Beneficiation and enrichment method for high-oxidation molybdenum ore

Abstract

The invention provides a beneficiation and enrichment method for high-molybdenum oxide ore, which comprises the following steps of: performing fraction magnetic separation on a product after ore grinding, regrinding magnetic separation coarse particle tailings, mixing the reground product with magnetic separation fine fraction tailings to perform low-potential sulphide ore flotation, performing oxidized ore flotation on sulphide ore flotation tailings, and the like. And finally, the molybdenum concentrate with the high recovery rate and grade is obtained, the molybdenum ore separation and enrichment effect is achieved, and the fine disseminated-particle-size refractory molybdenum oxide ore resources in the high-oxidation-type molybdenum ore are effectively and comprehensively recycled. In order to quickly optimize and obtain the optimal condition of oxidized ore flotation, the flotation inhibitor with the good inhibition effect is determined through the pure ore flotation test, the flotation collecting agent with the high selectivity is selected through the molecular simulation calculation method, and the flotation efficiency and selectivity are improved. The method provided by the invention can be widely applied to the fields of development of high-oxidation molybdenum ore mines and recycling of fine-fraction refractory molybdenum oxide ore resources in tailings after sulfuration flotation.

Description

Technical Field

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

[0002] my country's total molybdenum resources are very rich, and in 2022, China's molybdenum reserves ranked first in the world. However, my country's molybdenum resource mining has accounted for more than 40% of the global total mining for many years, and my country's molybdenum resource reserve advantage is gradually weakening. 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] In nature, there are about 30 kinds of molybdenum-containing minerals, among which molybdenite, molybdenite and other sulfide molybdenum ores are easy to separate and recover by flotation because of their good natural floatability and large mineralization particle size. In addition, molybdenum oxide is a difficult-to-select molybdenum mineral. Because they are naturally hydrophobic minerals, they have good dispersion and stability in the slurry. They are also not easy to combine with collectors during flotation, thus affecting the flotation products; and there are many types of molybdenum oxide, and the physical and chemical properties of the surfaces of various molybdenum oxide minerals are quite different; the density of molybdenum oxide ore is generally around 4.6g / cm³, the hardness is low, and it is easy to break. These physical properties make molybdenum oxide ore prone to over-grinding and muddling during the grinding process, increasing the difficulty of flotation. In addition, the embedded particle size of molybdenum oxide ore is generally fine, and fine-grained ore is more likely to be mixed with other minerals, reducing flotation selectivity.

[0004] Minerals such as molybdenum ore (MoO3), calcium molybdenum ore (CaMoO4), iron molybdenum ore [Fe2(MoO4)3], wulfenite 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, natural hydrophilicity, and are extremely difficult to recover by flotation.

[0006] At present, the treatment schemes for molybdenum ores with high oxidation rates in mining enterprises can be roughly divided into two categories: one is to obtain low-grade molybdenum concentrate by mixed flotation of molybdenum sulfide and molybdenum oxide, and then use hydrometallurgical process to produce ammonium molybdate products; the other is to obtain molybdenite concentrate products by wet leaching of molybdenum oxide minerals, and then flotation of the leached residue. When using flotation process to treat molybdenum oxide ore with high oxidation rate, the concentrate grade and recovery rate are often not achieved at the same time. This is because the flotation collector has poor selectivity for molybdenum oxide ore and the inhibitor's inhibitory ability is difficult to stabilize. This results in either no separation effect of flotation or more molybdenum ore is lost in the tailings. Therefore, further efficient recovery process solutions need to be developed. 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: a. Classify 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 the pulp are respectively separated into magnetic minerals and pulp by a wet high-intensity magnetic separator. The magnetic minerals are collected as high-intensity magnetic concentrates to separate the oxidized molybdenum ore contained in the iron oxides; the non-magnetic minerals are discharged as tailings, so that other non-magnetic molybdenum-containing minerals are initially enriched in the non-magnetic pulp; b. re-grinding the non-magnetic ore pulp with a particle size greater than 0.150 mm, and the ground product and the non-magnetic ore pulp with a particle size less than 0.150 mm are subjected to low-potential sulfidation flotation operation; c. The above regrinding and fine-grained non-magnetic slurry are used as feed for low-potential sulfide flotation, and 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; 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, oxidation flotation ore with higher molybdenum grade and non-magnetic tailings with lower molybdenum grade are obtained; e. The strong magnetic concentrate and the oxidative flotation concentrate are combined to serve as raw materials for the preparation of ammonium molybdate products by hydrometallurgy; the sulfide flotation concentrate is further refined to improve the grade of the sulfide molybdenum ore; the oxidative flotation non-magnetic tailings are discharged as the final tailings of the beneficiation process.

