A method for beneficiation and enrichment of highly oxidized molybdenum ore

Abstract

The present invention provides a beneficiation and enrichment method for highly oxidized molybdenum ore. The method comprises magnetic separation of the grinding product according to particle size, regrinding the coarse magnetic tailings, mixing the regrinding product with the fine magnetic tailings for low-potential sulfide flotation, and flotation of the sulfide flotation tailings for oxide ore. The method ultimately produces a molybdenum concentrate with high recovery and grade, achieving both molybdenum ore separation and enrichment, and effectively and comprehensively recovering the finely interbedded, difficult-to-separate oxidized molybdenum ore resources in highly oxidized molybdenum ore. To rapidly optimize and obtain optimal conditions for oxide ore flotation, the present invention utilizes pure mineral flotation tests to determine a flotation depressant with high inhibitory effect, and utilizes molecular simulation calculations to select a highly selective flotation collector, thereby improving flotation efficiency and selectivity. The method proposed in the present invention is widely applicable to the development of highly oxidized molybdenum mines and the recovery and utilization of fine, difficult-to-separate oxidized molybdenum ore resources in tailings after sulfide flotation.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing and enrichment technology, in particular to a mineral processing and enrichment method for highly oxidized molybdenum ore. Background Art

[0002] Nowadays, the grade of ore deposits is generally low, and the shortage of molybdenum resources has become an indisputable fact. Therefore, it is urgent to solve the problem of separation and enrichment of difficult-to-select molybdenum resources.

[0003] There are over 30 molybdenum-containing minerals found in nature. Among them, sulfide-molybdenum ores such as molybdenite and molybdenite have advantages such as good natural floatability and large particle size, making them easy to separate and recover via flotation. Molybdenum oxides, on the other hand, are difficult to separate. Due to their naturally hydrophobic nature, they are well dispersed and stable in the slurry. They also resist binding to collectors during flotation, which affects the flotation product. Furthermore, there are numerous types of molybdenum oxides, and their surface physical and chemical properties vary widely. Molybdenum oxide ore generally has a density of around 4.6 g / cm³, a low hardness, and is easily crushed. These physical properties make it prone to over-grinding and sliming during grinding, increasing the difficulty of flotation. Furthermore, molybdenum oxide ore generally has a finer particle size, making it more likely to be mixed with other minerals, reducing flotation selectivity.

[0004] Minerals such as molybdenum ore (MoO3), molybdenum calcium ore (CaMoO4), iron molybdenum ore [Fe2(MoO4)3], molybdenum lead ore and molybdenum-containing goethite are often found in high oxidation rate molybdenum deposits.

[0005] This type of molybdenum oxide minerals are mostly secondary minerals formed after the oxidation of molybdenite. They have incomplete crystallization, small crystals, low hardness, easy over-grinding, and natural hydrophilicity, making flotation recovery extremely difficult.

[0006] Currently, mining companies generally use two treatment options for highly oxidized molybdenum ores: one involves flotation of a mixture of molybdenum sulfide and molybdenum oxide to obtain a lower-grade molybdenum concentrate, which is then processed through hydrometallurgical processes to produce ammonium molybdate. The other involves wet leaching of the molybdenum oxide minerals, followed by flotation of the residue to obtain a molybdenite concentrate. When flotation is used to treat highly oxidized molybdenum oxide ores, achieving both high concentrate grade and high recovery is often compromised. This is due to the poor selectivity of flotation collectors for molybdenum oxide ores and the difficulty maintaining a stable inhibitory capacity. This results in either ineffective flotation separation or significant molybdenum ore loss in the tailings. Therefore, further development of efficient recovery solutions is needed. Summary of the Invention

[0007] The purpose of the present invention is to solve the defects of the above-mentioned prior art and provide a method for beneficiation and enrichment of highly oxidized molybdenum ore.

[0008] A method for beneficiation and enrichment of highly oxidized molybdenum ore comprises the following steps:

[0009] a. Classifying the primary grinding pulp into two parts with a particle size greater than 0.150 mm and a particle size less than 0.150 mm. The two parts of pulp are respectively separated by a wet high-intensity magnetic separator to separate magnetic minerals and pulp. The magnetic minerals are collected as high-intensity magnetic concentrate to separate the molybdenum oxide ore contained in the iron oxide; the non-magnetic minerals are discharged as tailings, so that other non-magnetic molybdenum-containing minerals are initially enriched in the non-magnetic pulp;

[0010] b. regrinding the non-magnetic slurry with a particle size greater than 0.150 mm, and the ground product and the non-magnetic slurry with a particle size less than 0.150 mm are fed into a low-potential sulfide flotation operation;

