Molybdenum mineral content measuring method

Abstract

The invention provides a molybdenum mineral content measuring method, and belongs to the field of process mineralogy, and the method comprises the following steps: carrying out ore grinding, ore washing and desliming treatment on a to-be-measured sample to obtain slurry and ore washing concentrate; the ore washing concentrate is subjected to gravity separation, and gravity separation concentrate and gravity separation tailings are obtained through separation; mixing the slime and the gravity concentrate to obtain a mixed sample, and performing molybdenum phase analysis to obtain the content of molybdenum oxide; an automatic mineralogical analysis sample of the mixed sample and an automatic mineralogical analysis sample of the gravity separation tailings are prepared respectively, automatic mineralogical analysis is carried out, and a molybdenite content correction coefficient and a molybdenum oxide content correction coefficient are calculated; and calculating the content of various molybdenum minerals in the to-be-detected sample in combination with the correction coefficient and the mineral content data. By optimizing the sample preparation process, molybdenite oxidation is reduced, and the mineral recognition accuracy is improved. Molybdenum oxide and molybdenum sulfide are treated separately, different correction processes are adopted, and the accuracy of ore molybdenum mineral measurement is improved in a targeted mode.

Description

Technical Field

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

[0002] As a transition metal with important strategic value, molybdenum occupies an irreplaceable position in modern industry and high-tech fields by virtue of its unique physical and chemical properties. Molybdenum has an ultra-high melting point, excellent mechanical strength, outstanding corrosion resistance, and good thermal and electrical conductivity, making it a core material in key fields such as high-end manufacturing, military defense, new energy, and semiconductors. With the global industrial technology upgrade and the booming development of emerging industries, the application scope of molybdenum continues to expand, and the market demand shows a long-term stable growth trend.

[0003] In nature, molybdenum mainly occurs in the form of molybdenite in porphyry-type, skarn-type, and quartz-vein-type deposits, and often forms symbiotic relationships with metal minerals such as copper and tungsten. In addition to molybdenite, molybdenum-containing minerals with economic value also include wulfenite, powellite, etc. Molybdenite is extremely prone to oxidation under supergene conditions, forming secondary minerals such as molybdic ocher and ferrimolybdite, and its economic value is not high. Molybdenite has a typical hexagonal crystal system layered structure and is extremely easy to be peeled into thin flakes, with a significant particle size effect. When the fine particles are less than 1μm, they may be misjudged as other sulfides; wulfenite has significant high-density characteristics and relatively low molybdenum content, which all pose significant challenges to the accurate determination of molybdenum content. In addition, in industrial production practice, molybdenite, as the most important molybdenum industrial mineral, is usually concentrated by flotation. Its production process includes: the raw ore is crushed and ground and then molybdenum concentrate is obtained through flotation, the concentrate is oxidized and roasted to produce molybdenum trioxide, and finally metal molybdenum products are obtained through reduction smelting. However, due to the complex production process, diverse intermediate products, variable material compositions, 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 obvious 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 art, the present application provides a method for measuring the content of molybdenum minerals, aiming to solve the technical problem of low accuracy of the existing molybdenum mineral content determination methods.

[0006] The present application provides a method for measuring the content of molybdenum minerals, including the following steps: S1. Grind the sample to be measured, and then perform washing and desliming to obtain slime and washed concentrate; S2. Conduct gravity separation on the washed ore concentrate to separately obtain gravity separation concentrate and gravity separation tailings; S3. Mix the slime and the gravity separation concentrate to obtain a mixed sample with a yield of d; S4. Conduct molybdenum phase analysis on the mixed sample to obtain the molybdenum trioxide content g; S5. Prepare automatic mineralogy analysis samples of the mixed sample and the gravity separation tailings, denoted as a and b respectively, conduct automatic mineralogy analysis, and measure the molybdenum mineral contents as M aj and M bj , where j = 1, 2, 3..., representing molybdenite, lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species respectively; Measure the molybdenum element content of the molybdenum trioxide mineral in sample a as h j , where j≥2, representing lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species; The total molybdenum content in the molybdenum trioxide mineral of sample a is B, B = ∑(M aj *h j ), where j≥2, representing lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species; S6. Calculate the molybdenite content correction coefficient O1, 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 particle, and n is the particle number; S nm is the area of the region, and m is the number of regions divided by the nth particle; F nm= S nm 0.5 , is the simulated thickness of each region; S7. Calculate the molybdenum trioxide content correction coefficient O2, where O2 = g / B; S8. Combine the correction coefficients and mineral content data to calculate the contents of various molybdenum minerals in the sample to be measured; among them, the molybdenite content: M1 = M b1 *d*O1 + (1 - d)*M a1 ; The molybdenum trioxide mineral content: M j =(M bj *d + (1 - d)*M aj )*O2, where j≥2, representing lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species.

