A method for separating nickel-molybdenum uranium ore

Abstract

This invention provides a method for separating nickel-molybdenum-uranium ore through beneficiation and metallurgy, belonging to the field of beneficiation and metallurgical technology. The separation method provided by this invention includes the following steps: mixing nickel-molybdenum-uranium ore, a dispersant, an activator, an inhibitor, a collector, and a frother, followed by sequential frothing and flotation to obtain nickel-molybdenum concentrate and uranium-bearing tailings; subjecting the uranium-bearing tailings to acid leaching to obtain a leachate and tailings; adsorbing the leachate with a strongly basic anion exchange resin, followed by sequential solid-liquid separation, rinsing, and pH adjustment to obtain a uranium concentrate. Example results show that the recovery rates of nickel and molybdenum obtained by this invention are greater than 80%, the uranium leaching rate is greater than 96%, and the uranium recovery rate is greater than 91%.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology, and particularly relates to a method for the separation of nickel-molybdenum-uranium ore. Background Technology

[0002] Uranium is a naturally occurring radioactive element that spontaneously emits alpha rays. Ingestion of uranium can cause internal pollution and radiation hazards to the body. Strict regulations govern radiation protection and limits the amount of radioactive material in food. With increasing demand for new energy sources and the continuous development and utilization of nuclear energy, my country's demand for natural uranium is growing daily. The mining and smelting of uranium ore inevitably produces uranium waste and tailings containing naturally occurring radioactive nuclides.

[0003] Therefore, researching a process for separating nickel, molybdenum, and uranium from such ores to obtain nickel-molybdenum concentrate and ammonium uranate products is of great significance for the development and utilization of such ores. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a method for the beneficiation and separation of nickel-molybdenum-uranium ore. The separation method provided by this invention can effectively separate and recover nickel, molybdenum, and uranium, efficiently process nickel-molybdenum-uranium ore, reduce resource waste, and lower uranium pollution.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for the beneficiation and separation of nickel-molybdenum-uranium ore, comprising the following steps:

[0007] After mixing nickel-molybdenum-uranium ore, dispersant, activator, inhibitor, collector and frother, the mixture is subjected to frothing and flotation in sequence to obtain nickel-molybdenum concentrate and uranium-bearing tailings;

[0008] The uranium-bearing tailings were subjected to acid leaching to obtain leaching solution and tailings residue;

[0009] After the leachate is adsorbed by a strongly basic anion exchange resin, solid-liquid separation, rinsing, and pH adjustment are performed sequentially to obtain a uranium concentrate.

[0010] The leaching time is 6–10 hours;

[0011] The mass ratio of the activator to the nickel-molybdenum-uranium ore is 100-200 g / t;

[0012] The mass ratio of the inhibitor to nickel-molybdenum-uranium ore is 1000–2000 g / t;

[0013] The rinsing solution is a NaCl solution with a pH value of 1.2 to 2.0.

[0014] Preferably, the mass ratio of the dispersant to the nickel-molybdenum-uranium ore is 100–500 g / t.

[0015] Preferably, the mass ratio of the collector to the nickel-molybdenum-uranium ore is 1000–2000 g / t.

[0016] Preferably, the mass ratio of the foaming agent to the nickel-molybdenum-uranium ore is 10–40 g / t.

[0017] Preferably, the pH value after pH adjustment is >9.