[0011] c. The above regrinding and fine-grained non-magnetic slurry are used as feed for low-potential sulfide flotation. Sulfiding agent, sulfide flotation collector and frother are added. After two roughing and two scavenging, four portions of sulfide flotation ore with higher molybdenum grade and non-magnetic tailings with lower molybdenum grade are obtained;

[0012] d. The non-magnetic tailings pulp from the above sulfide flotation is used as feed for oxidation flotation, and a regulator, inhibitor, oxidation flotation collector and frother are added. After one roughing and two scavenging processes, oxidation flotation ore with higher molybdenum grade and non-magnetic tailings with lower molybdenum grade are obtained;

[0013] e. The above-mentioned high-intensity magnetic separation concentrate and the oxidative flotation ore are combined to serve as raw materials for the hydrometallurgical preparation of ammonium molybdate products; the above-mentioned sulfide flotation ore is further refined to improve the grade of the sulfide molybdenum ore; the above-mentioned oxidative flotation non-magnetic tailings are discharged as the final tailings of the mineral processing process.

[0014] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the particle size of the primary grinding product is less than 0.150 mm, accounting for 40-60%; and the particle size of the fine-grained ore after classification is less than 0.074 mm, accounting for 70-90%.

[0015] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the wet high-intensity magnetic separator refers to an industrial vertical ring or flat ring high-intensity magnetic separator, a vertical ring or flat ring pulsating high-gradient high-intensity magnetic separator, or a combination of two or more devices, the magnetic separation field strength is 0.8~1.8T, and the slurry concentration is 20~40% by mass.

[0016] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the particle size of the non-magnetic slurry regrinding product is less than 0.074 mm, accounting for 75-95%.

[0017] Furthermore, in the beneficiation and enrichment method of highly oxidized molybdenum ore as described above, during the low-potential sulfidation flotation slurry adjustment process, the pulp potential is controlled below -80mV after the sulfiding agent is added, and subsequent dosing flotation is performed after reaching the potential.

[0018] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the sulfiding agent is one or a combination of two of sodium sulfide, sodium sulfite, and monovalent copper ions, the addition amount of roughing I is 800~1600g / t, the addition amount of roughing II is 400~800g / t, and the addition amount of scavenging is 0~400g / t, and the addition amount is based on the number of grams of reagent added per ton of flotation ore.

[0019] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the sulfide flotation collector is one or a combination of xanthate and black medicine, the addition amount for roughing I is 60-100 g / t, the addition amount for roughing II is 30-50 g / t, and the addition amount for scavenging is 30-50 g / t, and the addition amount is based on the number of grams of the agent added per ton of flotation ore.

[0020] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the oxidizing flotation adjuster is one or a combination of two agents selected from soda ash, caustic soda, and lime, and the added amount is based on the pH value of the ore pulp, and the pH value of the ore pulp is controlled to be 8-10.

[0021] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the foaming agent is one or a combination of two agents selected from pine oil, No. 2 oil, mixed fatty alcohols, methyl isobutyl carbinol, and ether alcohols, and the addition amount for roughing is 30-50 g / t, and the addition amount for scavenging is 10-30 g / t, and the addition amount is based on the number of grams of the agent added per ton of flotation ore.

[0022] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, in the oxidation flotation process, the flotation reagent is selected based on the results of pure gangue mineral flotation tests and molecular simulation calculations.

[0023] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the mineral used in the pure gangue mineral flotation is the main gangue mineral in the actual ore, and the mineral particle size is the same as the feed particle size during the actual ore flotation. The pure mineral flotation test is a test to select the best inhibitor under the best corresponding gangue mineral collection system; the tested reagents include water glass, acidic water glass, a mixture of water glass and metal ions, sodium alginate, CMC, sodium humate, and sodium pyrophosphate.

[0024] The basis for selecting the inhibitor is to select the inhibitor with the greatest comprehensive inhibition degree for each gangue mineral, the most stable inhibition effect at each pulp pH, and the least inhibitory effect on molybdenum calcium ore as the best flotation inhibitor.

[0025] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the optimal collection system includes an optimal collector dosage, an optimal slurry pH, an optimal slurry temperature, an optimal stirring speed, and an optimal flotation time.

[0026] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the molecular simulation calculation is performed by modeling the main oxidized molybdenum ore in the ore, calculating the adsorption energy of different collector molecules on the surface of the oxidized molybdenum ore, and simulating the adsorption process of each collector on the surface of the oxidized molybdenum ore; the calculated reagent molecules include oleic acid, sodium oleate, oxidized paraffin soap, benzohydroxamic acid, alkylhydroxamic acid, hexadecylpyridinium chloride, and dodecylamine.

