Method for measuring molybdenum mineral content

Abstract

The present application provides a method for measuring the content of molybdenum minerals, which belongs to the field of process mineralogy, wherein the sample to be tested is subjected to grinding, washing and desludging treatment to obtain ore slime and washed ore concentrate; the washed ore concentrate is subjected to gravity separation to separate gravity separation concentrate and gravity separation tailings; the ore slime and gravity separation concentrate are mixed to obtain a mixed sample, and molybdenum phase analysis is performed to obtain the molybdenum oxide content; automatic mineralogical analysis samples of the mixed sample and gravity separation tailings are prepared separately, and automatic mineralogical analysis is performed to calculate the correction coefficient of the molybdenite content and the correction coefficient of the molybdenum oxide content; the content of various molybdenum minerals in the sample to be tested is calculated by combining the correction coefficient and the mineral content data. The present application reduces the oxidation of molybdenite and improves the accuracy of mineral identification by optimizing the sample preparation process. Molybdenum oxide and molybdenum sulfide are treated separately, and different correction processes are adopted to specifically improve the accuracy of ore molybdenum mineral measurement.

Description

Technical Field

[0001] The present invention relates to the technical field of process mineralogy, and in particular to a method for measuring the content of molybdenum minerals. Background Art

[0002] Molybdenum, a strategically important transition metal, holds an irreplaceable position in modern industry and high-tech fields thanks to its unique physical and chemical properties. Its ultra-high melting point, exceptional mechanical strength, excellent corrosion resistance, and excellent thermal and electrical conductivity make it a core material in key sectors such as high-end manufacturing, military defense, new energy, and semiconductors. With global industrial technological advancements and the vigorous development of emerging industries, the application scope of molybdenum continues to expand, and market demand is showing a long-term, stable growth trend.

[0003] In nature, molybdenum occurs primarily as molybdenite in porphyry, skarn, and quartz vein deposits, often forming symbiotic associations with metallic minerals such as copper and tungsten. In addition to molybdenite, other economically valuable molybdenum-bearing minerals include wolfenite and calcium molybdenite. Molybdenite is highly susceptible to oxidation under supergene conditions, forming secondary minerals such as molybdenum fluoride and ferromolybdenum fluoride, which are of low economic value. Molybdenite has a typical hexagonal layered structure and is easily exfoliated into thin flakes. Particle size effects are significant, and fine particles smaller than 1μm can be misidentified as other sulfides. Wolfenite, on the other hand, has a significant high density and relatively low molybdenum content, both of which pose significant challenges for accurate determination of molybdenum content. Furthermore, in industrial production, molybdenite, the primary industrial molybdenum mineral, is typically enriched by flotation. The production process involves crushing and grinding the raw ore, followed by flotation to obtain a molybdenum concentrate. The concentrate is then oxidized and roasted to produce molybdenum trioxide, which is then reduced and smelted to produce metallic molybdenum products. However, due to the complex production process, diverse intermediate products, variable material composition, and the special flaky structure characteristics of molybdenite (which is prone to morphological misjudgment due to orientation problems in automatic mineralogical analysis), these factors together lead to significant deviations in the molybdenum content determination results.

[0004] In view of this, it is necessary to design an improved method for measuring the content of molybdenum minerals to solve the above problems. Summary of the Invention

[0005] In view of the technical problems existing in the background technology, the present application provides a method for measuring the content of molybdenum minerals, aiming to solve the technical problem of low accuracy of existing methods for measuring the content of molybdenum minerals.

[0006] The present application provides a method for measuring the content of molybdenum minerals, comprising the following steps:

[0007] S1. The sample to be tested is ground, and then washed and desludged to obtain sludge and washed concentrate;

[0008] S2. The washed ore concentrate is subjected to gravity separation to obtain a gravity separation concentrate and gravity separation tailings;

[0009] S3. Mixing the sludge and the gravity concentrate to obtain a mixed sample with a yield of d;

[0010] S4. The mixed sample was subjected to molybdenum phase analysis to obtain a molybdenum oxide content g;

[0011] S5. Prepare the mixed sample and the gravity separation tailings automatic mineralogical analysis samples, denoted as a and b, and perform automatic mineralogical analysis to measure the molybdenum mineral content, respectively, M aj and M bj , j is 1, 2, 3, ..., representing molybdenite, wolfenite, molybdenite and other oxygen-containing molybdenum minerals;

[0012] The molybdenum content of sample a molybdenum oxide mineral was measured to be h j , where j ≥ 2, representing wulfenite, molybdenite and other oxygen-containing molybdenum minerals;