[0007] As a further improvement of the present application, in step S1, the grinding fineness of the grinding treatment is that the content of -0.074mm is 85.0 - 95.0%.

[0008] As a further improvement of the present application, the washing ore yield is 1 - 20%.

[0009] As a further improvement of the present application, in step S2, the flotation reagent for gravity separation is kerosene, and the addition amount is 50 - 300 g / t.

[0010] As a further improvement of the present application, the gravity separation yield is 0.1 - 10.0%.

[0011] As a further improvement of the present application, in step S6, the splitting method of molybdenite particles is: along the long axis direction, with the short axis as the side, split into m square areas.

[0012] The beneficial effects of the present application are as follows: The present application provides a method for measuring the molybdenum mineral content. By performing grinding, washing and desliming treatment on the sample to be measured, slime and washed ore concentrate are obtained; the washed ore concentrate is subjected to gravity separation to separate the gravity separation concentrate and the gravity separation tailings; the slime and the gravity separation concentrate are mixed to obtain a mixed sample, and molybdenum phase analysis is performed to obtain the content of molybdenum oxide; automatic mineralogy analysis samples of the mixed sample and the gravity separation tailings are respectively prepared, and automatic mineralogy analysis is performed to calculate the molybdenite content correction coefficient and the molybdenum oxide content correction coefficient; combined with the correction coefficient and the mineral content data, the content of various molybdenum minerals in the sample to be measured is calculated. By optimizing the sample preparation process, the present application reduces the oxidation of molybdenite and improves the accuracy of mineral identification. The molybdenum oxide and molybdenum sulfide are separately treated, and different correction processes are adopted to specifically improve the accuracy of molybdenum mineral measurement in the ore.

[0013] The present application adopts a morphological correction algorithm to solve the measurement deviation caused by the three-dimensional model assumption of flaky molybdenite. Through the combined analysis of washing, gravity separation and automatic mineralogy, multi-parameter correction improves the measurement accuracy of molybdenum content. This method is applicable to complex molybdenum ores (such as mixed ores containing molybdenite, lead molybdate, and molybdenum oxide), and can meet the requirements of industrial production, geological exploration, and beneficiation process optimization. In addition, this method can also be used for accurate measurement of molybdenite dissociation degree data, reducing measurement errors caused by special morphology.

[0014] The above description is only an overview of the technical solution of the present application. In order to be able to understand the technical means of the present application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features and advantages of the present application more obvious and understandable, the specific embodiments of the present application are hereinafter specifically exemplified. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0016] Figure 1 It is a flowchart of the method for measuring the molybdenum mineral content provided by this application; Figure 2 It is a schematic diagram of the segmentation of a molybdenite particle in an embodiment of this application; Figure 3 It is another schematic diagram of the segmentation of a molybdenite particle in an embodiment of this application. Detailed implementation manners

[0017] The embodiments of the technical solutions of this application will be described in detail below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solutions of this application, so they are only examples and cannot be used to limit the protection scope of this application.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field 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 accompanying drawing descriptions are intended to cover non-exclusive inclusion.

[0019] Referring to "embodiments" in this context means that the specific features, structures, or characteristics described in connection with the embodiments can be included in at least one embodiment of this application. The phrase appears in various places in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.

[0020] Due to the variety of molybdenum-containing minerals, the determination of molybdenum content is prone to result deviations due to factors such as mineral characteristics, industrial production processes, and analysis errors.

[0021] To solve the technical problem of low accuracy in the method for measuring the molybdenum mineral content, this application provides a method for measuring the molybdenum mineral content. This method has the characteristics of fitting the actual sample and accurate measurement data. It differentially processes molybdenum oxide minerals and molybdenite through ore washing and gravity separation respectively to reduce cross-interference. Further, it realizes the three-dimensional morphology restoration through geometric segmentation and thickness simulation, and systematically eliminates the error sources through two-level correction coefficients. It is applicable to the measurement of molybdenum minerals in mixed and complex molybdenum ores to support the optimization of beneficiation processes and resource assessment.