[0009] 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%; after classification, the particle size of the fine-grained ore is less than 0.074 mm, accounting for 70-90%.

[0010] 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 percentage.

[0011] Furthermore, in the above-mentioned method for beneficiation and enrichment 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%.

[0012] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, during the low-potential sulfidation flotation slurry adjustment process, the slurry potential is controlled below -80mV after the sulfiding agent is added, and subsequent flotation with additional chemicals is performed after reaching the potential.

[0013] Furthermore, in the above-mentioned method for beneficiation and enrichment 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, which is based on the grams of reagent added per ton of flotation mineral.

[0014] Furthermore, in the above-mentioned beneficiation and enrichment method of highly oxidized molybdenum ore, the sulfide flotation collector is one of yellow medicine and black medicine or a combination of two agents, the addition amount of roughing I is 60~100g / t, the addition amount of roughing II is 30~50g / t, and the addition amount of scavenging is 30~50g / t, and the addition amount is based on the grams of agent added per ton of flotation mineral.

[0015] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the oxidizing flotation adjusting agent 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 slurry, and the pH value of the slurry is controlled to be 8-10.

[0016] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the frother is one or a combination of two of pine oil, 2# oil, mixed fatty alcohol, methyl isobutyl carbinol, and ether alcohols, the roughing addition amount is 30~50g / t, and the scavenging addition amount is 10~30g / t, and the addition amount is based on the grams of the agent added per ton of flotation mineral.

[0017] Furthermore, in the above-mentioned method for beneficiation and enrichment 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.

[0018] 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, the mineral particle size is the same as the feed particle size of the actual ore flotation, and the pure mineral flotation test is a test for selecting 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.

[0019] The basis for selecting the inhibitor is to select the inhibitor with the highest comprehensive inhibition degree for each gangue mineral, the most stable inhibition effect at each slurry pH, and the least inhibitory effect on molybdenum calcium ore as the best flotation inhibitor.

[0020] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the optimal collection system comprises an optimal collector dosage, an optimal slurry pH, an optimal slurry temperature, an optimal stirring speed, and an optimal flotation time.

[0021] Furthermore, in the above-mentioned method for beneficiation and enrichment 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; wherein the calculated reagent molecules include oleic acid, sodium oleate, oxidized paraffin soap, benzohydroxamic acid, alkylhydroxamic acid, hexadecylpyridinium chloride, and dodecylamine.

[0022] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the modeling process utilizes molecular modeling software to perform first-principles optimization on the molybdenum oxide ore to obtain the most reasonable crystal structure with the lowest energy, and then performs sectioning 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.

[0023] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the molybdenum oxide surface model is expanded to 1.5 to 2 times 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 the molybdenum oxide dissociation surface and the flotation collector molecule adsorption model.

[0024] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the simulation calculation adopts the first principle calculation of the adsorption model, and uses CASTEP or DMol3 module to calculate the adsorption energy, wherein the convergence standard (SCFtolerance) is 1×10 -5 ~1×10 -8 eV / atom, the cutoff energy (Energy cutoff) is set to 400~1000eV.

[0025] Furthermore, in the above-mentioned method for beneficiation and enrichment 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 drug molecules, or determine whether there is adsorption between the mineral surface and the drug molecules; where ∆E represents the adsorption energy between the mineral surface and the drug molecules, and E complex It represents the total energy of the adsorption model between the mineral surface and the drug molecule, 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.

[0026] Furthermore, in the above-mentioned method for beneficiation and enrichment of highly oxidized molybdenum ore, the adsorption model is a model in which the minimum adsorption energy is obtained by adjusting the distance and adsorption sites between the reagent and the mineral for multiple times. The adsorbent in the model is used as the best collector for actual mineral separation. In the present invention, the total energy of the adsorption model of the mineral surface and the reagent molecule is selected according to the principle of minimum adsorption energy; the adsorption model is a model in which the minimum adsorption energy is obtained by adjusting the distance and adsorption sites between the reagent and the mineral for N times, and N is a positive integer greater than or equal to 1.