[0018] The present invention provides a method for the beneficiation and separation of nickel-molybdenum-uranium ore, comprising the following steps: mixing nickel-molybdenum-uranium ore, dispersant, activator, inhibitor, collector, and frother, and then sequentially performing frothing and flotation to obtain nickel-molybdenum concentrate and uranium-bearing tailings; subjecting the uranium-bearing tailings to acid leaching to obtain leachate and tailings; adsorbing the leachate with a strongly basic anion exchange resin, and then sequentially performing solid-liquid separation, rinsing, and pH adjustment to obtain uranium concentrate; the leaching time is 6-10 hours; the mass ratio of the activator to the nickel-molybdenum-uranium ore is 100-200 g / t; the mass ratio of the inhibitor to the nickel-molybdenum-uranium ore is 1000-2000 g / t; the rinsing solution is a NaCl solution with a pH of 1.2-2.0. This invention achieves efficient separation of nickel, molybdenum, and uranium by sequentially frothing and flotation of nickel-molybdenum ore, causing the nickel-molybdenum concentrate to float while uranium is enriched in the uranium-bearing tailings, thus improving the recovery rate of nickel and molybdenum. Uranium leachate is obtained by leaching the uranium-bearing tailings. Further solid-liquid separation, rinsing, and pH adjustment effectively improve the uranium recovery rate. The separation method provided by this invention is simple to operate. Example results show that the recovery rates of nickel and molybdenum obtained by this invention are greater than 80%, the uranium leaching rate is greater than 96%, and the uranium recovery rate is greater than 91%. Attached Figure Description

[0019] Figure 1 This is a process flow diagram of the nickel-molybdenum-uranium ore beneficiation and separation process used in Example 1. Detailed Implementation

[0020] This invention provides a method for the beneficiation and separation of nickel-molybdenum-uranium ore, comprising the following steps:

[0021] After mixing nickel-molybdenum-uranium ore, dispersant, activator, inhibitor, collector and frother, the mixture is subjected to frothing and flotation in sequence to obtain nickel-molybdenum concentrate and uranium-bearing tailings;

[0022] The uranium-bearing tailings were subjected to acid leaching to obtain leaching solution and tailings residue;

[0023] After the leachate is adsorbed by a strongly basic anion exchange resin, solid-liquid separation, rinsing, and pH adjustment are performed sequentially to obtain a uranium concentrate.

[0024] Unless otherwise specified, all raw materials used in this invention are commercially available products in the art.

[0025] This invention involves mixing nickel-molybdenum-uranium ore, dispersant, activator, inhibitor, collector, and frother, and then sequentially performing frothing and flotation to obtain nickel-molybdenum concentrate and uranium-bearing tailings.

[0026] In this invention, the nickel grade in the nickel-molybdenum-uranium ore is preferably 1.35–2.20%, more preferably 1.57–2.12%; the molybdenum grade is preferably 2.35–3.04%, more preferably 2.86–3.03%; and the uranium grade is preferably 0.03%. Preferably, the nickel-molybdenum-uranium ore is sequentially crushed and wet-milled before being mixed with a dispersant, activator, inhibitor, collector, and frother. The preferred mixing order of the nickel-molybdenum-uranium ore, dispersant, activator, inhibitor, collector, and frother is: mixing the nickel-molybdenum-uranium ore with the dispersant for 2 minutes, the activator for 2 minutes, the inhibitor for 3 minutes, the collector for 3 minutes, and the frother for 1 minute. The preferred particle size of the crushed nickel-molybdenum-uranium ore is 1–3 mm. The wet milling is preferably performed in a ball mill. The present invention does not impose any special limitations on the specific operation method of the wet milling, as long as the particle size after wet milling is greater than 85% to -0.074mm.

[0027] In this invention, the dispersant is preferably sodium hexametaphosphate or sodium pyrophosphate, and in the embodiments of this invention, sodium hexametaphosphate is more preferred. In this invention, the mass ratio of the dispersant to nickel-molybdenum-uranium ore is preferably 100-500 g / t, and more preferably 300 g / t. In this invention, the dispersant can improve the dispersibility of mineral particles in the slurry, facilitating the improvement of the separation efficiency of nickel-molybdenum concentrate and uranium-bearing tailings in subsequent foaming and flotation processes. In this invention, the activator is preferably copper sulfate or lead nitrate, and in the embodiments of this invention, copper sulfate is more preferred. In this invention, the mass ratio of the activator to nickel-molybdenum-uranium ore is preferably 100-200 g / t, and more preferably 160 g / t. In this invention, the inhibitor is preferably water glass or carboxymethyl cellulose, and in the embodiments of this invention, water glass is more preferred. In this invention, the mass ratio of the inhibitor to nickel-molybdenum-uranium ore is preferably 1000-2000 g / t, and more preferably 1300 g / t. In this invention, the collector is preferably kerosene or diesel oil, and in this embodiment, kerosene is more preferred. In this invention, the mass ratio of the collector to nickel-molybdenum-uranium ore is preferably 1000-2000 g / t, and more preferably 1500 g / t. In this invention, the foaming agent is preferably pine oil or methyl isobutyl methanol, and in this embodiment, pine oil is more preferred. In this invention, the mass ratio of the foaming agent to nickel-molybdenum-uranium ore is preferably 10-40 g / t, and more preferably 25 g / t.