[0013] The total molybdenum content in the molybdenum oxide mineral of sample a is B, B=∑(M aj *h j ), where j ≥ 2, representing wulfenite, molybdenite and other oxygen-containing molybdenum minerals;

[0014] S6. Calculate the correction factor O1 for molybdenite content, where O1=∑k n / n;

[0015] k n =2*(∑f nm *S nm ) / S n 1.5 ;

[0016] S n is the area of ​​a single molybdenite grain, and n is the grain number;

[0017] S nm is the area of ​​the region, m is the number of regions segmented by the nth particle;

[0018] F nm= S nm 0.5 , simulated thickness of each region;

[0019] S7. Calculate the correction factor O2 for the molybdenum oxide content, where O2 = g / B;

[0020] S8. Combine the correction coefficient and mineral content data to calculate the content of various molybdenum minerals in the sample to be tested; among them, the content of molybdenite: M1=M b1*d*O1+(1-d)*M a1 ;

[0021] Molybdenum oxide mineral content: M j =(M bj *d+(1-d)*M aj )*O2, where j≥2, represents wulfenite, molybdenite and other oxygen-containing molybdenum minerals.

[0022] As a further improvement of the present application, in step S1, the grinding fineness of the grinding treatment is -0.074 mm and the content is 85.0~95.0%.

[0023] As a further improvement of the present application, the ore washing yield is 1-20%.

[0024] As a further improvement of the present application, in step S2, the flotation agent for gravity selection is kerosene, and the addition amount is 50-300 g / t.

[0025] As a further improvement of the present application, the gravity separation yield is 0.1-10.0%.

[0026] As a further improvement of the present application, in step S6, the molybdenite particles are divided into m square areas along the long axis direction with the short axis as the side.

[0027] The beneficial effects of this application are:

[0028] The present application provides a method for measuring the content of molybdenum minerals, which comprises grinding, washing and desludging the sample to be tested to obtain ore slime and washed ore concentrate; re-selecting the washed ore concentrate to separate the re-selection concentrate and re-selection tailings; mixing the ore slime and re-selection concentrate to obtain a mixed sample, performing molybdenum phase analysis, and obtaining the molybdenum oxide content; preparing automatic mineralogical analysis samples of the mixed sample and the re-selection tailings respectively, performing automatic mineralogical analysis, and calculating the correction coefficient of the molybdenite content and the correction coefficient of the molybdenum oxide content; combining the correction coefficient and the mineral content data to calculate the content of various molybdenum minerals in the sample to be tested. The present application reduces the oxidation of molybdenite and improves the accuracy of mineral identification by optimizing the sample preparation process. Molybdenum oxide and molybdenum sulfide are treated separately, and different correction processes are adopted to specifically improve the accuracy of ore molybdenum mineral measurement.

[0029] This application utilizes a morphology correction algorithm to address measurement errors associated with flaky molybdenite due to three-dimensional model assumptions. By combining washing, re-selection, and automated mineralogical analysis, multi-parameter correction improves the accuracy of molybdenum content determination. This method is applicable to complex molybdenum ores (such as mixed ores containing molybdenite, wolfenite, and molybdenum oxide), meeting the needs of industrial production, geological exploration, and mineral processing process optimization. Furthermore, this method can also be used to accurately measure the degree of dissociation of molybdenite, reducing measurement errors caused by its unique morphology.

[0030] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] To more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings used in this application. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0032] Figure 1 Flow chart of the method for measuring molybdenum mineral content provided in this application;

[0033] Figure 2 This is a schematic diagram of the segmentation of a molybdenite particle in an embodiment of the present application;

[0034] Figure 3 This is a schematic diagram of the segmentation of another type of molybdenite particles in an embodiment of the present application. DETAILED DESCRIPTION

[0035] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0037] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0038] Due to the large variety of molybdenum-containing minerals, the determination of molybdenum content is prone to deviations in results due to factors such as mineral characteristics, industrial production processes and analytical errors.

[0039] In order to solve the technical problem of low accuracy of molybdenum mineral content determination methods, the present application provides a method for measuring molybdenum mineral content. The method has the characteristics of being consistent with actual samples and having accurate measurement data. It differentially treats molybdenum oxide minerals and molybdenite through washing and re-selection to reduce cross-interference, and further realizes three-dimensional morphological restoration through geometric segmentation and thickness simulation. The error source is systematically eliminated through a two-level correction coefficient. The method is suitable for molybdenum mineral measurement in mixed complex molybdenum ores to support mineral processing process optimization and resource assessment.