[0027] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the modeling process uses molecular modeling software to perform first-principles optimization on the molybdenum oxide ore to obtain the lowest energy and most reasonable crystal structure, and then performs cross-section processing to obtain the surface model of the most easily dissociated surface, sets a vacuum layer of 10~20Å, and fixes the bottom 3~5 layers of atoms at the same time, and then performs first-principles optimization to obtain the surface model of the molybdenum oxide dissociation surface.

[0028] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the molybdenum oxide surface model is expanded to 1.5 to 2 times the size of the flotation collector model in the x and y directions, and then the flotation collector model is placed on the molybdenum oxide surface model at a distance of 1.5 to 3 Å to obtain a molybdenum oxide dissociation surface and a flotation collector molecule adsorption model.

[0029] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the simulation calculation is a first-principle calculation of the adsorption model, and the adsorption energy calculation is performed using CASTEP or DMol3 module, wherein the convergence standard (SCFtolerance) is 1×10 -5 ~1×10 -8 eV / atom, the energy cutoff is set to 400~1000eV.

[0030] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the adsorption energy is calculated by the adsorption energy formula: ∆E=E complex -E mineral +E agent Calculate the adsorption energy between the mineral surface and the reagent molecules, or determine whether there is adsorption between the mineral surface and the reagent molecules; where ∆E represents the adsorption energy between the mineral surface and the reagent molecules, and E complex Represents the total energy of the adsorption model between the mineral surface and the reagent molecules, E mineral Represents the energy of the mineral surface model, Eagent Indicates the energy of the drug molecular model; ∆E, E complex 、E mineral and E agent The unit is eV.

[0031] Furthermore, in the above-described method for beneficiation and enrichment of highly oxidized molybdenum ore, the adsorption model is a model obtained by repeatedly adjusting the distance between the reagent and the mineral and the adsorption sites to achieve the lowest adsorption energy. The adsorbent in this model serves as the optimal collector for actual mineral separation. In the present invention, the total energy of the adsorption model between the mineral surface and the reagent molecules is selected based on the principle of lowest adsorption energy; the adsorption model is a model obtained by adjusting the distance between the reagent and the mineral and the adsorption sites N times to achieve the lowest adsorption energy, where N is a positive integer greater than or equal to 1.

[0032] The advantages of the present invention are:

[0033] 1. The present invention adopts a strong magnetic separation process to select magnetic minerals in the raw ore, thereby preliminarily enriching the molybdenum oxide ore contained in the iron oxide. The embedded particle size of this type of molybdenum oxide ore is extremely fine and difficult to separate through subsequent processes. Compared with the conventional process of mixed flotation of sulfide ore and oxide ore, this process enriches this type of extremely fine-grained molybdenum oxide ore, removes a large amount of magnetic iron oxide in advance, reduces the impact of iron oxide on subsequent flotation processes, reduces the material handling volume of subsequent operations, improves the overall molybdenum grade and recovery rate in the concentrate, and significantly improves the separation efficiency of subsequent mineral processing operations;

[0034] 2. Most of the molybdenum-containing minerals in highly oxidized molybdenum ores are embedded in very fine particles. It is difficult to dissociate the coarse particles into monomers, and the fine particles are easily muddied and difficult to separate. Therefore, it is difficult to recover them using the conventional "grinding-magnetic separation-flotation" process. The present invention classifies the primary grinding products and magnetically separates the coarse and fine particles respectively, so that the molybdenum in the coarse magnetic separation concentrate has a higher grade and recovery rate. The coarse non-magnetic minerals are regrinded, and the regrinded products are mixed with the fine non-magnetic minerals to enter the flotation operation, thereby reducing the processing capacity during regrinding, reducing the phenomenon of mineral muddiing due to over-grinding, and improving the effect of subsequent flotation operations;

[0035] 3. Sulfide molybdenum ore is generally colloidal sulfide molybdenum ore, which has no fixed crystal structure and a wide particle size range. Fine-grained colloidal sulfide molybdenum ore is difficult to combine with flotation reagents. The present invention adopts a low-potential flotation process for sulfide ore flotation, prolongs the action time between the reagent and the mineral, and increases the adsorption strength of the reagent on the surface of the sulfide mineral. It can basically completely separate the molybdenum sulfide minerals in the original ore, and make the sulfide flotation tailings basically free of molybdenum sulfide minerals, reduce the interference of the sulfide ore on the subsequent oxidation flotation, and improve the recovery rate of the molybdenum ore in the whole process;