[0028] In this invention, the mixing method is preferably mechanical stirring, the stirring rate is preferably 1860 r / min, and the stirring time is preferably 10 min. In this invention, the foaming method is preferably air foaming. This invention does not have a specific limitation on the flotation method; any flotation method well known to those skilled in the art can be used. This invention achieves efficient separation of nickel, molybdenum, and uranium by sequentially subjecting nickel-molybdenum-uranium ore to foaming and flotation, causing the nickel-molybdenum concentrate to float and uranium to concentrate in the uranium-bearing tailings, thereby improving the recovery rate of nickel and molybdenum.

[0029] After obtaining uranium-containing tailings, the present invention performs acid leaching on the uranium-containing tailings to obtain leaching solution and tailings residue.

[0030] The present invention preferably involves sequentially subjecting the uranium-bearing tailings to sedimentation, solid-liquid separation, and drying to obtain dry uranium-bearing tailings, which are then sequentially mixed with water and concentrated sulfuric acid for acid leaching. In this invention, the sedimentation method is preferably natural sedimentation. The present invention does not have a specific limitation on the solid-liquid separation method; any solid-liquid separation method well-known to those skilled in the art can be used, such as stirring. The present invention preferably involves drying the solid slag obtained after solid-liquid separation. In this invention, the drying method is preferably air drying at room temperature.

[0031] In this invention, the water is preferably deionized water, and the mass ratio of water to dry weight uranium-containing tailings is 1:1 to 1:1.2. In this invention, the concentrated sulfuric acid preferably has a mass concentration of 98%, and the mass ratio of concentrated sulfuric acid to dry weight uranium-containing tailings is preferably 1:40. In this invention, the acid leaching method is preferably performed by mechanical stirring for a period of time followed by continuous leaching. In this invention, the mechanical stirring rate is preferably 1860 r / min, and mechanical stirring is preferably performed once every 5-15 minutes, with each stirring lasting 6-12 minutes. In this invention, mechanical stirring is preferably performed until the dry weight uranium-containing tailings, water, and concentrated sulfuric acid are uniformly mixed, followed by continuous leaching for 6-10 hours. This invention improves the uranium leaching rate by leaching the obtained uranium-containing tailings. When the continuous leaching time is <6 hours, the uranium leaching rate is below 90%; when the continuous leaching time is >10 hours, the uranium leaching rate essentially no longer increases.

[0032] After obtaining the leachate, the present invention uses a strongly basic anion exchange resin to adsorb the leachate, and then performs solid-liquid separation, rinsing and pH adjustment in sequence to obtain uranium concentrate.

[0033] In this invention, the ion exchange resin is preferably a strongly basic anion exchange resin, more preferably 210×7, 408(Ⅱ) type, D261, or D263. In this invention, the ratio of the strongly basic anion exchange resin to the leachate is preferably 120–160 g / L, more preferably 135–145 g / L. This invention does not specifically limit the mixing method; conventional mixing methods in the art are acceptable. The mixing time is preferably 40–80 min, more preferably 45–65 min. In this invention, the solid-liquid separation method is preferably sieving. This invention obtains uranium-containing resin through solid-liquid separation. In this invention, the rinsing solution is preferably a NaCl solution, the mass concentration of which is preferably 1–2%, more preferably 1.6%; the pH value of the NaCl solution is preferably 1.2–2.0, more preferably 1.5. In this invention, the volume ratio of the rinsing solution to the uranium-containing resin obtained through solid-liquid separation is 3–5:1. This invention removes particulate residues and impurities from uranium-containing resin by rinsing. The specific rinsing procedure is not particularly limited; any rinsing method well-known to those skilled in the art can be used. In this invention, the pH adjuster is preferably ammonia, and the adjusted pH value is >9, more preferably 9.8.