[0040] Please refer to Figure 1 , the embodiment of the present application provides a method for measuring the content of molybdenum minerals, comprising the following steps:

[0041] S1. The sample to be tested is ground, and then washed and desludged to obtain sludge and washed concentrate;

[0042] S2. Gravity separation of the washed ore concentrate to obtain gravity separation concentrate and gravity separation tailings;

[0043] S3. Mixing the ore slime and the gravity separation concentrate to obtain a mixed sample with a yield of d, indicating the mass ratio of the mixed sample to the sample to be tested;

[0044] S4. The mixed sample was subjected to molybdenum phase analysis to obtain the molybdenum oxide content g;

[0045] S5. Prepare the mixed sample and the gravity separation tailings automatic mineralogical analysis samples, record them as a and b, and perform automatic mineralogical analysis. The molybdenum mineral contents are M aj and M bj , j is 1, 2, 3, ..., representing molybdenite, wolfenite, molybdenite and other oxygen-containing molybdenum minerals;

[0046] The molybdenum content of sample a molybdenum oxide mineral was measured to be h j , where j ≥ 2, representing wulfenite, molybdenite and other oxygen-containing molybdenum minerals;

[0047] The total molybdenum content in the molybdenum oxide mineral of sample a is B, B=∑(M aj *h j ), where j ≥ 2, representing wulfenite, molybdenite and other oxygen-containing molybdenum minerals;

[0048] S6. Calculate the correction factor O1 for molybdenite content, where O1=∑k n / n;

[0049] k n =2*(∑f nm *S nm ) / S n 1.5 ;

[0050] Sn is the area of ​​a single molybdenite grain, and n is the grain number;

[0051] S nm is the area of ​​the region, m is the number of regions segmented by the nth particle;

[0052] F nm= S nm 0.5 , simulated thickness of each region;

[0053] S7. Calculate the correction factor O2 for the molybdenum oxide content, where O2 = g / B;

[0054] S8. Combine the correction coefficient and mineral content data to calculate the content of various molybdenum minerals in the sample to be tested; among them, the content of molybdenite: M1=M b1 *d*O1+(1-d)*M a1 ;

[0055] Molybdenum oxide mineral content: M j =(M bj *d+(1-d)*M aj )*O2, where j≥2, represents wulfenite, molybdenite and other oxygen-containing molybdenum minerals.

[0056] In the technical solution of the embodiment of the present application, 1-3 kg of the sample to be tested is selected for grinding and washing and desludging. The sludge is mainly enriched in molybdenum oxide minerals, containing a small amount of molybdenite, which is mainly fine-grained minerals. The influence of the ore slime on the subsequent measurement of molybdenite is eliminated, and the misidentification of minerals is reduced; the gravity separation can adopt the Nielsen gravity separation equipment, and the centrifugal parameters are 10-40G; 5.0-7.0 g of the mixed sample and the gravity separation tailings are sampled respectively to prepare automatic mineralogical analysis samples. Specifically, the preparation of automatic mineralogical analysis samples includes rolling, mixing, ultrasonic vibration, side cutting after solidification, secondary inlaying, grinding and polishing, and carbon spraying. Through fine sample preparation, the error in the analysis process can be reduced and the reliability of the results can be improved. The grinding and polishing adopts abrasives with a particle size of ≤0.5 μm and a grinding and polishing time of ≥10 min. The sample is analyzed as soon as possible after preparation, or stored in a nitrogen environment to reduce the misidentification of molybdenum minerals caused by oxidation of the molybdenite edge; when performing automatic mineralogical analysis, it is preferred to accelerate the electric Raising the voltage to 10-15 kV can balance the signal penetration depth and resolution, reduce the signal overlap and mixed peak problems of molybdenum and sulfur elements, and preferably use a low beam current mode (1-5 nA) in combination with a charge neutralization device (such as a low vacuum mode) to reduce charge accumulation, improve image quality, and further optimize the test and analysis conditions. For the analysis of molybdenite, a combination of BSE (backscattered electron imaging) grayscale and EDS (energy dispersive X-ray spectroscopy) spectrum matching is used to avoid relying solely on the grayscale threshold. BSE is used for spatial positioning and preliminary screening, and EDS is used for precise chemical composition and structural ratio verification. The two work together to confirm the matching of minerals and improve the accuracy of test data. Through improved automatic mineralogical analysis, three-dimensional morphology reconstruction technology is introduced to correct the morphological misjudgment of the flaky structure of molybdenite. The total content of molybdenum oxide minerals is further corrected to compensate for errors caused by factors such as uneven molybdenum content in molybdenum minerals, sample preparation sedimentation, and sample segregation.