[0036] 4. For molybdenum oxide ore, since molybdenum oxide ore generally has incomplete crystallization, small crystals, low hardness, easy over-grinding, and natural hydrophilicity, the flotation recovery of molybdenum oxide ore is extremely difficult, especially the selection of flotation reagents is very difficult. The collectors generally have poor selectivity and cannot obtain high-grade molybdenum oxide ore. The inhibitors generally have an inhibitory effect on the molybdenum oxide ore, resulting in a low concentrate recovery rate. The present invention uses pure mineral flotation tests to determine flotation inhibitors with better inhibitory effects, and uses molecular simulation calculation methods to select flotation collectors with stronger selectivity, thereby improving flotation efficiency and selectivity, and effectively improving the grade and recovery rate of molybdenum in the oxide flotation concentrate product. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The figure is a flow chart of the beneficiation and enrichment method of highly oxidized molybdenum ore of the present invention.

[0038] Figure 2 This is a molecular simulation calculation of linoleic acid and oleic acid agents on the surface of molybdenum calcium ore in Comparative Example 5 of the present invention. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described below in conjunction with examples, but is not limited thereto.

[0040] The oxidation rate of molybdenum in a difficult-to-process uranium-molybdenum ore in Hebei Province reaches 71.4%. Process mineralogy research shows that the original ore contains 0.28% molybdenum. The molybdenum minerals in the ore are mainly oxide molybdenite, followed by sulfide molybdenite. Nearly 50% of the molybdenum ore is extremely fine-grained oxide molybdenite embedded in iron oxides, and about 20% of the molybdenum ore is oxide molybdenum ore embedded in gangue minerals or independently mineralized, mainly molybdenite, with some molybdenum sulphide and trace blue molybdenite. About 30% of the molybdenum ore is sulfide molybdenum ore, mainly colloidal sulfide molybdenite, with some molybdenite. Pyrite, hematite and limonite are other major metallic minerals in the ore, with a small amount of sphalerite, galena, zircon, magnetite, ilmenite and monazite. The main gangue minerals are quartz, orthoclase, muscovite and biotite. The molybdenum-containing minerals in the ore samples are generally fine-grained and closely embedded with other minerals. In addition, the molybdenum-containing minerals are generally low in hardness, brittle and easily muddied, making it difficult to separate them into monomers through conventional grinding. A large amount of molybdenum ore is contained in iron oxides, and the particle size of this part of the molybdenum ore is extremely fine and cannot be separated. The vast majority of the iron oxides in the original ore are hematite and limonite, which can only be separated by strong magnetic separation. The particle size range of colloidal sulfide molybdenum ore is wide, and although it is hydrophobic, it is difficult to float because it does not have a complete crystal form. The crystallization of molybdenum calcium ore is poor, the monomer particle size of molybdenum calcite minerals is extremely fine, and the molybdenum oxide minerals are closely embedded in the gangue minerals and are hydrophilic, making flotation recovery extremely difficult.

[0041] In order to more efficiently and comprehensively recycle and utilize the molybdenum resources in the ore, a large number of experimental research projects have been carried out on various mineral processing and enrichment process schemes such as flotation, magnetic separation, gravity separation, color separation, and magnetic separation-flotation, targeting the difficult-to-select molybdenum minerals in the highly oxidized molybdenum ore. In addition, a large number of theoretical research projects on pure mineral flotation experiments and molecular simulation calculations have been carried out to select the theoretically optimal flotation agent. The highly oxidized, fine-grained molybdenum ore cannot obtain molybdenum concentrate or middling products with high molybdenum grade and recovery rate by using single flotation, magnetic separation, gravity separation, and color separation, and the purpose of effectively separating and enriching the molybdenum resources in the original ore cannot be achieved.

[0042] Example 1

[0043] In order to solve the above technical difficulties, based on a large number of mineral processing test studies, the present invention proposes a new mineral processing and enrichment method of "classification-magnetic separation-coarse particle regrinding-low-potential sulfide flotation-oxidation flotation" combined process, which obtains a molybdenum grade of 0.830% and a recovery rate of 29.23% in magnetic iron oxides; the roughing molybdenum grade of 0.342% by sulfide flotation and the molybdenum recovery rate of 28.56% by sulfide flotation; the roughing molybdenum grade of 0.245% by oxidation flotation and the molybdenum recovery rate of 29.53% by oxidation flotation; the molybdenum recovery rate of the total separation process is 87.31%.