[0027] The advantages of the present invention are: 1. Since the present invention adopts a strong magnetic separation process to select the magnetic minerals in the raw ore, the molybdenum oxide ore contained in the iron oxide is initially enriched. The embedded particle size of this type of molybdenum oxide ore is extremely fine and difficult to be separated by subsequent processes. Compared with the conventional process of mixed flotation of sulfide ore and oxide ore, this type of extremely fine-grained molybdenum oxide ore is enriched, a large amount of magnetic iron oxide is discarded in advance, the influence of iron oxide on the subsequent flotation process is reduced, the material processing volume of subsequent operations is reduced, the grade and recovery rate of molybdenum in the overall concentrate are improved, and the sorting efficiency of subsequent mineral processing operations is significantly improved; 2. Most of the molybdenum-containing minerals in highly oxidized molybdenum ores are embedded in very fine particles. It is difficult to separate the coarse particles, and the over-fine particles are easy to be muddy 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, and the coarse non-magnetic minerals are re-grinded. The re-grinded products are mixed with the fine non-magnetic minerals to enter the flotation operation, thereby reducing the processing volume during re-grinding, reducing the phenomenon of over-grinding and muddling of minerals, and improving the effect of subsequent flotation operations; 3. Sulfide molybdenum ore is generally colloidal sulfide molybdenum ore, which has no fixed crystal structure and a wide range of particle sizes. 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 sulfide mineral surface on the reagent, so that the molybdenum sulfide minerals in the original ore can be basically completely separated, and the sulfide flotation tailings basically do not contain molybdenum sulfide minerals, thereby reducing the interference of sulfide ore on subsequent oxidation flotation and improving the recovery rate of molybdenum ore in the whole process; 4. For molybdenum oxide ore, since molybdenum oxide ore generally has the characteristics of incomplete crystallization, small crystals, low hardness, easy over-grinding, and natural hydrophilicity, it is extremely difficult to flotation and recover molybdenum oxide ore, especially the selection of flotation reagents is very difficult. Collectors generally have poor selectivity and cannot obtain high-grade molybdenum oxide ore. Inhibitors generally have an inhibitory effect on 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 oxidized flotation concentrate products. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention is a flow chart of the beneficiation and enrichment method of highly oxidized molybdenum ore.

[0029] Figure 2 The 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 is used to model. DETAILED DESCRIPTION

[0030] 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 implementation examples, but the present invention is not limited thereto.

[0031] The oxidation rate of molybdenum in a difficult-to-select uranium-molybdenum ore in Hebei Province reaches 71.4%. Through process mineralogy research, it is found that the original ore contains 0.28% molybdenum, and the molybdenum minerals in the ore are mainly oxidized molybdenum ore, followed by sulfide molybdenum ore. Nearly 50% of the molybdenum ore is extremely fine-grained oxidized molybdenum ore embedded in iron oxides, and about 20% of the molybdenum ore is oxidized molybdenum ore embedded in gangue minerals or independently mineralized, mainly molybdenum calcium ore, some molybdenum fluoride and trace blue molybdenite, about 30% of the molybdenum ore is sulfide molybdenum ore, mainly colloidal sulfide molybdenite, and some molybdenite; pyrite, hematite and limonite are other major metal minerals in the ore, and there are also small amounts of sphalerite, galena, zircon, magnetite, ilmenite, monazite, and 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 of low 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 oxide molybdenum minerals are closely embedded in the gangue minerals and are hydrophilic, making flotation recovery extremely difficult.

[0032] In order to more efficiently and comprehensively recycle the molybdenum resources in the ore, a large number of experimental studies on various mineral processing and enrichment process schemes such as flotation, magnetic separation, gravity separation, color separation, magnetic separation-flotation, etc. have been carried out for the difficult-to-select molybdenum minerals in the highly oxidized molybdenum ore. In addition, a large number of theoretical studies 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 cannot achieve the purpose of effectively separating and enriching the molybdenum resources in the original ore.

[0033] Example 1 In order to solve the above technical problems, on the basis of 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, and obtains a molybdenum grade of 0.830% and a recovery rate of 29.23% in the magnetic iron oxide; a rough molybdenum grade of 0.342% by sulfide flotation, and a molybdenum recovery rate of 28.56% by sulfide flotation; a rough molybdenum grade of 0.245% by oxidation flotation, and a molybdenum recovery rate of 29.53% by oxidation flotation; and a molybdenum recovery rate of 87.31% in the total separation process.

