Method for detecting high-content manganese element in ore

Abstract

The invention relates to a method for detecting high-content manganese element in ore, which comprises the following steps: weighing an ore sample, placing the ore sample in a beaker, adding deionized water until the weighed ore sample is wet, and adding hydrochloric acid; heating until the solution is clear, and adding hydrofluoric acid, citric acid and tartaric acid; adding nitric acid, continuously heating to nearly dry, cooling, adding deionized water, adding hydrochloric acid, and heating until salt is dissolved; after cooling, transferring into a volumetric flask, adding deionized water into the beaker to obtain a washing solution, transferring the washing solution into the volumetric flask together, adding deionized water to dilute to a scale line, and uniformly shaking to obtain a final solution to be detected; and detecting the content of the manganese element in the final to-be-detected solution as the content of the manganese element in the ore sample. The method is simple to operate, the content of the manganese element in the ore sample can be rapidly obtained, the detection efficiency of the ore sample is effectively improved, the requirement for equipment in the detection process is low, the detection result is reliable and stable, the error of the detection result is small, expensive auxiliary reagents are not needed, and the detection cost is effectively reduced.

Description

Technical Field

[0001] The present application relates to the technical field of nonferrous metal beneficiation, and in particular to a method for detecting high-content manganese in ore. Background Art

[0002] In the analysis and detection of non-ferrous metal ore components, manganese content is one of the elements that must be detected. The determination methods of manganese in non-ferrous metal ores include ferrous ammonium sulfate titration, permanganate spectrophotometry, potassium permanganate potentiometric titration, etc. The previous atomic absorption detection range is 0.005% to 5.00%.

[0003] The ammonium ferrous sulfate titration method has a long operating process during the detection process, and the ammonium ferrous sulfate standard solution is extremely unstable. It is calibrated too frequently during use, which affects the accuracy of the test results (detection range ≥ 1%). In the permanganate spectrophotometry method, sulfuric acid and nitric acid are used for acidification, and hazardous chemicals such as sulfuric acid and potassium periodate, platinum crucibles, etc. are used. The acidity has a certain influence on the color development and affects the stability of the test results. It is mainly used for the determination of trace manganese content in ores (detection range 0.005% to 2.00%). In the potassium permanganate potentiometric titration method, potassium permanganate and ammonium ferrous sulfate standard solutions are titrated. The ammonium ferrous sulfate standard solution is extremely unstable. It is calibrated too frequently during use, which causes a certain waste of the standard solution and affects the accuracy of the test results (detection range 5% to 10.00%).

[0004] The manganese content that needs to be analyzed in mining, mineral processing, geological exploration, experimental samples, etc. increases year by year at a rate of 3% in sample volume. The traditional detection method is used to analyze the sulfur content, which is cumbersome, time-consuming, and has high labor and reagent costs. The current cost of sulfur content testing is about 1.2 million yuan, and the detection cost is relatively high. Summary of the invention

[0005] In order to solve or partially solve the problems existing in the related art, the present application provides a method for detecting high-content manganese in ore, which can quickly obtain the manganese content in the ore sample and effectively improve the detection efficiency of the ore sample.

[0006] The first aspect of the present application provides a method for detecting high-content manganese in ore, comprising the following steps:

[0007] Weigh the ore sample and place it in a beaker, add deionized water until the ore sample is moistened, then add hydrochloric acid to prepare a primary test solution; the mass fraction of hydrochloric acid is 36.5%;

[0008] After the primary test solution is heated until the solution is clear, hydrofluoric acid, citric acid and tartaric acid are added to dissolve and obtain the primary test solution; the heating temperature of the primary test solution is 200-280°C.

[0009] Among them, 2 ml of hydrofluoric acid with a mass fraction of 5%, 5 ml of citric acid with a mass fraction of 2%, and 5 ml of tartaric acid with a mass fraction of 10% were added.

[0010] Add nitric acid to the first-level test solution, continue heating until it is nearly dry, add deionized water after cooling, and then add hydrochloric acid and heat until the salt is dissolved to obtain a second-level test solution; the mass fraction of nitric acid is 68.0%;

[0011] After cooling, the secondary test solution is transferred into a volumetric flask, deionized water is added into the beaker to obtain a washing solution, the washing solution is transferred into a volumetric flask, deionized water is added to dilute to the scale line, and then shaken to obtain the final test solution;

[0012] The manganese content in the final test solution is detected as the manganese content in the ore sample.

