quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and brought to a final volume of 250 mL. The filtrate was then concentrated on a hot plate until sulfuric acid fumes were just generated. After cooling slightly, 2 mL of hydrogen peroxide was added, and the flask was immediately returned to the hot plate. Heating was performed, with hydrogen peroxide added in two portions, 2 mL each time. After the bubbles disappeared, heating was repeated until sulfuric acid fumes were produced. The beaker was removed and allowed to cool slightly. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added. The mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The two leaching solutions were combined and the acidity was adjusted to 15-20% with hydrochloric acid. The solution was then transferred to a 100 mL volumetric flask and brought to volume. ICP-OES analysis showed that the manganese concentration was 8.44 μg / mL, and the blank value was 0.02 μg / mL. The calculated mass fraction of manganese in the manganese oxide was 0.42%. S4. Determination of manganese in silicates: The filter residue obtained in step S3, along with the filter paper, was placed in a 100 mL corundum crucible and heated to 700 °C in a muffle furnace for ashing. After ashing, 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid were added to the crucible, and the mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching, with the acidity controlled at 15-20%. The solution was transferred to a 100 mL volumetric flask and diluted to volume, then shaken well. The manganese concentration in the solution was determined by ICP-OES to be 5.82 μg / mL, with a blank value of 0.02 μg / mL. The calculated mass fraction of manganese in the silicates was 0.29%. S5. Weigh 0.2g of the same sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid, and heat on a hot plate to 280℃ for digestion. After digestion, add hydrochloric acid to adjust the acidity to 15-20%, and transfer to a 100mL volumetric flask and make up to volume. Accurately pipette 5.00mL of the solution into another 100mL volumetric flask, dilute to volume, and shake well. ICP-OES analysis showed that the manganese concentration in the diluted solution was 2.54μg / mL, the blank value was 0.01μg / mL, and the total manganese content was calculated to be 2.53%.

[0053] The sum of the manganese content of each phase is 1.50% + 0.32% + 0.42% + 0.29% = 2.53%, which is in perfect agreement with the total manganese content of 2.53%. This indicates that the method in this embodiment completely separates the phases without cross-contamination or leakage, and the measurement results are accurate and reliable.