[0034] The following detailed description of the nickel-molybdenum-uranium ore beneficiation and separation method provided by the present invention, with reference to specific embodiments, should not be construed as limiting the scope of protection of the present invention.

[0035] Example 1

[0036] Nickel-molybdenum-uranium ore with nickel, molybdenum, and uranium grades of 1.35%, 2.86%, and 0.03%, respectively, was crushed to a particle size of less than 3 mm. It was then wet-milled in a ball mill until the particle size was >85% (-0.074 mm). Sodium hexametaphosphate (200 g / t) was added sequentially, followed by stirring and slurry preparation for 2 minutes; copper sulfate (120 g / t) was added, followed by stirring and slurry preparation for 2 minutes; water glass (1200 g / t) was added, followed by stirring and slurry preparation for 3 minutes; kerosene (1300 g / t) was added, followed by stirring and slurry preparation for 3 minutes; and pine oil (25 g / t) was added, followed by stirring and slurry preparation for 1 minute. Air was then introduced to create bubbles, and flotation was performed. The froth product and the product in the flotation tank were collected separately to obtain nickel-molybdenum concentrate and uranium-bearing tailings.

[0037] After natural settling, the uranium-bearing flotation tailings are subjected to solid-liquid separation to obtain solid slag and water. The solid slag is then air-dried at room temperature to obtain dry weight uranium-bearing tailings.

[0038] Add 80g of deionized water to 80g of dry uranium-containing tailings, and then add 2g of 98% sulfuric acid while stirring. Stir every 8 minutes for 10 minutes each time until the slurry is uniformly stirred. Continue leaching for 8 hours to obtain leachate and tailings.

[0039] Add 6g of 408(II) type strong base anion exchange resin to every 50mL of leachate, stir to ensure full contact between the slurry and resin for 60min, then sieve to separate the leachate from the resin and obtain uranium-containing resin. Rinse the resin multiple times with 1% NaCl solution (3 times the volume of the resin) with a pH of 1.5 to remove particulate residues and impurities. The rinsing solution yields a uranium-rich solution.

[0040] Ammonia is added to the uranium-rich solution to adjust the pH value to be greater than 9, thus obtaining the uranium enrichment product.

[0041] The recovery rates of the recovered nickel, molybdenum, and uranium were calculated, and the results are shown in Table 1.

[0042] Figure 1 The diagram below shows the process flow chart for the beneficiation and separation of nickel-molybdenum-uranium ore used in Example 1. In this example, the nickel-molybdenum-uranium ore is crushed and wet-milled in sequence, followed by foaming and flotation to obtain nickel-molybdenum concentrate and uranium-bearing tailings. The uranium-bearing tailings are leached to obtain leachate and tailings. The leachate is mixed with a strong alkaline anion exchange resin and then subjected to solid-liquid separation, rinsing, and pH adjustment in sequence to obtain uranium concentrate, i.e., precipitated uranium product.

[0043] Example 2

[0044] Nickel-molybdenum-uranium ore with nickel, molybdenum, and uranium grades of 2.12%, 3.04%, and 0.025%, respectively, was crushed to a particle size of less than 3 mm. Then, it was wet-milled in a ball mill to a particle size of -0.074 mm > 85%. Sodium hexametaphosphate 220 g / t was added and stirred for 2 min, copper sulfate 120 g / t was added and stirred for 2 min, water glass 1300 g / t was added and stirred for 3 min, kerosene 1350 g / t was added and stirred for 3 min, and pine oil 25 g / t was added and stirred for 1 min. Then, air was introduced to create bubbles, and flotation was performed. The froth product and the product in the tank were collected separately to obtain nickel-molybdenum concentrate and uranium-bearing tailings.