[0034] Figure 1 The flow chart of the ore dressing 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: The conclusion drawn from the flotation test of pure gangue minerals is: 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 for selecting the best inhibitor under the best corresponding gangue mineral collection system; the tested reagents include water glass, acidic water glass, a mixed reagent of water glass and metal ions, sodium alginate, CMC, sodium humate, and sodium pyrophosphate.

[0035] The selection basis of the inhibitor is to select the inhibitor with the greatest comprehensive inhibition degree for each gangue mineral, the most stable inhibition effect under each pulp pH, and the least inhibition effect on molybdenum calcium ore as the best flotation inhibitor; In this embodiment, compared with sodium alginate, CMC, sodium humate, sodium pyrophosphate and other inhibitors, water glass inhibitors have good inhibitory effects on various gangue minerals in actual mines, among which the 1:1 mixed solution of water glass aluminum sulfate has the best inhibitory effect. Therefore, the 1:1 mixed solution of water glass aluminum sulfate is selected as the inhibitor in the actual mineral oxidation flotation process; Molecular simulation calculations led to the following conclusions: The mineral surface model used in the molecular simulation calculation is molybdenite in the actual ore, and the reagent models include oleic acid, sodium oleate, oxidized paraffin soap, benzohydroxamic acid, alkyl hydroxamic acid, chlorohexadecylpyridinium, and dodecylamine. Before the surface energy calculation, the geometric optimization of the molybdenite unit cell was first performed, and the molybdenite {001} crystal plane model was used to calculate the binding energy between the molybdenum and the reagent. The vacuum layer of the crystal plane model was 15 Å. The adsorption energy calculation was performed using the CASTEP module, and the convergence standard was 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.

[0036] Generally speaking, the lower the calculated adsorption energy ∆E is, the better the collector's collection effect on molybdenum calcium ore is. However, the selectivity of the collector also needs to be judged in combination with the adsorption strength of the gangue minerals in the actual mine. Therefore, the collector's collection effect on gangue minerals calculated during the flotation of pure minerals is re-selected.

[0037] In this embodiment, compared with oxidized paraffin soap, benzohydroxamic acid, alkylhydroxamic acid, hexadecylpyridinium chloride, dodecylamine and other collecting agents, the oleic acid collector has a lower binding energy on the surface of molybdenum calcium ore and has a higher selectivity than other agents. Therefore, after comprehensive calculation and analysis, oleic acid agents are selected as collectors in the actual mineral oxidation flotation process.

[0038] 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. Perform 1.6T high-intensity magnetic separation on the two parts of slurry to obtain two parts of high-intensity magnetic separation concentrate and two parts of magnetic separation tailings; 4) Grind 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 perform low-potential sulfide flotation operation together with the magnetic tailings with a particle size less than 0.150 mm; 5) The pulp is subjected to two roughing and two scavenging low-potential sulfide flotation. In the roughing, 800g / t sodium sulfide, 80g / t xanthate and 40g / t methyl isobutyl carbinol (MIBC) are added. In the scavenging, 400g / t sodium sulfide, 40g / t xanthate and 20g / t MIBC are added. Finally, the tailings are scavenged for 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. 6) The tailings obtained in step (5) were added with 400 g / t 1:1 mixed solution of water glass aluminum sulfate, 100 g / t sodium oleate and 40 g / t MIBC for roughing of oxide ore, and the roughing tailings were subjected to two scavengings, and the scavengings were added with 200 g / t 1:1 mixed solution of water glass aluminum sulfate, 50 g / t sodium oleate and 20 g / t MIBC; the scavenging tailings were the final selected tailings. The separation results are shown in Table 1.

[0039] .

[0040] Example 2 The method of Example 1 is used to separate and recover molybdenum, and a scavenging is added to the tailings of the strong magnetic separation, and then the products of the two magnetic separations are subjected to a magnetic concentration, and the selected tailings and the magnetic separation tailings enter the next separation process together; the oxide ore collector is changed to linoleic acid. The molybdenum grade in the magnetic iron oxide is 1.086%, and the recovery rate is 35.44%; the sulfide flotation roughing molybdenum grade is 0.310%, and the sulfide flotation molybdenum recovery rate is 24.44%; the oxidation flotation roughing molybdenum grade is 0.292%, and the oxidation flotation molybdenum recovery rate is 25.61%; the total selection process molybdenum recovery rate is 84.49%.