[0054] Example 5 This embodiment provides a phase analysis method for manganese in ore, using ores with different manganese contents than in Example 1, and includes the following steps: S1. Determination of Manganese in Manganese Ore: Manganese ore samples were crushed, ground, and sieved to obtain samples with a particle size less than 0.075 mm. The samples were dried at 105℃ to constant weight. 0.1 g of the ore sample was weighed into a 150 mL Erlenmeyer flask, and 50 mL of a 5 g / L silver nitrate solution was added as the extraction solvent. The flask was shaken horizontally for 25 minutes at a frequency of 50 times / minute. After shaking, the sample was filtered using a single-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 100 mL to obtain the first filtrate and the first filter residue. The first filtrate was then placed in an electric... Concentrate the solution to 20 mL on a hot plate, being careful to cover it with a watch glass to prevent it from drying out. Add 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid to the concentrate, and heat to 280 °C for digestion. After digestion, add hydrochloric acid to adjust the acidity to 15-20%, transfer to a 100 mL volumetric flask, and dilute to volume with deionized water. Pipette 5 mL from this volumetric flask and dilute to a final volume of 100 mL. Perform ICP-OES analysis; the measured value is 2.85 μg / mL, and the blank value is 0.05 μg / mL. The calculated manganese mass fraction in the manganese ore is 5.60%. S2. Determination of manganese in manganese carbonate: The first filter residue obtained in step S1, along with the filter paper, was transferred to a 150 mL Erlenmeyer flask. 50 mL of 25 g / L aluminum nitrate solution was added as the extraction solvent. A watch glass was placed on the flask, and the mixture was heated on a 170°C hot plate for 10 minutes. Then, 1 mL of the first inhibitor (isoamyl alcohol to isoamyl acetate volume ratio 5:1) was added, and heating continued for 40 minutes. After cooling to room temperature, the mixture was filtered using double-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 250 mL. The second filtrate and the second filter residue were collected. The second filtrate was concentrated to 20 mL on a hot plate, and 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added. The mixture was heated to 280 °C for digestion. After digestion, the acidity was adjusted to 15-20% with hydrochloric acid, and the solution was transferred to a 100 mL volumetric flask and diluted to volume. 5 mL of the diluted solution was then transferred to a 100 mL volumetric flask and analyzed by ICP-OES. The measured value was 2.73 μg / mL, and the blank value was 0.03 μg / mL. The calculated mass fraction of manganese in manganese carbonate was 5.40%. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2, along with the filter paper, was placed in a 150 mL Erlenmeyer flask. 25 mL of 2% sulfurous acid solution and 0.5 mL of the second inhibitor (1:1 volume ratio of n-butanol to ethyl acetate) were added. The flask was placed on a horizontal shaker and shaken at 180 times / minute for 25 minutes. The mixture was filtered using double-layer quantitative filter paper. The Erlenmeyer flask and filter residue were washed with deionized water. The filtrate was collected and diluted to 50 mL. 15 mL of hydrochloric acid, 10 mL of nitric acid, and 3 mL of perchloric acid were added to the filtrate. The mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching. The acidity was adjusted to 15-20%. The filtrate was then stored for later use. The filtered residue, along with the filter paper, was transferred to another 150 mL Erlenmeyer flask. 50 mL of hydroxylamine sulfate-sulfuric acid solution (hydroxylamine sulfate concentration 30 g / L, sulfuric acid volume fraction 1%) was added. The flask was heated on a 170°C hot plate for 10 minutes. 0.5 mL of the second inhibitor was added, and heating continued for another 50 minutes. The mixture was cooled to room temperature and filtered using a single layer of quantitative filter paper. The Erlenmeyer flask and residue were washed with deionized water. The filtrate was collected and diluted to 250 mL. The filtrate was then heated on a hot plate until sulfuric acid fumes were just generated. After cooling slightly, 2 mL of hydrogen peroxide was added, and the flask was immediately returned to the hot plate for heating. Hydrogen peroxide was added in two separate additions. Add 2 mL each time, and reheat until sulfuric acid fumes are produced after the bubbles disappear. Remove the beaker, let it cool slightly, add 15 mL hydrochloric acid, 10 mL nitric acid, and 3 mL perchloric acid, and heat to 280℃ on a hot plate for digestion. After digestion, add hydrochloric acid for leaching. Combine the two leaching solutions and adjust the acidity to 15-20% with hydrochloric acid. Transfer to a 100 mL volumetric flask and make up to volume. Take 5 mL of this solution and make up to volume in a 100 mL volumetric flask. ICP-OES analysis shows that the manganese concentration in the diluted solution is 4.43 μg / mL, and the blank value is 0.02 μg / mL. The calculated mass fraction of manganese in the manganese oxide is 8.82%. S4. Determination of manganese in silicates: The filter residue obtained in step S3, along with the filter paper, was placed in a 100 mL corundum crucible and heated to 700 °C in a muffle furnace for ashing. After ashing, 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid were added to the crucible, and the mixture was heated to 280 °C on a hot plate for digestion. After digestion, hydrochloric acid was added for leaching, with the acidity controlled at 15-20%. The solution was transferred to a 100 mL volumetric flask and diluted to volume, then shaken well. The manganese concentration in the solution was determined by ICP-OES to be 12.86 μg / mL, with a blank value of 0.02 μg / mL. The calculated mass fraction of manganese in the silicates was 1.28%. S5. Weigh 0.1g of the same sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid, and heat on a hot plate to 280℃ for digestion. After digestion, add hydrochloric acid to adjust the acidity to 15-20%, and transfer to a 100mL volumetric flask and make up to volume. Take 5.00mL of the solution from this flask into another 100mL volumetric flask, dilute to volume, and shake well. ICP-OES analysis showed that the manganese concentration in the diluted solution was 10.56μg / mL, the blank value was 0.01μg / mL, and the total manganese content was calculated to be 21.1%.