[0045] After natural settling, the uranium-bearing flotation tailings are subjected to solid-liquid separation to obtain solid slag and water. The solid slag is then air-dried at room temperature to obtain dry weight uranium-bearing tailings.

[0046] Add 80g of deionized water to 80g of dry uranium-containing tailings, and then add 2g of 98% sulfuric acid while stirring. Stir every 10 minutes for 10 minutes each time until the slurry is uniformly stirred. Continue leaching for 9 hours to obtain leachate and tailings.

[0047] Add 7g of 408(II) type strong base anion exchange resin to every 50mL of leachate, stir to ensure full contact between the slurry and resin for 60min, then sieve to separate the leachate from the resin and obtain uranium-containing resin. Rinse the resin multiple times with 1% NaCl solution (3 times the volume of the resin) with a pH of 1.5 to remove particulate residues and impurities. The rinsing solution yields a uranium-rich solution.

[0048] Ammonia is added to a uranium-rich solution to adjust the pH value to be greater than 9, resulting in precipitated uranium, i.e., uranium enrichment product.

[0049] The recovery rates of the recovered nickel, molybdenum, and uranium were calculated, and the results are shown in Table 1.

[0050] Example 3

[0051] Nickel-molybdenum-uranium ore with nickel, molybdenum, and uranium grades of 1.57%, 2.35%, and 0.032%, respectively, was crushed to less than 3 mm. Then, it was wet-milled in a ball mill to a particle size of -0.074 mm > 85%. Sodium hexametaphosphate 100 g / t was added and stirred for 2 min, copper sulfate 100 g / t was added and stirred for 2 min, water glass 1000 g / t was added and stirred for 3 min, kerosene 1000 g / t was added and stirred for 3 min, and pine oil 10 g / t was added and stirred for 1 min. Then, air was introduced to create bubbles, and flotation was performed. The froth product and the product in the tank were collected separately to obtain nickel-molybdenum concentrate and uranium-bearing tailings.

[0052] After natural settling, the uranium-bearing flotation tailings are subjected to solid-liquid separation to obtain solid slag and water. The solid slag is then air-dried at room temperature to obtain dry weight uranium-bearing tailings.

[0053] Add 80g of deionized water to 80g of dry uranium-bearing tailings, then add 2g of 98% sulfuric acid while stirring. Stir every 10 minutes for 10 minutes each time until the slurry is homogeneous. Continuously leach for 9 hours to obtain leachate and tailings. Add 7g of D261 strong base anion exchange resin to every 50mL of leaching slurry. Stir to ensure full contact between the slurry and resin for 60 minutes, then sieve to separate the leachate from the resin, obtaining uranium-containing resin. Rinse the resin multiple times with a 1% NaCl solution (pH 1.5, 3 times the resin volume) to remove particulate residues and impurities. The rinsing solution yields a uranium-rich solution.

[0054] Ammonia is added to the uranium-rich solution to adjust the pH value to be greater than 9, thus obtaining the uranium enrichment product.

[0055] The recovery rates of the recovered nickel, molybdenum, and uranium were calculated, and the results are shown in Table 1.

[0056] Example 4

[0057] Nickel-molybdenum-uranium ore with nickel, molybdenum, and uranium grades of 2.20%, 3.03%, and 0.031%, respectively, was crushed to a particle size of less than 3 mm. It was then wet-milled in a ball mill until the particle size was >85% (-0.074 mm). Sodium hexametaphosphate (500 g / t) was added sequentially, followed by stirring and slurry preparation for 2 minutes; copper sulfate (200 g / t) was added, followed by stirring and slurry preparation for 2 minutes; water glass (2000 g / t) was added, followed by stirring and slurry preparation for 3 minutes; kerosene (2000 g / t) was added, followed by stirring and slurry preparation for 3 minutes; and pine oil (40 g / t) was added, followed by stirring and slurry preparation for 1 minute. Air was then introduced to create bubbles, and flotation was performed. The froth product and the product in the flotation tank were collected separately to obtain nickel-molybdenum concentrate and uranium-bearing tailings.