[0044] Figure 1 The flow chart of the beneficiation and enrichment method of highly oxidized molybdenum ore of the present invention is as follows: Figure 1 As shown, the method provided by the present invention comprises the following steps:

[0045] The conclusions drawn from the flotation test of pure gangue minerals are as follows:

[0046] The minerals used in the pure gangue mineral flotation are the main gangue minerals in the actual ore, and the mineral particle size is the same as the feed particle size during the actual ore flotation. The pure mineral flotation test is a test to select the best inhibitor under the best corresponding gangue mineral collection system; the tested reagents include water glass, acidic water glass, a mixture of water glass and metal ions, sodium alginate, CMC, sodium humate, and sodium pyrophosphate.

[0047] The selection criteria for the inhibitors are to select the inhibitors that have the greatest comprehensive inhibition on each gangue mineral, the most stable inhibition effect at each pulp pH, and the least inhibition effect on molybdenum calcium ore as the best flotation inhibitor;

[0048] In this embodiment, compared with inhibitors such as sodium alginate, CMC, sodium humate, and sodium pyrophosphate, water glass inhibitors have a good inhibitory effect on various gangue minerals in actual mines, among which a 1:1 mixed solution of water glass and aluminum sulfate has the best inhibitory effect. Therefore, a 1:1 mixed solution of water glass and aluminum sulfate is selected as an inhibitor in the actual mineral oxidation flotation process.

[0049] Molecular simulation calculations led to the conclusion that:

[0050] The mineral surface model used in the molecular simulation calculations was molybdenite, a mineral found in actual ores. The reagent models included oleic acid, sodium oleate, oxidized paraffin soap, benzohydroxamic acid, alkyl hydroxamic acid, hexadecylpyridinium chloride, and dodecylamine. Before surface energy calculations, the molybdenite unit cell was geometrically optimized. The binding energy between the molybdenite {001} crystal face model and the reagents was calculated, with a 15 Å vacuum layer. Adsorption energy calculations were performed using the CASTEP module, with a convergence criterion of 1×10 -6 eV / atom, the cutoff energy is set to 600eV, and the total energy E of the adsorption model of molybdenum calcium ore {001} surface and reagent molecules is calculated. complex , the energy E of the molybdenum calcium ore {001} surface model mineral and the energy E of each drug molecular model agent , through the adsorption energy formula: ∆E=E complex -E mineral +E agent Calculate the adsorption energy between the mineral surface and the reagent molecules.

[0051] Generally speaking, the lower the calculated adsorption energy ∆E, the better the collector's collection effect on molybdenum calcium ore. However, the selectivity of the collector also needs to be judged in combination with the adsorption intensity of the gangue minerals in the actual mine. Therefore, the collector's collection effect on gangue minerals calculated during pure mineral flotation should be re-selected.

[0052] In this embodiment, compared with collecting agents such as oxidized paraffin soap, benzohydroxamic acid, alkylhydroxamic acid, cetylpyridinium chloride, and dodecylamine, oleic acid collectors have lower binding energy on the surface of molybdenum calcium ore and higher selectivity than other agents. Therefore, after comprehensive calculation and analysis, oleic acid collectors are selected as collectors in the actual mineral oxidation flotation process.

[0053] 3) Grind the ore sample to a fineness of less than 0.150 mm, accounting for 50%, and separate it into two parts with a particle size greater than 0.150 mm and a particle size less than 0.150 mm. The two parts of ore pulp are subjected to 1.6T high-intensity magnetic separation to obtain two parts of high-intensity magnetic separation concentrate and two parts of magnetic separation tailings;

[0054] 4) Regrinding the magnetic tailings with a particle size greater than 0.150 mm to a fineness of less than 0.074 mm, accounting for 90%, and subjecting the ground products to low-potential sulfide flotation together with the magnetic tailings with a particle size less than 0.150 mm;

[0055] 5) The pulp is subjected to two roughing and two scavenging low-potential sulfide flotation. 800g / t sodium sulfide, 80g / t xanthate, and 40g / t methyl isobutyl carbinol (MIBC) are added to the roughing process. 400g / t sodium sulfide, 40g / t xanthate, and 20g / t MIBC are added to the scavenging process. Finally, the tailings are scavenged and subjected to oxide ore flotation. After the addition of sodium sulfide, the pulp Eh is -102.1mV, and then the collector (xanthate) and frother (methyl isobutyl carbinol) are added.

[0056] 6) The tailings obtained in step (5) were added with 400 g / t of a 1:1 mixed solution of water glass aluminum sulfate, 100 g / t of sodium oleate, and 40 g / t of MIBC for roughing of the oxide ore. The roughing tailings were subjected to two scavenging operations. The scavenging operations included adding 200 g / t of a 1:1 mixed solution of water glass aluminum sulfate, 50 g / t of sodium oleate, and 20 g / t of MIBC. The scavenging tailings were the final sorted tailings. The separation results are shown in Table 1.