[0055] The sum of the manganese content of each phase is 5.60% + 5.40% + 8.82% + 1.28% = 21.1%, which is in perfect agreement with the total manganese content of 21.1%. This indicates that the method in this embodiment completely separates the phases without cross-contamination or leakage, and the measurement results are accurate and reliable.

[0056] Comparative Example 1 Comparative Example 1 provides a phase analysis method for manganese in ore. Compared with Example 4, the only difference is that in step S2, no first inhibitor is added. The measured value is 8.45 μg / mL, the blank value is 0.03 μg / mL, and the calculated mass fraction of manganese in manganese carbonate is 0.42%. Other experimental parameters and conditions are basically the same as those in Example 4, and will not be repeated here.

[0057] Comparative Example 2 Comparative Example 2 provides a phase analysis method for manganese in ore. Compared with Example 5, the only difference is that in step S3, no second inhibitor is added. The measured value is 4.73 μg / mL, the blank value is 0.02 μg / mL, and the calculated mass fraction of manganese in manganese oxide is 9.42%. Other experimental parameters and conditions are basically the same as those in Example 5, and will not be repeated here.

[0058] Comparative Example 3 Comparative Example 3 provides a phase analysis method for manganese in ore. Compared with Example 1, the only difference is that in step S3, manganese oxide is leached with sulfuric acid hydroxylamine-sulfuric acid solution in one step. The measured value is 2.77 μg / mL, the blank value is 0.02 μg / mL, and the calculated mass fraction of manganese in manganese oxide is 5.50%. Other experimental parameters and conditions are basically the same as those in Example 1, and will not be repeated here.

[0059] Comparative Example 4 Comparative Example 4 provides a phase analysis method for manganese in ore. Compared with Example 1, the only difference is that in step S3, manganese oxide is leached with sulfurous acid solution in one step. The measured value is 3.28 μg / mL, the blank value is 0.02 μg / mL, and the calculated mass fraction of manganese in manganese oxide is 6.52%. Other experimental parameters and conditions are basically the same as those in Example 1, and will not be repeated here.

[0060] Comparative Example 5 Comparative Example 5 provides a phase analysis method for manganese in ore. Compared with Example 1, the only difference is that in step S2, the volume ratio of isoamyl alcohol to isoamyl acetate in the first inhibitor is 2:1, the measured value is 0.98 μg / mL, the blank value is 0.03 μg / mL, and the calculated mass fraction of manganese in manganese carbonate is 0.095%. Other experimental parameters and conditions are basically the same as in Example 1, and will not be repeated here.

[0061] Comparative Example 6 Comparative Example 6 provides a phase analysis method for manganese in ore. Compared with Example 1, the only difference is that in step S3, the volume ratio of n-butanol to ethyl acetate in the second inhibitor is 2:1, the measured value is 3.54 μg / mL, the blank value is 0.02 μg / mL, and the calculated mass fraction of manganese in manganese oxide is 7.04%. Other experimental parameters and conditions are basically the same as in Example 1, and will not be repeated here.

[0062] The test results of each embodiment and comparative example are shown in Table 1.

[0063] Table 1. Test results for each embodiment and comparative example. As shown in Table 1, the sum of the manganese contents of each phase in the embodiments of this application is in perfect agreement with the total manganese measured value, proving that the method has excellent accuracy and self-consistency in ores with different manganese contents. In Comparative Example 1, without the first inhibitor, some manganese oxides were dissolved by aluminum nitrate leaching agent and mistakenly included in the manganese carbonate phase, leading to cross-contamination. In Comparative Example 2, without the second inhibitor, some manganese in the silicate was dissolved by hydroxylamine sulfate-sulfuric acid solution and mistakenly included in the manganese oxide phase. In Comparative Example 3, manganese oxides were leached in one step using only hydroxylamine sulfate, and the measured value of manganese oxides was only 5.50%, lower than the 7.02% of the two-step method, while the silicate content was as high as 1.58%, indicating that the one-step leaching was incomplete and there was serious cross-contamination. In Comparative Example 4, manganese oxides were leached in one step using only sulfurous acid, and the measured value of manganese oxides was 6.52%, while the silicate content was 0.56%, which was also less effective than the two-step method. In Comparative Example 5, the volume ratio of isoamyl alcohol to isoamyl acetate in the first inhibitor was 2:1, exceeding the range of (3~5):1. The measured value of manganese carbonate increased from 0.075% to 0.095%, while manganese oxide decreased slightly to 7.00%, indicating that the inhibition effect decreased when the ratio was too low, resulting in a higher concentration of manganese carbonate. In Comparative Example 6, the volume ratio of n-butanol to ethyl acetate in the second inhibitor was 2:1, exceeding the range of 0.8~1.2:1. The measured value of manganese oxide increased slightly to 7.04%, while silicate decreased to 0.037%, indicating that excessive inhibition occurred when the ratio was too high, resulting in a lower concentration of silicate.