[0022] Please refer to Figure 1 , an embodiment of the present application provides a method for measuring the molybdenum mineral content, including the following steps: S1. Grind the sample to be measured, and then perform ore washing and desliming to obtain slime and ore washing concentrate; S2. Perform gravity separation on the ore washing concentrate to separate and obtain gravity separation concentrate and gravity separation tailings; S3. Mix the slime and the gravity separation concentrate to obtain a mixed sample, and the yield is d, which represents the mass ratio of the mixed sample to the sample to be measured; S4. Perform molybdenum phase analysis on the mixed sample to obtain the molybdenum oxide content g; S5. Prepare automatic mineralogy analysis samples of the mixed sample and the gravity separation tailings, denoted as a and b, respectively, and perform automatic mineralogy analysis to measure the molybdenum mineral contents as M aj and M bj , where j is 1, 2, 3..., representing molybdenite, lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species, respectively; Measure the molybdenum element content of the molybdenum oxide mineral in sample a as h j , where j≥2, representing lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species; The total molybdenum content in the molybdenum oxide mineral of sample a is B, B = ∑(M aj *h j ), where j≥2, representing lead molybdate, calcium molybdate, and other oxygen-containing molybdenum mineral species; S6. Calculate the molybdenite content correction coefficient O1, 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 particle, and n is the particle number; S nm is the area of the region, and m is the number of regions divided by the nth particle; F nm= S nm 0.5 , is the simulated thickness of each region; S7. Calculate the molybdenum oxide content correction coefficient O2, where O2 = g / B; S8. Combine the correction coefficient and the mineral content data to calculate the content of various molybdenum minerals in the sample to be measured; among them, the molybdenite content: M1 = M b1 *d*O1 + (1 - d)*M a1 ; The molybdenum oxide mineral content: Mj =(M bj *d + (1 - d)*M aj )*O2, where j ≥ 2, representing the types of powellite, wulfenite and other molybdenum-containing oxygen minerals.

[0023] 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 to remove slime. The slime is mainly enriched with molybdenum oxide minerals, containing a small amount of molybdenite, mainly fine-grained minerals, excluding the influence of slime on the subsequent measurement of molybdenite and reducing the misidentification of minerals; the gravity separation can use Nelson gravity separation equipment, and the centrifugal parameter is 10 - 40 G; 5.0 - 7.0 g of the mixed sample and the gravity separation tailings are respectively sampled to prepare an automatic mineralogy analysis sample. Specifically, the preparation of the automatic mineralogy analysis sample includes rolling, mixing with glue, ultrasonic oscillation, side cutting after curing, secondary embedding, grinding and polishing, and carbon spraying treatment. Through the 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 uses abrasive with a particle size ≤ 0.5 μm, and the grinding and polishing time is ≥ 10 min. Analyze as soon as possible after preparation, or store it in a nitrogen environment to reduce the misidentification of molybdenum minerals caused by the oxidation of the edge of molybdenite; when performing automatic mineralogy analysis, it is preferred to accelerate the voltage to 10 - 15 kV, which can balance the signal penetration depth and resolution, reduce the signal overlap and peak mixing problems of molybdenum and sulfur elements, and it is preferred to use a low beam current mode (1 - 5 nA) and be equipped with a charge neutralization device (such as a low vacuum mode) to reduce charge accumulation and improve the image quality, further optimizing the test analysis conditions; for the analysis of molybdenite, the combination of BSE (backscattered electron imaging) gray scale and EDS (energy dispersive X-ray spectroscopy analysis) spectrum matching is adopted, avoiding relying solely on the gray scale threshold, using BSE for spatial positioning and preliminary screening, and then using EDS for precise verification of chemical composition and structural ratio, and the two cooperate to confirm the matching of minerals, improving the accuracy of test data; through the improved automatic mineralogy analysis, the three-dimensional morphology reconstruction technology is introduced to correct the morphological misjudgment of the flaky structure of molybdenite; further, the total content of molybdenum oxide minerals is corrected, and the errors caused by factors such as uneven molybdenum content, sample sedimentation during sample preparation, and sample segregation in molybdenum minerals are supplemented.

[0024] Further, in some embodiments, in step S1, the grinding fineness of the grinding treatment is that the content of -0.074 mm is 85.0 - 95.0%.