[0013] The step of detecting the manganese content in the final test solution includes:

[0014] preparing a manganese standard stock solution, and preparing standard solutions of different concentrations using the manganese standard stock solution;

[0015] The absorbance of the standard solution was measured by flame atomic absorption spectrometer, and a standard working curve of manganese was drawn;

[0016] The absorbance of the final test solution is detected, and the corresponding manganese content value is found in the manganese standard working curve.

[0017] The technical solution provided by this application may have the following beneficial effects:

[0018] The present application provides a method for detecting high-content manganese in ore. The method is simple to operate, can quickly obtain the manganese content in the ore sample, effectively improves the detection efficiency of the ore sample, has low requirements on equipment during the detection process, and the detection results are reliable and stable. The error of the measurement results is small, and no expensive auxiliary reagents are required, which effectively reduces the detection cost.

[0019] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The above and other objects, features and advantages of the present application will become more apparent through a more detailed description of exemplary embodiments of the present application in conjunction with the accompanying drawings, wherein the same reference numerals generally represent the same components in the exemplary embodiments of the present application.

[0021] Figure 1 It is a flow chart of the detection method shown in Example 1 of the present application. DETAILED DESCRIPTION

[0022] The embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although the embodiments of the present application are shown in the accompanying drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided to make the present application more thorough and complete, and to fully convey the scope of the present application to those skilled in the art.

[0023] It should be understood that although the terms "first", "second", "third", etc. may be used in this application to describe various information, this information should not be limited to these terms. These terms are only used to distinguish the same type of information from each other. For example, without departing from the scope of this application, the first information may also be referred to as the second information, and similarly, the second information may also be referred to as the first information. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0024] In the description of the present application, it should be understood that the terms "length", "width", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating the orientation or position relationship, are based on the orientation or position relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0025] Unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0026] The technical solution of the embodiments of the present application is described in detail below with reference to the accompanying drawings.

[0027] Embodiment 1:

[0028] like Figure 1 The detection method of high content of manganese in the ore shown is as follows:

[0029] S1. Weigh the ore sample and place it in a beaker. Add a small amount of deionized water to moisten it and then add hydrochloric acid to prepare the primary test solution.

[0030] Weigh 0.1000-0.5000g of sample into a 150mL beaker, moisten it with a small amount of deionized water, and add 10mL of hydrochloric acid, the mass fraction of which is 36.5%.

[0031] Add a few drops to about 1 mL of deionized water to wet the sample according to the number of samples to be sampled. A small amount of deionized water is added to wet the sample and provide a suitable solution environment to facilitate the dissolution and reaction of the sample. The purpose of wetting the sample is to increase the contact area between the sample and the hydrochloric acid and promote the reaction and dissolution of the sample. By wetting the sample, the surface area of ​​the sample increases, the reaction rate of the sample with the hydrochloric acid is faster, and the dissolution is more thorough. In addition, wetting the sample can also reduce the accumulation and surface tension of the sample, which is conducive to a more uniform dissolution and reaction of the sample in the solution.

[0032] S2. After the primary test solution is heated until the solution is clear, hydrofluoric acid, citric acid and tartaric acid are added to dissolve and obtain the primary test solution.

[0033] Place the beaker on a hot plate at 200°C to 280°C and heat for 3 to 8 minutes. The solution in the beaker gradually clarifies during the heating process. When the solution is completely clear, add 2 ml of 5% hydrofluoric acid, 5 ml of 2% citric acid, and 5 ml of 10% tartaric acid and dissolve for 3 to 5 minutes.

[0034] Hydrofluoric acid, citric acid and tartaric acid have strong solubility and can convert the manganese element in the ore into easily soluble manganese ions.

[0035] In step 2, hydrofluoric acid, citric acid and tartaric acid react chemically with manganese ore in the ore. The specific reaction mechanism is as follows:

[0036] Hydrofluoric acid reacts with manganese ore to form manganese fluoride:

[0037] MnO2+4HF→MnF2+2H2O

[0038] Citric acid reacts with manganese ions to form manganese citrate complex:

[0039] Mn2++3C6H8O7→Mn(C6H7O7)3+3H+

[0040] Tartaric acid reacts with manganese ions to form manganese tartrate complex:

[0041] Mn2++4C4H6O6→Mn(C4H4O6)2+2H+

[0042] The above reaction converts the manganese element in the ore into manganese ions dissolved in the solution, further expanding the measurement range of manganese element.

[0043] S3. Add nitric acid to the first-level test solution, continue heating until it is nearly dry, add deionized water after cooling, and then add hydrochloric acid and heat until the salts are dissolved to obtain the second-level test solution.

