Method for mechanically activating and extracting molybdenum from refractory molybdenum ore

Abstract

The present application relates to the field of nonferrous metallurgy, and particularly relates to a method for extracting molybdenum from refractory molybdenum ore by mechanical activation. The method comprises the following steps: step S1: mechanically crushing colloidal sulfur molybdenum ore to below 2 mm; step S2: adding an activation agent and water in a predetermined ratio to the molybdenum ore particles with a particle size of 2 mm or less after crushing, and ball-milling and activating to obtain activated ore; step S3: adding a leaching solution to the activated ore according to a solid-liquid ratio, controlling the leaching temperature at 20-100 DEG C, and leaching for 1-12 hours; and step S4: after leaching, separating the solid and liquid to recover molybdenum in the leaching solution. The present application can efficiently leach molybdenum in colloidal sulfur molybdenum ore into a solution, and the process is simple, environmentally friendly, and can realize efficient utilization of refractory colloidal sulfur molybdenum ore and associated minerals.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metallurgy technology, and in particular to a method for mechanically activating and extracting molybdenum from refractory molybdenum ore. Background Technology

[0002] Molybdenum metal typically does not exist naturally in its monomeric form but is associated with other elements. Although more than 20 molybdenum-bearing minerals have been discovered, only molybdenite is of industrial value for mining. Molybdenite sulfide, a colloidal amorphous molybdenum sulfide, can be transformed into hexagonal molybdenite by heating, making it one of the most difficult molybdenum minerals to process. Although molybdenite sulfide and molybdenite have the same mineral composition, the lower formation temperature of molybdenite leads to incomplete crystallization during formation, resulting in significant differences in their mineral properties. Molybdenite sulfide is an amorphous mineral, mostly occurring as colloidal aggregates. It has a fine grain size, is difficult to liberate from individual particles, is prone to mud formation, and has poor floatability, making it difficult to effectively recover molybdenum using traditional physical beneficiation and metallurgical techniques.

[0003] Currently, there are many methods for processing this type of molybdenum ore, including oxidative roasting-acid leaching, strong magnetic separation-acid leaching, acid-stirred high-temperature curing, heap leaching, and pressure leaching, among other molybdenum recovery technologies. Conventional acid or alkaline leaching typically uses acid or alkali as the leaching agent, along with oxidants such as hydrogen peroxide and potassium permanganate, followed by heating and stirring. The leaching rate is low, generally only around 50%. To reduce leaching costs, some studies have used methods such as acid-stirred high-temperature curing and heap leaching, but the leaching rates are not ideal. While oxidative roasting can improve leaching efficiency, the low SO2 concentration produced during roasting makes it difficult to produce acid, and the volatilization of smoke and dust contributes to environmental pollution. High-temperature pressure leaching is a relatively environmentally friendly leaching technology that can significantly improve molybdenum leaching efficiency; however, the process is complex, requires sophisticated production equipment, and has high production and equipment investment costs, limiting its application.

[0004] Overall, the aforementioned methods suffer from limitations such as low molybdenum recovery rates, high production costs, and potential environmental pollution, making them difficult to promote and apply in industrial production. With societal development, human demand for molybdenum resources is increasing, and existing easily processed molybdenum resources are insufficient to meet this demand. Therefore, conducting research on refractory molybdenum ore resources and developing an economical, efficient, and environmentally friendly process for utilizing molybdenum ore resources is of great significance. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a method for mechanically activating and extracting molybdenum from refractory molybdenum ore, which can efficiently leach molybdenum from sulphur molybdenum ore into a solution. The process is simple and environmentally friendly, and realizes the efficient utilization of refractory sulphur molybdenum ore and its associated minerals.

[0006] This invention provides a method for mechanically activating and extracting molybdenum from refractory molybdenum ore, comprising the following steps:

[0007] Step S1: Mechanically crush the molybdenum ore to below 2mm;

[0008] Step S2: Add activator and water to the molybdenum ore particles with a particle size of less than 2 mm after crushing, and ball mill to activate them to obtain activated minerals;

[0009] Step S3: Add the activated minerals to the leaching solution according to the liquid-solid ratio, control the leaching temperature at 20℃~100℃, and leaching time at 1~12 hours;

[0010] Step S4: After leaching is completed, solid-liquid separation is performed to recover molybdenum from the leachate.

[0011] Preferably, in step S2, the activator is one or more of sodium hypochlorite, calcium hypochlorite, sodium chlorate, hydrogen peroxide, manganese dioxide, potassium permanganate, sodium carbonate, sodium bicarbonate, sodium oxide, calcium oxide, calcium hydroxide, and potassium hydroxide.

[0012] Preferably, in step S2, the amount of activator added is no more than 10% of the mass of molybdenum ore.

[0013] Preferably, in step S2, the amount of water added is no more than 10% of the mass of molybdenum ore.

[0014] Preferably, in step S3, the liquid-to-solid ratio is 0.1 to 5.

[0015] Preferably, in step S3, the mass concentration of the leachate does not exceed 20%.

[0016] Preferably, in step S3, the leachate is a sulfuric acid solution, hydrochloric acid solution, nitric acid solution, acetic acid solution, sodium hydroxide solution, ammonia water, or potassium hydroxide solution.