[0057] Furthermore, in some embodiments, in step S1, the grinding fineness of the grinding treatment is -0.074 mm and the content is 85.0-95.0%.

[0058] In the technical solution of the embodiment of the present application, grinding the ore to an appropriate fineness can ensure uniform mineral particle size, promote the separation of molybdenite from other minerals, facilitate subsequent ore washing and re-selection operations, and reduce deviations in the analysis process.

[0059] Furthermore, in some embodiments, the washing yield is 1-20%.

[0060] In the technical solution of the embodiment of the present application, the yield of washed concentrate is controlled, and fine particles and molybdenum oxide minerals are discharged, which helps to purify molybdenite.

[0061] Furthermore, in some embodiments, in step S2, the flotation agent for gravity separation is kerosene, the addition amount is 50-300 g / t, and the gravity separation yield is 0.1-10.0%.

[0062] In the technical solution of the embodiment of the present application, flotation agents are added to promote the entry of molybdenite into the gravity separation tailings, reduce the content of magnetic minerals and high-density molybdenum minerals, further increase the molybdenite content, and increase measurement accuracy.

[0063] Furthermore, in some embodiments, in step S6, the molybdenite particles are divided into m square regions along the long axis direction and with the short axis as the side.

[0064] In the technical solution of the embodiment of the present application, the specific analysis method of molybdenite is as follows:

[0065] The area of ​​a single molybdenite is measured as Sn (n is the particle number), and it is selected to be divided into m parts. The division method is: along the long axis direction, with the short axis as the side, divide m squares, and the area of ​​the molybdenite in the square is Snm equivalent square area; the conventional measurement method converts the measured area ratio into a volume ratio. The default minerals are all three-dimensional isometric crystal minerals, that is, cubic form, while molybdenite is a special flaky morphology mineral. When the conventional measurement mode is used for analysis, the data results have large errors and need to be restored to their actual form. The main purpose of particle correction is morphology correction.

[0066] Some specific examples are listed below. It should be noted that the examples described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0067] Example

[0068] This embodiment provides a method for measuring the content of molybdenum minerals, comprising the following steps:

[0069] S1. 3.0 kg of sample was selected for testing and ground to a grinding fineness of -0.074 mm and a content of 90.00%. The ore was then washed and desludged, and the washing yield was 10%, to obtain sludge and washed concentrate.

[0070] S2. Gravity separation of the washed concentrate sample was performed with a 5% yield, yielding a concentrate and tailings. Gravity separation was performed using a Nielsen gravity separation device with 100 g / t kerosene as a flotation agent, and a low centrifuge speed of 20 G.

[0071] S3. Mix the ore slime and the gravity separation concentrate to obtain a mixed sample with a yield of d = 14.50%;

[0072] S4. The mixed sample was sampled and subjected to molybdenum phase analysis, and the molybdenum oxide content g = 0.42%;

[0073] S5. 6.0 g of each of the mixed sample and the gravity separation tailings were sampled for automatic mineralogical analysis. Samples a and b were obtained by rolling, mixing, ultrasonic vibration for 30 minutes, side cutting after solidification, secondary mounting, grinding and polishing, and carbon spraying. When grinding, 1000 mesh or above abrasives were preferably used, and the surface was ground smooth. When polishing, abrasives were selected to 0.5 μm or less, and the grinding and polishing time was controlled to be more than 10 minutes. Automatic mineralogical analysis was performed on samples a and b with an acceleration voltage of 15 kV, using a low beam mode (5 nA) and a low vacuum mode. For the analysis of molybdenite, a combination of BSE grayscale and EDS spectrum matching (Mo / S ratio ≈ 1:2) was used to confirm the matching of minerals and improve the accuracy of the test data. The specific molybdenum mineral M aj and M bj The contents are detailed in Table 1, where j is 1, 2, and 3, representing molybdenite, wolfenite, and calcium molybdenite.

[0074] Calculate the total molybdenum content B in molybdenum oxide of sample a:

[0075] B=∑M aj *h j =0.24%*26.14%+0.62%*47.64%=0.36%; (j is 2 and 3, representing wulfenite and molybdenum calcium ore, respectively)

[0076] Table 1 Molybdenum mineral content measurement results

[0077]

[0078] S6. Measure the area of ​​a single molybdenite as S n (n is the particle number), the segmentation method is as follows Figures 2 to 3 As shown, Figure 2 Taking the medium particle as an example, it is divided into 8 parts, and the area and simulated thickness of each part are shown in Table 2.