[0025] In the technical solution of the embodiment of the present application, grinding to an appropriate fineness can ensure uniform mineral particle size, promote the separation of molybdenite from other minerals, facilitate subsequent washing and gravity separation operations, and reduce the deviation in the analysis process.

[0026] Further, in some embodiments, the washing yield is 1 - 20%.

[0027] In the technical solution of the embodiment of the present application, controlling the yield of washed ore concentrate and discharging fine-grained and molybdenum oxide minerals helps to purify molybdenite.

[0028] Further, in some embodiments, in step S2, the flotation reagent for gravity separation is kerosene, the addition amount is 50 - 300 g / t, and the gravity separation yield is 0.1 - 10.0%.

[0029] In the technical solution of the embodiment of the present application, adding a flotation reagent promotes molybdenite to enter the gravity separation tailings, reduces the content of magnetic minerals and molybdenum minerals with a large specific gravity, further increases the molybdenite content, and improves the measurement accuracy.

[0030] Further, in some embodiments, in step S6, the molybdenite particle segmentation method is: along the long axis direction, with the short axis as the side, m square regions are segmented.

[0031] In the technical solution of the embodiment of the present application, the specific analysis method of molybdenite is as follows: Measure the area of a single molybdenite as Sn (n is the particle number), and select to divide it into m parts. The segmentation method is: along the long axis direction, with the short axis as the side, m squares are segmented. The area of molybdenite in the square is Snm, which is equivalent to the area of the square. In the conventional measurement method, the measured area ratio is converted into a volume ratio. By default, the minerals are all three-dimensional isometric crystal system minerals, that is, cubic in shape, while molybdenite is a special flaky mineral. When analyzed using the conventional measurement mode, the data results have large errors, and its actual shape needs to be restored. The main purpose of particle correction is shape correction.

[0032] The following lists some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain the present application and should not be construed as a limitation to the present application. For those embodiments where specific technologies or conditions are not indicated, they shall be carried out according to the technologies or conditions described in the literature in the field or according to the product instructions. For reagents or instruments whose manufacturers are not indicated, they are all conventional products that can be obtained through commercial purchase.

[0033] Embodiment This embodiment provides a method for measuring the molybdenum mineral content, including the following steps: S1. Select 3.0 kg of the sample to be measured, perform grinding, and the grinding fineness is 90.00% with a particle size of -0.074 mm. Then, perform washing and desliming, and the washing yield is 10%, obtaining slime and washed ore concentrate; S2. Perform gravity separation on the washed ore concentrate sample, and the gravity separation yield is 5%, obtaining gravity separation concentrate and gravity separation tailings; The gravity separation uses a Nelson gravity separation device, adding the flotation reagent kerosene: 100 g / t, with a low centrifugal speed and a 20G centrifugal parameter setting; S3. Mix the slime and the gravity separation concentrate to obtain a mixed sample, and the yield is d = 14.50%; S4. Take a sample of the mixed sample for molybdenum phase analysis, and obtain that the content of molybdenum oxide g = 0.42%; S5. Take 6.0 g samples of the mixed sample and the said gravity separation tailings respectively to prepare automatic mineralogy analysis samples. Through rolling, mixing with glue, ultrasonic oscillation for 30 min, solidification, side cutting, secondary embedding, grinding and polishing, carbon spraying treatment, samples a and b are obtained; When grinding, abrasives of 1000 mesh and above are preferably used until the surface is smooth. When polishing, abrasives of 0.5 μm and below are selected, and the grinding and polishing time is controlled above 10 min; Automatic mineralogy analysis is carried out on samples a and b, the acceleration voltage is up to 15 kV, and the low beam current mode (5 nA) and low vacuum mode are used; For the analysis of molybdenite, the combination of BSE gray scale and EDS spectrum matching (Mo / S ratio ≈ 1:2) is adopted to confirm the matching of minerals and improve the accuracy of test data; The specific molybdenum minerals M aj and M bj contents are shown in Table 1, where j is 1, 2, 3, representing molybdenite, lead molybdate and calcium molybdate.

[0034] Calculate the total molybdenum content B in molybdenum oxide of sample a: B = ∑M aj *h j = 0.24% * 26.14% + 0.62% * 47.64% = 0.36%; (j is 2, 3, representing lead molybdate and calcium molybdate respectively) Table 1 Measurement results of molybdenum mineral content S6. Measure the area of a single molybdenite as S n (n is the particle number), and the segmentation method is as Figures 2 to 3 shown. Taking the particle in Figure 2 as an example, it is divided into 8 parts, and the area and simulated thickness of each part are shown in Table 2.