[0041] The magnetic field intensity of the strong magnetic scavenging is 1.6T. The flotation reagent system of the oxide ore is as follows: 400g / t 1:1 mixed solution of water glass aluminum sulfate, 100g / t linoleic acid and 40g / t MIBC are added to the roughing for the oxide ore roughing, and the roughing tailings are scavenged twice, and 200g / t 1:1 mixed solution of water glass aluminum sulfate, 50g / t linoleic acid and 20g / t MIBC are added to the scavenging. The separation results are shown in Table 2.

[0042] .

[0043] Example 3 The method of Example 1 was used to separate and recover molybdenum, and some concentrating and scavenging steps were added: an additional scavenging step was added to the tailings of the strong magnetic separation, and then the products of the two magnetic separations were subjected to a magnetic concentration, and the concentrating tailings and the magnetic separation tailings were entered into the next separation process together; the sulfide flotation rough concentrate was concentrated. The molybdenum grade in the magnetic iron oxide was 1.167%, and the recovery rate was 38.28%; the sulfide flotation roughing molybdenum grade was 0.336%, the concentrating molybdenum grade was 0.725%, and the sulfide flotation molybdenum recovery rate was 26.32%; the oxidation flotation roughing molybdenum grade was 0.217%, and the oxidation flotation molybdenum recovery rate was 19.16%; the total selection process molybdenum recovery rate was 83.75%.

[0044] The magnetic field strength of the strong magnetic sweeping separation is 1.6T, the reagent system for sulfide ore selection is 1500g / t sodium sulfide, 80g / t xanthate and 40g / t methyl isobutyl carbinol (MIBC), and the slurry point is -102.3mV. The separation results are shown in Table 3.

[0045] .

[0046] Comparative Example 1 The method of Example 1 was used to separate and recover molybdenum, except that during the flotation of the oxide ore, the flotation was carried out without adding any inhibitor. The results are shown in Table 4.

[0047] .

[0048] Under the comparative conditions, the roughing molybdenum grade of the oxide ore was 0.096%, the tailings grade was 0.088%, the molybdenum recovery rate in the oxidation flotation was 31.62%, and the yield was 56.86%. This result is due to the fact that in the oxidation flotation process, there is no inhibitor to act on the gangue minerals, which causes the gangue minerals to float more, and the flotation is not selective, resulting in a significant decrease in the concentrate grade.

[0049] Comparative Example 2 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 process was directly performed without regrinding after magnetic separation. The results are shown in Table 5.

[0050] .

[0051] Under the comparative conditions, the molybdenum grade of magnetic concentrate was 0.346% and the recovery rate was 20.58%, the molybdenum grade of sulfide ore rougher was 0.223% and the recovery rate was 47.50%, and the molybdenum recovery rate in oxidation flotation was 30.18%. This result is because the mineral particles are too fine in the grinding stage, resulting in mudification, which leads to a decrease in magnetic recovery rate and serious flotation entrainment, which causes the gangue minerals to float together with the target minerals, resulting in no selectivity in flotation, resulting in a low concentrate grade.

[0052] Comparative Example 3 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.

[0053] .

[0054] Under the comparative conditions, the roughing molybdenum grade of sulfide ore is 0.182% and the recovery rate is 11.97%. This result is because the pulp potential is high during the flotation stage of sulfide ore, and sodium sulfide is not fully reacted on the surface of the mineral, resulting in low flotation grade and recovery rate of sulfide ore, and the sulfide molybdenum ore cannot be completely separated.

[0055] Comparative Example 4 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.

[0056] .

[0057] Under the comparative conditions, the roughing molybdenum grade of the oxide ore was 0.122%, the tailings grade was 0.106%, the molybdenum recovery rate in the oxidation flotation was 22.57%, and the yield was 41.10%. This result is due to the fact that in the oxidation flotation process, the inhibitor not only acts on the gangue minerals, but also on the target oxide ore, causing the target mineral to float less, the flotation is not selective, and the concentrate recovery rate and grade are significantly reduced.

[0058] Comparative Example 5 The method of Example 1 was used to separate and recover molybdenum, except that during the flotation of the oxide ore, the collector was linoleic acid. The results are shown in Table 8.

[0059] .