[0079] Table 2 Particle segmentation calculation results

[0080]

[0081] Calculate the molybdenite content correction coefficient O1, where O1=∑k n / n;

[0082] k n =2*(∑f nm *S nm ) / S n 1.5 ;

[0083] S n 1.5 =16709.2371 1.5 =2,159,906.41;

[0084] k1=2*(1074.5284*32.78+5792.7321*76.11+……+136.1889*11.67) / 2,159,906.41=0.96;

[0085] O1=∑k n / n=(0.96+0.93+0.95+……) / 5673=0.94.

[0086] S7. Calculate the correction factor O2 for the molybdenum oxide content and further correct the total content of the molybdenum oxide mineral to compensate for errors caused by factors such as uneven molybdenum content in the molybdenum mineral, sample preparation sedimentation, and sample segregation. O2 = g / B = 0.42% / 0.36% = 1.167.

[0087] S8. Calculate the molybdenum mineral content in the sample to be tested:

[0088] Molybdenite content:

[0089] M1=M b1 *d*O1+(1-d)*M a1 =11.23%*14.50%*0.94+3.55%*85.50%=4.57%;

[0090] Molybdenite content:

[0091] M2=(M b2 *d+(1-d)*M a2 )*O2=(0.06%*14.50%+0.24%*85.50%)*1.167=0.25%;

[0092] Molybdenum calcium ore content:

[0093] M3=(M b3 *d+(1-d)*M a3 )*O2=(0.11%*14.50%+0.62%*85.50%)*1.167=0.64%.

[0094] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A method for measuring the content of molybdenum minerals, characterized in that: The following steps are involved: S1. The sample to be tested is ground, and then washed and desludged to obtain sludge and washed concentrate; S2. The washed ore concentrate is subjected to gravity separation to obtain a gravity separation concentrate and gravity separation tailings; S3. Mixing the sludge and the gravity concentrate to obtain a mixed sample with a yield of d; S4. The mixed sample was subjected to molybdenum phase analysis to obtain a molybdenum oxide content g; S5. Prepare the mixed sample and the gravity separation tailings automatic mineralogical analysis samples, denoted as a and b, and perform automatic mineralogical analysis to measure the molybdenum mineral content, respectively, M aj and M bj , j is 1, 2, 3, ..., representing molybdenite, wolfenite, molybdenite and other oxygen-containing molybdenum minerals; The molybdenum content of sample a molybdenum oxide mineral was measured to be h j , where j ≥ 2, representing wulfenite, molybdenite and other oxygen-containing molybdenum minerals; The total molybdenum content in the molybdenum oxide mineral of sample a is B, B=∑(M aj *h j ), where j ≥ 2, representing wulfenite, molybdenite and other oxygen-containing molybdenum minerals; S6. Calculate the correction factor O1 for molybdenite content, where O1=∑k n / n; k n =2*∑(f nm *S nm ) / S n 1.5 ; S n is the area of ​​a single molybdenite grain, and n is the grain number; S nm is the area of ​​the region, m is the number of regions segmented by the nth particle; f nm= S nm 0.5 , is the simulated thickness of each region; S7. Calculate the correction factor O2 for the molybdenum oxide content, where O2 = g / B; S8. Combine the correction coefficient and mineral content data to calculate the content of various molybdenum minerals in the sample to be tested; among them, the content of molybdenite: M1=M b1 *d*O1+(1-d)*M a1 ; Molybdenum oxide mineral content: M j =(M bj *d+(1-d)*M aj )*O2, where j≥2, represents wulfenite, molybdenite and other oxygen-containing molybdenum minerals.

2. The method for measuring the content of molybdenum minerals according to claim 1, wherein In step S1, the grinding fineness of the grinding treatment is -0.074 mm and the content is 85.0-95.0%.

3. The method for measuring the content of molybdenum minerals according to claim 2, wherein: The washing yield is 1~20%.

4. The method for measuring the content of molybdenum minerals according to claim 1, wherein In step S2, the flotation agent for gravity separation is kerosene, and the addition amount is 50-300 g / t.

5. The method for measuring the content of molybdenum minerals according to claim 4, wherein: The gravity separation yield is 0.1~10.0%.

6. The method for measuring the content of molybdenum minerals according to claim 1, wherein: In step S6, the molybdenite particles are divided into m square regions along the long axis direction and with the short axis as the side.

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