[0044] Add 10 ml of 5% nitric acid, continue heating, evaporate until almost dry, add deionized water after cooling, add 10 mL of hydrochloric acid and heat to dissolve the salts. The mass fraction of hydrochloric acid is 36.5%.

[0045] S4. After cooling, transfer the secondary test solution into a volumetric flask. Add deionized water into the beaker, transfer the washing solution into the volumetric flask, add deionized water to dilute to the scale line and shake well to obtain the final test solution.

[0046] The cooled solution was transferred into a volumetric flask, the solution in the beaker was washed clean, and the washing liquid was transferred into a 100mL or 500ml volumetric flask (the size of the volumetric flask is determined according to the actual manganese content, and a certain amount of acid is added in proportion), diluted to the scale line with deionized water and shaken to obtain the final test solution.

[0047] S5. Using flame atomic absorption spectrometer to detect the manganese content in the final test solution, and obtain the manganese content in the ore sample.

[0048] The specific steps are:

[0049] S51. Prepare standard manganese stock solution (Solution A): weigh 2.7485 g manganese sulfate (MnSO4, pre-calcined at 400°C to 500°C to constant weight, placed in a dry burner), dissolve it in water, transfer it into a 1000 mL volumetric flask, and dilute to the mark. This solution contains 1 mg / mL manganese.

[0050] S52. Prepare manganese standard stock solution (solution B): Accurately transfer 50.00 mL of manganese standard stock solution (A) into a 500 mL volumetric flask and dilute to volume with water. This solution contains 100 ug / mL manganese.

[0051] S53. Establish a manganese standard working curve: prepare standard solutions of different concentrations according to the manganese content in the ore sample, accurately transfer 0.00mL, 0.50mL, 1.00mL, 3.00mL, 5.00mL, and 7mL of manganese standard solution (liquid B) into a volumetric flask of 100mL, make up to volume with hydrochloric acid (1+49), adjust to zero with zero standard solution, place each standard solution on a flame atomic absorption spectrometer for measurement, measure the absorbance of the standard solution series, and draw a manganese standard working curve with manganese concentration as the horizontal axis and absorbance as the vertical axis.

[0052] S54, placing the solution to be tested in S4 in a flame atomic absorption spectrometer for measurement to obtain the absorbance of the solution to be tested, and searching for the corresponding manganese content value on the manganese standard working curve according to the absorbance value.

[0053] Comparative Example 1:

[0054] The ammonium ferrous sulfate titration method is used to determine the manganese content in the ore. The steps are as follows:

[0055] Weigh 0.1000-0.5000g of the sample into a 300mL conical flask, add 8mL phosphoric acid and 2mL sulfuric acid, heat and decompose, and shake while dissolving. When the liquid surface is calm and there are no bubbles, add 1mL perchloric acid, continue heating until there are no bubbles (about 7 minutes), remove, cool to about 70℃, add 80mL water, cool to room temperature, add 5 drops of 5g / L sodium diphenylamine xanthate solution, and add ammonium ferrous sulfate standard solution until the pink color fades (colorless), which is the end point.

[0056] Comparative Example 2:

[0057] The permanganate spectrophotometric method is used to determine the manganese content in the ore. The steps are as follows:

[0058] Weigh 0.150-0.5000g of the sample into a platinum crucible, add 1ml sulfuric acid (1+1), 1ml nitric acid, 10ml hydrofluoric acid, place on a hot plate and heat to decompose, evaporate until sulfuric acid smoke appears, remove and cool slightly, rinse the inner wall of the crucible with water, heat again until sulfuric acid smoke disappears, remove and cool. Add 1ml sulfuric acid (1+1) and 10ml water to the crucible, heat and dissolve until the solution is transparent, transfer to a 50ml volumetric flask, dilute to volume with water, shake well for testing.

[0059] Comparative Example 3:

[0060] The potassium permanganate potentiometric titration method is used to determine the manganese content in the ore. The steps are as follows:

[0061] Weigh 0.1000g to 0.2000g of the sample into a 250ml polytetrafluoroethylene beaker, add 7ml hydrochloric acid, heat for 10 minutes, then remove, add 3ml nitric acid, 5ml perchloric acid, and 5ml hydrofluoric acid, place on a hot plate and heat until the sample is completely decomposed and evaporated until sulfuric acid smoke appears. After the remaining volume is about 0.5ml, remove and cool slightly, add 15ml water, boil until soluble salts are dissolved, and cool. Quickly add 75ml saturated sodium pyrophosphate solution, adjust the pH value with sulfuric acid (1+1) and ammonia water (1+1), insert a platinum-silver or platinum-tungsten electrode, turn on the stirrer, and titrate with potassium permanganate standard solution under constant stirring until the instrument pointer deflects significantly, and the analysis result is obtained.