[0064] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method for phase analysis of manganese in ore, characterized in that, Includes the following steps: S1. Determination of manganese in sulfur-manganese ore: Weigh the ore sample, add silver nitrate solution as the leaching agent, shake to leach, filter and separate to obtain the first filtrate and the first filter residue; after digestion, the manganese content of the first filtrate is determined by inductively coupled plasma atomic emission spectrometry. S2. Determination of manganese in manganese carbonate: The first filter residue obtained in step S1 was added to aluminum nitrate solution as an extractant, heated and leached, and a first inhibitor was added during the leaching process. After filtration and separation, a second filtrate and a second filter residue were obtained. After digestion, the manganese content of the second filtrate was determined by inductively coupled plasma atomic emission spectrometry. The first inhibitor was a mixed solution of isoamyl alcohol and isoamyl acetate. S3. Determination of manganese in manganese oxides: The second filter residue obtained in step S2 was sequentially leached and digested using sulfurous acid solution and hydroxylamine sulfate-sulfuric acid solution as leaching agents, and a second inhibitor was added during the leaching process. After treatment, a third filter residue was obtained. The digestion solutions were combined, and the manganese content was determined by inductively coupled plasma atomic emission spectrometry. The second inhibitor was a mixed solution of n-butanol and ethyl acetate. S4. Determination of manganese in silicates: The third filter residue obtained in step S3 was subjected to ashing and digestion in sequence, and the manganese content was determined by inductively coupled plasma atomic emission spectrometry.

2. The method for phase analysis of manganese in ore according to claim 1, characterized in that, In step S1, the concentration of the silver nitrate solution is 4~6 g / L, the shaking leaching time is 20~30 minutes, and the shaking frequency is 40~60 times / minute.

3. The method for phase analysis of manganese in ore according to claim 1, characterized in that, In step S2, the concentration of the aluminum nitrate solution is 20~30 g / L, and the leaching temperature is 160~180℃.

4. The method for phase analysis of manganese in ore according to claim 3, characterized in that, The volume ratio of isoamyl alcohol to isoamyl acetate in the first inhibitor is (3~5):

1.

5. The method for phase analysis of manganese in ore according to claim 1, characterized in that, In step S3, the mass fraction of the sulfurous acid solution is 1-3%; the concentration of hydroxylamine sulfate in the hydroxylamine-sulfuric acid solution is 25-35 g / L, and the volume fraction of sulfuric acid is 0.5-1.5%.

6. The method for phase analysis of manganese in ore according to claim 5, characterized in that, The volume ratio of n-butanol to ethyl acetate in the second inhibitor is (0.8~1.2):

1.

7. The method for phase analysis of manganese in ore according to claim 1, characterized in that, In step S4, the ashing temperature is 650~750℃.

8. The method for phase analysis of manganese in ore according to claim 1, characterized in that, The particle size of the ore sample is less than 0.075 mm.

9. The method for phase analysis of manganese in ore according to claim 1, characterized in that, Digestion is performed using a mixed acid solution, which is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, and perchloric acid. After digestion, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%.

10. The method for phase analysis of manganese in ore according to claim 9, characterized in that, It also includes a total manganese determination step: weigh another ore sample, perform total digestion with a mixed acid solution, and determine the total manganese content using inductively coupled plasma atomic emission spectrometry.

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