[0057] .

[0058] Example 2

[0059] The method of Example 1 was used to separate and recover molybdenum. A scavenging step was added to the high-intensity magnetic separation tailings, followed by a magnetic concentration step on the products from the two magnetic separations. The concentrated tailings and the magnetic separation tailings were then fed together into the next separation step. Linoleic acid was used as the oxide ore collector. A molybdenum grade of 1.086% and a recovery rate of 35.44% were obtained in the magnetic iron oxides. A roughing molybdenum grade of 0.310% and a recovery rate of 24.44% were obtained through sulfide flotation. A roughing molybdenum grade of 0.292% and a recovery rate of 25.61% were obtained through oxidation flotation. The total molybdenum recovery rate for the entire separation process was 84.49%.

[0060] The magnetic field strength for the high-strength magnetic scavenging separation was 1.6 T. The oxide ore flotation reagent system was as follows: 400 g / t of a 1:1 mixture of water glass and aluminum sulfate, 100 g / t of linoleic acid, and 40 g / t of MIBC were added to the roughing process. The roughing tailings were scavenged twice, with 200 g / t of a 1:1 mixture of water glass and aluminum sulfate, 50 g / t of linoleic acid, and 20 g / t of MIBC added to the scavenging process. The separation results are shown in Table 2.

[0061] .

[0062] Example 3

[0063] The method of Example 1 was used to separate and recover molybdenum, with the addition of several concentrating and scavenging steps: an additional scavenging step was added to the tailings from the high-intensity magnetic separation, followed by a magnetic concentrating step on the products from the two magnetic separations. The concentrating tailings and the magnetic separation tailings were then fed together into the next separation process; the sulfide flotation rough concentrate was then concentrating. A molybdenum grade of 1.167% and a recovery rate of 38.28% were obtained in the magnetic iron oxides; a roughing molybdenum grade of 0.336% was obtained from the sulfide flotation, a concentrating molybdenum grade of 0.725%, and a sulfide flotation molybdenum recovery rate of 26.32%; a roughing molybdenum grade of 0.217% was obtained from the oxidation flotation, and a molybdenum recovery rate of 19.16% was obtained from the oxidation flotation; and the total molybdenum recovery rate of the separation process was 83.75%.

[0064] The magnetic field strength for the strong magnetic sweeping separation was 1.6 T. The sulfide ore concentration reagent system consisted of 1500 g / t sodium sulfide, 80 g / t xanthate, and 40 g / t methyl isobutyl carbinol (MIBC). The slurry pressure was -102.3 mV. The separation results are shown in Table 3.

[0065] .

[0066] Comparative Example 1

[0067] The method of Example 1 was used to separate and recover molybdenum, except that the flotation of the oxide ore was carried out without adding any inhibitor. The results are shown in Table 4.

[0068] .

[0069] Under these comparative conditions, the rougher molybdenum grade of the oxide ore was 0.096%, the tailings grade was 0.088%, and the molybdenum recovery rate and yield in the oxidation flotation were 31.62% and 56.86%, respectively. This result is due to the lack of inhibitors acting on the gangue minerals during the oxidation flotation process, which increases the flotation of gangue minerals and results in a lack of flotation selectivity, leading to a significant decrease in concentrate grade.

[0070] Comparative Example 2

[0071] The method of Comparative Example 1 was used to separate and recover molybdenum, except that the grinding particle size was controlled to be less than 0.044 mm, accounting for 50%, and flotation was directly performed after magnetic separation without regrinding. The results are shown in Table 5.

[0072] .

[0073] Under these comparative conditions, the molybdenum grade of the magnetic concentrate was 0.346% with a recovery of 20.58%, the molybdenum grade of the sulfide rougher was 0.223% with a recovery of 47.50%, and the molybdenum recovery in the oxidation flotation was 30.18%. This result is due to the excessively fine mineral particles during the grinding stage, which results in mudification, a reduction in magnetic recovery, and severe flotation carryover, which causes gangue minerals to float together with the target minerals, resulting in a lack of flotation selectivity and a low concentrate grade.

[0074] Comparative Example 3

[0075] The method of Example 1 was used to separate and recover molybdenum, except that during sulfide flotation, the pulp potential Eh was set to -45.6 mV. The results are shown in Table 6.

[0076] .