[0017] Preferably, step S1 specifically comprises:

[0018] The molten molybdenum ore is mechanically crushed and then classified by particle size. Particles larger than 2 mm are reused for mechanical crushing.

[0019] Particles smaller than 2 mm are used in the subsequent step S2.

[0020] Preferably, the leaching temperature is 25°C to 80°C.

[0021] Preferably, the leaching time is 3 to 8 hours.

[0022] Compared with existing technologies, the present invention provides a method for mechanically activating and extracting molybdenum from refractory molybdenum ores. This method combines mechanical activation with wet leaching. By applying mechanical force to the mineral surface, it exposes the encapsulated fine molybdenum ore particles and alters the activation energy of the mineral surface, increasing the surface temperature and promoting the oxidation of molybdenum sulfide ore to generate readily soluble substances. This allows for the efficient leaching of molybdenum from the molybdenum sulfide ore into the solution. This invention is applicable not only to single molybdenum ores but also to associated molybdenum ores, such as nickel-molybdenum ores and uranium-molybdenum ores.

[0023] This invention requires no special equipment and can be carried out entirely under normal pressure. The process is simple to operate and environmentally friendly, enabling the efficient utilization of refractory molybdenum ore and its associated minerals. (See attached figures.)

[0024] Figure 1 The flowchart illustrates the method for mechanically activating and extracting molybdenum from difficult-to-process molybdenum ore according to the present invention. Detailed Implementation

[0025] To further understand the present invention, embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the present invention.

[0026] Embodiments of the present invention disclose a method for mechanically activating and extracting molybdenum from refractory molybdenum ore, such as... Figure 1 As shown, it includes the following steps:

[0027] Step S1: Mechanically crush the molybdenum ore to below 2mm;

[0028] Step S2: Add activator and water to the molybdenum ore particles with a particle size of less than 2 mm after crushing, and ball mill to activate them to obtain activated minerals;

[0029] Step S3: Add the activated minerals to the leaching solution according to the liquid-solid ratio, control the leaching temperature at 20℃~100℃, and leaching time at 1~12 hours;

[0030] Step S4: After leaching is completed, solid-liquid separation is performed to recover molybdenum from the leachate.

[0031] This invention utilizes a combination of mechanical crushing and wet leaching to leach molybdenum from calcareous molybdenum ore.

[0032] The following steps describe the method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to the present invention.

[0033] Step S1: Mechanically crush the molybdenum ore to below 2mm;

[0034] Specifically:

[0035] The molten molybdenum ore is mechanically crushed and then classified by particle size. Particles larger than 2 mm are reused for mechanical crushing.

[0036] Particles smaller than 2 mm are used in the subsequent step S2.

[0037] Step S2: Add activator and water to the molybdenum ore particles with a particle size of less than 2 mm after crushing, and ball mill to activate them to obtain activated minerals;

[0038] The activator is one or more of the following: sodium hypochlorite, calcium hypochlorite, sodium chlorate, hydrogen peroxide, manganese dioxide, potassium permanganate, sodium carbonate, sodium bicarbonate, sodium oxide, calcium oxide, calcium hydroxide, and potassium hydroxide.

[0039] The amount of activator added is no more than 10% of the mass of molybdenum ore.

[0040] The amount of water added shall not exceed 10% of the mass of the molybdenum ore.

[0041] Step S3: Add the activated minerals to the leaching solution according to the liquid-solid ratio, control the leaching temperature at 20-100℃, and leaching time at 1-12 hours;

[0042] The liquid-to-solid ratio is preferably 0.1 to 5, more preferably 1 to 3. The liquid-to-solid ratio is the ratio of the volume of the leachate to the amount of minerals, and the unit is mL / g.

[0043] The leachate is preferably a sulfuric acid solution, hydrochloric acid solution, nitric acid solution, acetic acid solution, sodium hydroxide solution, ammonia water, or potassium hydroxide solution.

[0044] The mass concentration of the leachate does not exceed 20%.

[0045] The leaching temperature is 20℃~100℃, preferably 20℃~80℃.

[0046] The leaching time is 1 to 12 hours, preferably 3 to 8 hours.

[0047] Step S4: After leaching is completed, solid-liquid separation is performed to recover molybdenum from the leachate.

[0048] Molybdenum can be extracted from the leachate by means of extraction or ion exchange.

[0049] This invention targets the difficult-to-flot-enrich molybdenum ore, employing a mechanical activation method. This method not only exposes the encapsulated molybdenum ore but also utilizes mechanical friction and impact forces to increase the activation energy of the mineral surface, efficiently activating the molybdenum ore. Subsequently, a wet leaching method is used to extract the molybdenum from the mineral into the leaching solution. This method can significantly improve the molybdenum leaching rate from molybdenum ore, thereby increasing the efficiency of molybdenum resource utilization. Furthermore, the method is simple, adaptable, environmentally friendly, and effective.

[0050] To further understand the present invention, the method for mechanically activating and extracting molybdenum from refractory molybdenum ore provided by the present invention will be described in detail below with reference to embodiments. The scope of protection of the present invention is not limited by the following embodiments.