[0035] Table 2 Particle segmentation calculation results Calculate the molybdenite content correction coefficient O1, where O1 = ∑k n / n; k n = 2 * (∑f nm *S nm ) / S n 1.5 ; S n 1.5 = 16709.2371 1.5 = 2,159,906.41; k1 = 2 * (1074.5284 * 32.78 + 5792.7321 * 76.11 + …… + 136.1889 * 11.67) / 2,159,906.41 = 0.96; O1 = ∑k n / n = (0.96 + 0.93 + 0.95 + ……) / 5673 = 0.94。

[0036] S7. Calculate the molybdenum oxide content correction coefficient O2, further correct the total content of molybdenum oxide minerals, and supplement the errors caused by factors such as uneven molybdenum content in molybdenum minerals, sample preparation sedimentation, and sample segregation. O2 = g / B = 0.42% / 0.36% = 1.167.

[0037] S8. Calculate the molybdenum mineral content data in the sample to be measured: Content of molybdenite: M1 = M b1 *d*O1 + (1 - d)*M a1 = 11.23% * 14.50% * 0.94 + 3.55% * 85.50% = 4.57%; Content of wulfenite: M2 = (M b2 *d + (1 - d)*M a2 ) * O2 = (0.06% * 14.50% + 0.24% * 85.50%) * 1.167 = 0.25%; Content of powellite: M3 = (M b3 *d + (1 - d)*M a3 ) * O2 = (0.11% * 14.50% + 0.62% * 85.50%) * 1.167 = 0.64%.

[0038] It should be noted that this application is not limited to the above embodiments. The above embodiments are only examples, and embodiments with the same structure and the same effect as the technical idea within the scope of the technical solution of this application are included in the technical scope of this application. In addition, within the scope of not departing from the gist of this application, various modifications that can be thought of by those skilled in the art to the embodiments, and other ways constructed by combining some constituent elements of the embodiments are also included in the scope of this application.

Claims

1. A method for measuring the content of molybdenum minerals, characterized in that, Including the following steps: S1. Grind the sample to be tested, and then perform ore washing and desliming to obtain slime and washed ore concentrate; S2. Perform gravity separation on the washed ore concentrate to separate gravity separation concentrate and gravity separation tailings; S3. Mix the slime and the gravity separation concentrate to obtain a mixed sample with a yield of d; S4. Perform molybdenum phase analysis on the mixed sample to obtain the molybdenum oxide content g; S5. Prepare the automatic mineralogy analysis samples of the mixed sample and the gravity separation tailings respectively, denoted as a and b, conduct automatic mineralogy analysis, and measure the molybdenum mineral contents as M aj and M bj , where j = 1, 2, 3..., representing molybdenite, lead molybdate, calcium molybdate and other oxygen-containing molybdenum mineral species respectively; The measured molybdenum element content of the molybdenum oxide mineral of sample a is h j , where j ≥ 2, representing the types of wulfenite, powellite and other oxygen-containing molybdenum minerals; The total molybdenum content in sample a molybdenum oxide minerals is B, B = ∑(M aj *h j ), where j ≥ 2, representing the types of powellite, powellite and other oxygen-containing molybdenum minerals; S6. Calculate the molybdenite content correction factor O1, 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 particle, and n is the particle number; S nm is the area of the region, and m is the number of regions divided by the nth particle; F nm= S nm 0.5 , which is the simulated thickness of each region; S7. Calculate the molybdenum oxide content correction coefficient O2, where O2 = g / B; S8. Combine the correction factor and the mineral content data to calculate the content of various molybdenum minerals in the sample to be measured; 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, representing the types of powellite, wulfenite and other oxygen-containing molybdenum minerals.

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

3. The method for measuring the molybdenum mineral content according to claim 2, characterized in that The ore washing yield is 1 - 20%.

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

5. The method for measuring the molybdenum mineral content according to claim 4, wherein The gravity separation yield is 0.1 - 10.0%.

6. The method for measuring the molybdenum mineral content according to claim 1, characterized in that, In step S6, the splitting method of molybdenite particles is: along the long axis direction, with the short axis as the side, split into m square areas.

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