[0062] Comparative Example 4:

[0063] Weigh 0.1000-0.5000g of the sample in a 150mL beaker, moisten it with a small amount of water, add 10mL of hydrochloric acid, place it on a hot plate at 200°C-280°C and heat it until the solution is clear, add 10mL of nitric acid 5%, dissolve it for 5min, add nitric acid and heat it for several minutes, evaporate it to nearly dryness, add water after cooling, add hydrochloric acid, heat to dissolve salts, transfer the cooled solution into a volumetric flask, wash the solution in the beaker, and transfer the washing liquid into a 100mL or 500mL volumetric flask (the volume is determined according to the actual manganese content, and a certain amount of acid is added in proportion), dilute it to the scale line with deionized water, shake it well, and wait for testing; use a flame atomic absorption spectrometer to detect the manganese content in the solution, so as to obtain the manganese content in the ore.

[0064] Determination comparison table

[0065]

[0066]

[0067] As can be seen from the above table, the determination of the permanganate spectrophotometry in Comparative Example 2 and the potassium permanganate potentiometric titration in Comparative Example 3 have certain limitations, and there are large errors in the determination of high-content manganese samples, and it is not feasible to use them to determine high-content manganese ores. Comparative Example 4 omitted the necessary technical features of Example 1 by adding hydrofluoric acid, citric acid and tartaric acid. The error was small when measuring low-content manganese samples, but there was a large error in the determination of high-content manganese samples, and it was not feasible to use them to determine high-content manganese ores.

[0068] The error between the test results obtained by Example 1 using the technical solution and the test results obtained by the ammonium ferrous sulfate titration method in Comparative Example 1 is relatively small. Therefore, it is feasible to use the technical solution to determine the manganese content in the ore. In addition, the detection process of this method has low requirements on equipment and does not require expensive auxiliary reagents, which effectively reduces the detection cost.

[0069] Finally, it should be noted that, in this article, relationships such as first and second, etc. are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms include, include or any other variations are intended to cover non-exclusive inclusion, so that a process, method, article or device that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0070] The units described as separate components may or may not be physically separated, and the components shown as units may or may not be physical units, that is, they may be located in one place or distributed on multiple network units. Some or all of the units may be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0071] The embodiments of the present application have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to the technology in the market, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A method for detecting high-content manganese in ore, characterized in that: The following steps are involved: Weigh an ore sample and place it in a beaker, add deionized water until the ore sample is moistened, then add hydrochloric acid to prepare a primary test solution; After heating the primary test solution until the solution is clear, hydrofluoric acid, citric acid and tartaric acid are added to dissolve and obtain a primary test solution; Add nitric acid to the first-level test solution, continue heating until it is nearly dry, add deionized water after cooling, and then add hydrochloric acid and heat until the salt is dissolved to obtain a second-level test solution; After cooling, the secondary test solution is transferred into a volumetric flask, deionized water is added into a beaker to obtain a washing solution, the washing solution is transferred into the volumetric flask, deionized water is added to dilute to the scale line, and then shaken to obtain the final test solution; The manganese content in the final test solution is detected as the manganese content in the ore sample.

2. The detection method according to claim 1, characterized in that: The step of detecting the manganese content in the final test solution comprises: preparing a manganese standard stock solution, and preparing standard solutions of different concentrations using the manganese standard stock solution; The absorbance of the standard solution is measured by flame atomic absorption spectrometer to draw a manganese standard working curve; The absorbance of the final test solution is detected, and the corresponding manganese content value is found in the manganese standard working curve.

3. The detection method according to claim 1, characterized in that: In the hydrofluoric acid, citric acid and tartaric acid, 2 ml of hydrofluoric acid with a mass fraction of 5%, 5 ml of citric acid with a mass fraction of 2%, and 5 ml of tartaric acid with a mass fraction of 10% are added.

4. The detection method according to claim 1, characterized in that: The mass fraction of the hydrochloric acid is 36.5%.

5. The detection method according to claim 1, characterized in that: The mass fraction of the nitric acid is 68.0%.

6. The detection method according to claim 1, characterized in that: The heating temperature of the primary test liquid is 200-280°C.

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