[0058] After natural settling, the uranium-bearing flotation tailings are subjected to solid-liquid separation to obtain solid slag and water. The solid slag is then air-dried at room temperature to obtain dry weight uranium-bearing tailings.

[0059] Add 80g of deionized water to 80g of dry uranium-bearing tailings, then add 2g of 98% sulfuric acid while stirring. Stir every 10 hours for 10 minutes each time until the slurry is homogeneous. Leach continuously for 9 hours to obtain leachate and tailings. Add 7g of D261 strong base anion exchange resin to every 50mL of leaching slurry. Stir to ensure full contact between the slurry and resin for 60 minutes, then sieve to separate the leachate from the resin, obtaining uranium-containing resin. Rinse the resin repeatedly with 1% NaCl solution (pH 1.5), three times the volume of the resin, to remove particulate residues and impurities. The rinsing solution yields a uranium-rich solution.

[0060] Ammonia is added to the uranium-rich solution to adjust the pH value to be greater than 9, thus obtaining the uranium enrichment product.

[0061] The recovery rates of the recovered nickel, molybdenum, and uranium were calculated, and the results are shown in Table 1.

[0062] Comparative Example 1

[0063] The specific implementation method is the same as in Example 1, except that the leaching time is changed to 5 hours. The experimental results are shown in Table 1.

[0064] Comparative Example 2

[0065] The specific implementation method is the same as in Example 2, except that the rinsing agent is changed to 1% sulfuric acid. The test results are shown in Table 1.

[0066] Comparative Example 3

[0067] The specific implementation method is the same as in Example 3, except that the amount of inhibitor water glass is changed to 200g / t. The experimental results are shown in Table 1.

[0068] Comparative Example 4

[0069] The specific implementation method is the same as in Example 4, except that the amount of copper sulfate activator is changed to 50g / t. The experimental results are shown in Table 1.

[0070] Table 1. Results of nickel-molybdenum-uranium ore beneficiation and separation tests in Examples 1-4 and Comparative Examples 1-4

[0071]

[0072] The experimental data above show that the separation method provided by the present invention can effectively separate and recover nickel, molybdenum and uranium, and efficiently process nickel, molybdenum and uranium ore. The recovery rate of nickel and molybdenum is greater than 80%, the leaching rate of uranium is greater than 96%, and the uranium recovery rate is greater than 91%.

[0073] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for the beneficiation and separation of nickel-molybdenum-uranium ore, comprising the following steps: After mixing nickel-molybdenum-uranium ore, dispersant, activator, inhibitor, collector and frother, the mixture is subjected to frothing and flotation in sequence to obtain nickel-molybdenum concentrate and uranium-bearing tailings; The uranium-bearing tailings were subjected to acid leaching to obtain leaching solution and tailings residue; After the leachate is adsorbed by a strongly basic anion exchange resin, solid-liquid separation, rinsing, and pH adjustment are performed sequentially to obtain a uranium concentrate. The leaching time is 6-10 hours; The mass ratio of the activator to the nickel-molybdenum-uranium ore is 100~200g / t; The mass ratio of inhibitor to nickel-molybdenum-uranium ore is 1000~2000 g / t; The rinsing solution is a NaCl solution with a pH value of 1.2 to 2.

0. The dispersant is sodium hexametaphosphate or sodium pyrophosphate; The activator is copper sulfate or lead nitrate; The inhibitor is water glass or carboxymethyl cellulose; The collector is kerosene or diesel oil; The foaming agent is pine oil or methyl isobutyl alcohol.

2. The separation method of claim 1, wherein, The mass ratio of the dispersant to the nickel-molybdenum-uranium ore is 100~500g / t.

3. The separation method of claim 1, wherein, The mass ratio of the collector to the nickel-molybdenum-uranium ore is 1000~2000 g / t.

4. The separation method of claim 1, wherein, The mass ratio of the foaming agent to the nickel-molybdenum-uranium ore is 10~40 g / t.

5. The separation method of claim 1, wherein, The pH value after pH adjustment is >9.

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