[0051] Example 1

[0052] The raw material used was monomolybdenum ore, in which molybdenum mainly exists in the form of sulphurite. The mineral was partially oxidized, and after drying, the molybdenum content in the mineral was measured to be 0.15%.

[0053] After crushing, the molybdenum ore is screened. Particles larger than 2mm are returned to the crushing system, while those smaller than 2mm are used for mechanical activation.

[0054] Take 200g of minerals with a particle size of less than 2mm, 1g of MnO2 and 5mL of water and add them to a ball mill. Start the ball mill and activate it for 2 hours. After separating the minerals from the grinding balls, leach them out.

[0055] 100g of activated minerals were placed in a leaching tank, and 100mL of a 5% sodium hydroxide solution was added. The mixture was heated to 60℃ and stirred for 4 hours before solid-liquid separation. Multiple experiments showed that after leaching, the molybdenum content in the slag decreased to below 0.04%, and the molybdenum leaching rate was above 70%.

[0056] The leachate can be extracted using methods such as extraction or ion exchange.

[0057] Example 2

[0058] The raw material used in this embodiment is uranium-molybdenum ore. The molybdenum in the mineral mainly exists in the form of uranium-molybdenite, which has a fine particle size and is difficult to utilize. Testing revealed that the mineral contains 0.53% molybdenum and 0.032% uranium.

[0059] After crushing, the uranium-molybdenum ore is screened. Particles larger than 2mm are returned to the crushing system, while those smaller than 2mm are used for mechanical activation.

[0060] Take 200g of minerals with a particle size of less than 2mm, add 5g of NaClO solution to the ball mill, start the ball mill to activate for 1 hour, and then leach the minerals after separating them from the grinding balls.

[0061] 100g of activated minerals were placed in a leaching tank, and 100mL of a 5% sulfuric acid solution was added. After stirring at room temperature for 6 hours, solid-liquid separation was performed. Multiple experiments showed that after leaching, the molybdenum content in the slag decreased to below 0.06%, and the uranium content decreased to 0.005%. The molybdenum leaching rate was over 80%, and the uranium leaching rate was approximately 70%.

[0062] The leachate can be extracted using methods such as extraction or ion exchange.

[0063] Example 3

[0064] The raw material used in this embodiment is nickel-molybdenum ore, which was tested and found to contain 3.2% molybdenum and 5.8% nickel.

[0065] After crushing, the nickel-molybdenum ore is screened. Particles larger than 2mm are returned to the crushing system, while those smaller than 2mm are used for mechanical activation.

[0066] Take 200g of minerals with a particle size of less than 2mm, add 10g of hydrogen peroxide to the ball mill, start the ball mill to activate for 3 hours, and then leach the minerals after separating them from the grinding balls.

[0067] 100g of activated minerals were placed in a leaching tank, and 100mL of a 10% hydrochloric acid solution was added. The mixture was heated to 80℃ and stirred for 3 hours, followed by solid-liquid separation. After leaching, the molybdenum content in the slag decreased to below 0.2%, and the nickel content decreased to 0.3%. The molybdenum leaching rate reached 95%, and the nickel leaching rate reached over 90%.

[0068] The leachate can be extracted using methods such as extraction or ion exchange.

[0069] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

[0070] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for mechanically activating and extracting molybdenum from refractory molybdenum ore, characterized in that, Includes the following steps: Step S1: Mechanically crush the molybdenum ore to below 2mm; Step S2: Add an activator and water to the crushed molybdenum ore particles with a particle size of less than 2 mm according to the specified ratio, and ball mill to activate the mineral, thereby obtaining the activated mineral; the activator is one or more of sodium hypochlorite, calcium hypochlorite, sodium chlorate, hydrogen peroxide, sodium carbonate, sodium bicarbonate, sodium oxide, calcium oxide, calcium hydroxide, and potassium hydroxide; the amount of activator added is no more than 10% of the mass of the molybdenum ore; Step S3: Add the activated minerals to the leaching solution according to the liquid-solid ratio, control the leaching temperature at 20℃~100℃, and leaching time at 1~12 hours; Step S4: After leaching is completed, solid-liquid separation is performed to recover molybdenum from the leachate.

2. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, In step S2, the amount of water added is no more than 10% of the mass of molybdenum ore.

3. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, In step S3, the liquid-to-solid ratio is 0.1 to 5.

4. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, In step S3, the mass concentration of the leachate does not exceed 20%.

5. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, In step S3, the leachate is a sulfuric acid solution, hydrochloric acid solution, nitric acid solution, acetic acid solution, sodium hydroxide solution, ammonia water, or potassium hydroxide solution.

6. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, Step S1 specifically involves: The molten molybdenum ore is mechanically crushed and then classified by particle size. Particles larger than 2 mm are reused for mechanical crushing. Particles smaller than 2 mm are used in the subsequent step S2.

7. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, The leaching temperature is 25℃~80℃.

8. The method for mechanically activating and extracting molybdenum from refractory molybdenum ore according to claim 1, characterized in that, The leaching time is 3 to 8 hours.

Images