[0060] Under the comparative conditions, the rough 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 due to the fact that in the oxidation flotation process, the selectivity of the collector on the molybdenum calcium ore is weaker than that of sodium oleate, which causes more floating of gangue minerals, resulting in a decrease in the concentrate recovery rate and grade compared with when oleic acid is used as a collector. The molecular simulation calculation results 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 the 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 0.150 mm and a particle size less than 0.150 mm. The two parts of the pulp are respectively separated by magnetic separation to separate the magnetic minerals and the pulp. The magnetic minerals are collected as strong magnetic separation concentrates to separate the oxidized molybdenum 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; b. re-grinding the non-magnetic ore pulp with a particle size greater than 0.150 mm, and the ground product and the non-magnetic ore pulp with a particle size less than 0.150 mm are subjected to low-potential sulfidation flotation operation; c. Use the regrinding and fine-grained non-magnetic slurry as the feed for low-potential sulfide flotation, add sulfiding agent, sulfide flotation collector and frother, and obtain sulfide flotation ore and non-magnetic tailings after two roughing and two scavenging. 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 after one roughing and two scavenging, obtaining oxidation flotation ore with higher molybdenum grade and non-magnetic tailings with lower molybdenum grade; e. The concentrate obtained by magnetic separation in step a and the middlings obtained by oxidation flotation in step d are combined to serve 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 sulfide molybdenum 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 amount of roughing I is 800-1600 g / t, the amount of roughing II is 400-800 g / t, and the amount of scavenging is 0-400 g / t. The amount is based on the grams of the agent added per ton of flotation minerals. The sulfide flotation collector is one of yellow medicine and black medicine or a combination of two medicines, the addition amount of roughing I is 60-100g / t, the addition amount of roughing II is 30-50g / t, and the addition amount of scavenging is 30-50g / t, and the addition amount is based on the grams of the added agent per ton of flotation mineral; The oxidation flotation regulator is one or a combination of 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 oxidation 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 amount added 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 alkylhydroxamic acid, with a roughing addition amount of 80-120 g / t and a scavenging addition amount of 40-60 g / t, which is based on the grams of the agent added per ton of flotation mineral; The foaming agent is one or a combination of two of pine oil, 2# oil, mixed fatty alcohol, methyl isobutyl carbinol, ether alcohols, the roughing addition amount is 30-50g / t, and the scavenging addition amount is 10-30g / t, and the addition amount is based on the grams of the agent added per ton of flotation mineral.

3. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, characterized in that: The particle size of the primary grinding product is less than 0.150 mm, accounting for 40-60%; the particle size of the fine-grained ore after classification is less than 0.074 mm, accounting for 70-90%.

4. 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.

5. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, characterized in that: The particle size of the non-magnetic slurry regrinding product is less than 0.074 mm, accounting for 75-95%.

6. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, characterized in that: During the low-potential sulfidation flotation slurry adjustment process, the pulp potential is controlled below -80mV after the sulfiding agent is added, and subsequent flotation with additional agents is performed after reaching the value.

7. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 1, characterized in that: 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 carried out 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; wherein 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-principle optimization on molybdenum oxide ore to obtain the most reasonable crystal structure with the lowest energy, and then perform section processing to obtain the surface model of the most easily dissociated surface, set the vacuum layer to 10-20Å, fix the bottom 3-5 layers of atoms, and then perform first-principle optimization to obtain the surface model of the molybdenum oxide dissociation surface; The molybdenum oxide surface model is enlarged to 1.5 to 2 times 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; The simulation calculation adopts the first principle calculation of the adsorption model and uses CASTEP or DMol3 module to calculate the adsorption energy, where the convergence standard is 1×10 -5 ~1×10 -8 eV / atom, the cutoff energy is set to 400~1000eV.

8. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 7, characterized in that: The mineral used in the pure gangue mineral flotation is the gangue mineral in the actual ore, and the mineral particle size is the same as the feed particle size of 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, the optimal slurry pH, the optimal slurry temperature, the optimal stirring speed, and the optimal flotation time.

9. The method for beneficiation and enrichment of a highly oxidized molybdenum ore according to claim 7, characterized in that: 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 drug molecules, or determine whether there is adsorption between the mineral surface and the drug molecules; where ∆E represents the adsorption energy between the mineral surface and the drug molecules, and E complex It represents the total energy of the adsorption model between the mineral surface and the drug molecule, 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 of 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.

10. A method for beneficiation and enrichment of highly oxidized molybdenum ore according to any one of claims 7 to 9, 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 with the lowest adsorption energy obtained by adjusting the distance and adsorption site between the agent and the mineral N times, and N is a positive integer greater than or equal to 1.

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