[0077] Under these comparative conditions, the rougher molybdenum grade of the sulfide ore was 0.182% and the recovery was 11.97%. This result is due to the high pulp potential during the sulfide ore flotation stage, which prevents the sodium sulfide from fully reacting on the mineral surface. This results in a low flotation grade and recovery rate, and the inability to completely separate the molybdenum sulfide ore.

[0078] Comparative Example 4

[0079] The method of Example 1 was used to separate and recover molybdenum, except that during the flotation of the oxide ore, the inhibitor was a 1:1 water glass and sulfuric acid mixed solution. The results are shown in Table 7.

[0080] .

[0081] Under these comparative conditions, the rougher molybdenum grade of the oxide ore was 0.122%, the tailings grade was 0.106%, and the molybdenum recovery rate and yield in the oxidation flotation were 22.57% and 41.10%. This result is due to the inhibitory effect on not only the gangue minerals but also the target oxide ore during the oxidation flotation process, resulting in reduced flotation of the target mineral, a lack of flotation selectivity, and a significant decrease in concentrate recovery and grade.

[0082] Comparative Example 5

[0083] The method of Example 1 was used to separate and recover molybdenum, except that linoleic acid was used as the collector during the flotation of the oxide ore. The results are shown in Table 8.

[0084] .

[0085] Under the conditions of this comparative example, the roughing molybdenum grade of the oxide ore was 0.191%, the tailings grade was 0.109%, the molybdenum recovery rate in the oxidation flotation was 24.72%, and the yield was 32.53%. This result is because in the oxidation flotation process, the selectivity of the collector for molybdenum calcium ore minerals is weaker than that of sodium oleate, causing more gangue minerals to float, resulting in a decrease in the concentrate recovery rate and grade compared to when oleic acid is used as a collector. The results of molecular simulation calculations show that the binding energy of linoleic acid reagent on the surface of molybdenum calcium ore is higher than that of oleic acid reagent, such as Figure 2 .

Claims

1. A method for beneficiation and enrichment of highly oxidized molybdenum ore, characterized in that: The following steps are involved: a. Classify the primary grinding pulp into two parts with a particle size greater than 0.150mm and a particle size less than 0.150mm. The two parts are respectively separated by magnetic separation to separate magnetic minerals and non-magnetic pulp. The magnetic minerals are collected as strong magnetic separation concentrate to separate the molybdenum oxide ore contained in the iron oxide; the non-magnetic minerals are discharged as tailings, so that other non-magnetic molybdenum-containing minerals are initially enriched in the non-magnetic pulp; the particle size of the primary grinding product is less than 0.150mm, accounting for 40-60%; after classification, the fine particle size is less than 0.074mm, accounting for 70-90%; b. Regrinding the non-magnetic slurry with a particle size greater than 0.150 mm, and subjecting the ground product to low-potential sulfide flotation together with the non-magnetic slurry with a particle size less than 0.150 mm; the particle size of the non-magnetic slurry regrinding product is less than 0.074 mm, accounting for 75-95%; c. Using the regrinding and fine-grained non-magnetic slurry as the feed for low-potential sulfide flotation, adding sulfiding agent, sulfide flotation collector and frother, and performing two roughing and two scavenging to obtain sulfide flotation ore and non-magnetic tailings; in the low-potential sulfide flotation slurry adjustment process, the slurry potential is controlled below -80mV after the sulfiding agent is added, and subsequent dosing flotation is carried out after reaching the value; d. Using the non-magnetic tailings pulp obtained from sulfide flotation as feed for oxidation flotation, adding regulators, inhibitors, oxidation flotation collectors and frothers, and undergoing one roughing and two scavenging processes, the oxidation flotation ore with a higher molybdenum grade and the non-magnetic tailings with a lower molybdenum grade are obtained; e. The concentrate obtained by magnetic separation in step a is combined with the middlings obtained by oxidation flotation in step d, which can be used as raw materials for preparing ammonium molybdate products by hydrometallurgy; the middlings obtained by sulfide flotation in step c are further refined to improve the grade of molybdenum sulfide ore; the non-magnetic tailings obtained by oxidation flotation in step d are discharged as the final tailings of the mineral processing process.

2. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, wherein: The sulfiding agent is one or a combination of two of sodium sulfide, sodium sulfite, and monovalent copper ions. The addition amount for roughing I is 800-1600 g / t, the addition amount for roughing II is 400-800 g / t, and the addition amount for scavenging is 0-400 g / t. The addition amount is based on the number of grams of the agent added per ton of flotation ore. The sulfide flotation collector is one or a combination of xanthate and black medicine. The addition amount for roughing I is 60-100 g / t, the addition amount for roughing II is 30-50 g / t, and the addition amount for scavenging is 30-50 g / t. The addition amount is based on the number of grams of the agent added per ton of flotation minerals. The oxidation flotation regulator is one or a combination of two agents selected from soda ash, caustic soda, and lime. The amount of the regulator to be added is based on the pH value of the slurry, and the pH value of the slurry is controlled to be 8-10. The oxidative flotation depressant is one or a combination of two agents selected from water glass, acidic water glass, and aluminum sulfate solution. The amount added for roughing is 400-1600 g / t, and the amount added for scavenging is 0-400 g / t. The addition amount is based on the number of grams of the agent added per ton of flotation minerals. The oxidative flotation collector is one or a combination of two of sodium oleate, oxidized paraffin soap, benzohydroxamic acid, and alkyl hydroxamic acid. The amount added in roughing is 80-120 g / t, and the amount added in scavenging is 40-60 g / t. The amount added is based on the number of grams of the agent added per ton of flotation minerals. The foaming agent is one or a combination of two agents selected from pine oil, No. 2 oil, mixed fatty alcohol, methyl isobutyl carbinol, and ether alcohols. The amount added in roughing is 30-50 g / t, and the amount added in scavenging is 10-30 g / t. The addition amount is based on the number of grams of the agent added per ton of flotation minerals.

3. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, wherein: The magnetic separation field strength is 0.8-1.8T, and the slurry concentration is 20-40% by mass.

4. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, wherein: In the oxidation flotation process, the flotation reagent is selected based on the results of pure gangue mineral flotation tests and molecular simulation calculations; The molecular simulation calculation is performed by modeling the main molybdenum oxide in the ore, calculating the adsorption energy of different collector molecules on the surface of the molybdenum oxide, and simulating the adsorption process of each collector on the surface of the molybdenum oxide. The calculated reagent molecules include oleic acid, sodium oleate, oxidized paraffin soap, benzohydroxamic acid, alkyl hydroxamic acid, hexadecylpyridinium chloride, and dodecylamine. The modeling process uses molecular modeling software to perform first-principles optimization on molybdenum oxide to obtain the lowest energy and most reasonable crystal structure, then performs cross-section processing to obtain the surface model of the most easily dissociated surface, sets a vacuum layer of 10 to 20 Å, and fixes the bottom 3 to 5 layers of atoms, and then performs first-principles optimization to obtain the surface model of the molybdenum oxide dissociation surface; The molybdenum oxide dissociation surface model is expanded to 1.5 to 2 times the size of the flotation collector model in the x and y directions, and then the flotation collector model is placed on the molybdenum oxide dissociation surface model at a distance of 1.5 to 3 Å to obtain a molecular adsorption model of the molybdenum oxide dissociation surface and the flotation collector; The simulation calculation is based on the first principle calculation of the adsorption model, and the adsorption energy is calculated using CASTEP or DMol3 module, where the convergence standard is 1×10 -5 ~1×10 -8 eV / atom, the cutoff energy is set to 400~1000eV.

5. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 4, wherein: The minerals used in the pure gangue mineral flotation are the gangue minerals in the actual ore, and the mineral particle size is the same as the feed particle size during the actual ore flotation. The pure mineral flotation test is a test to select the best inhibitor under the best corresponding gangue mineral collection system; The optimal corresponding gangue mineral collection system includes the optimal collector dosage, optimal slurry pH, optimal slurry temperature, optimal stirring speed, and optimal flotation time.

6. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 4, wherein: The adsorption energy is calculated by the adsorption energy formula: ∆E=E complex -E mineral +E agent Calculate the adsorption energy between the mineral surface and the reagent molecules, or determine whether there is adsorption between the mineral surface and the reagent molecules; where ∆E represents the adsorption energy between the mineral surface and the reagent molecules, and E complex Represents the total energy of the adsorption model between the mineral surface and the reagent molecules, E mineral Represents the energy of the mineral surface model, E agent Indicates the energy of the drug molecular model; ∆E, E complex 、E mineral and E agent The unit is eV; The basis for selecting the collector is to select the collector with the lowest adsorption energy between it and the mineral surface as the best flotation collector.

7. A method for beneficiation and enrichment of highly oxidized molybdenum ore according to any one of claims 4 to 6, characterized in that: The total energy of the adsorption model of the mineral surface and the agent molecule is selected according to the principle of minimum adsorption energy; the adsorption model is a model obtained by adjusting the distance and adsorption site between the agent and the mineral N times to obtain the lowest adsorption energy, where N is a positive integer greater than or equal to 1.

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