Microwave anhydrous curing upgrading method for primary polymetallic vanadium ore

Abstract

The invention discloses a primary multi-metal vanadium ore microwave anhydrous curing upgrading method which comprises the following steps: S1, microwave curing: weighing vanadium ore powder, adding sulfuric acid and water, uniformly stirring, heating in a microwave field, keeping the temperature for a period of time, and grinding a cured product into powder by using a vibration mill after curing; and S2, leaching and suction filtration: weighing the powder cured by microwaves in the S1, soaking the powder in deionized water at 80-90 DEG C according to a liquid-solid ratio of 0.5-2 during leaching, performing suction filtration by using a vacuum suction filtration machine after water leaching is completed, washing by using hot water, and finally taking a dried sample. According to the microwave anhydrous curing upgrading method for the primary multi-metal vanadium ore, the leaching rate of vanadium is increased, and therefore vanadium ore resources are effectively utilized.

Description

Technical Field

[0001] The invention relates to the technical field of vanadium-containing ore extraction technology, and in particular to a microwave anhydrous maturation and quality improvement method for primary polymetallic vanadium ore. Background Art

[0002] Vanadium is an important material for the preparation of high-tech products such as special steel, vanadium-titanium alloy, catalyst and vanadium liquid flow energy storage battery, and is widely used in modern industrial technology. Vanadium ore resources mainly include vanadium-titanium magnetite and vanadium-containing shale (including carbonaceous shale, mudstone shale, etc.). Shale vanadium ore accounts for 87% of my country's total vanadium reserves and is an important vanadium resource.

[0003] Shale vanadium ore is the main vanadium-containing resource mined as a separate vanadium deposit in my country. The existing vanadium ores mainly include two types, namely oxidized shale vanadium ore and primary shale vanadium ore. The vanadium in the oxidized shale vanadium ore is mainly on the surface of the mineral. Therefore, the existing acid leaching and other processes can be used to better extract vanadium. The vanadium in the primary shale vanadium ore is mainly present in the silicate lattice in an isomorphous form. The existing technologies such as acid leaching, blank microwave roasting-acid leaching and other processes have a low vanadium leaching rate, which makes the vanadium ore resources not effectively utilized and wasted. Summary of the invention

[0004] The object of the present invention is to provide a method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous ripening, so as to improve the leaching rate of vanadium and effectively utilize the vanadium ore resources.

[0005] The technical solution adopted by the microwave anhydrous ripening and upgrading method of a primary polymetallic vanadium ore disclosed in the present invention is:

[0006] A method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous ripening comprises the following steps:

[0007] S1, microwave aging: weigh vanadium ore powder, add sulfuric acid and water, stir evenly, heat in a microwave field and keep warm for a period of time, and after aging, use a vibration mill to grind the aging product into powder;

[0008] S2, leaching and filtration: weigh the microwave-cured powder in S1 and soak it in deionized water at 80-90°C. The liquid-to-solid ratio during leaching is 0.5-2. After the immersion is completed, use a vacuum filter to filter it, wash it with hot water, and finally take a dried sample.

[0009] As a preferred solution, the calculation formula of the leaching rate η is:

[0010] In the formula: m0, m1, m2—mass of raw materials, clinker and leaching residue (g); m*1—mass of clinker used in the leaching process (g); ω0, ω1, ω2—metal content in raw materials, clinker and leaching residue (wt.% or g / t).

[0011] As a preferred solution, in step S1, water may be added, and water and sulfuric acid may be added together and stirred uniformly.

[0012] As a preferred solution, the amount of water added is 1-20% of the mass of the vanadium ore.

[0013] As a preferred solution, the amount of sulfuric acid used is in the range of 40-75wt.%.

[0014] As a preferred solution, the microwave field ripening temperature ranges from 175°C to 275°C.

[0015] As a preferred solution, the insulation time ranges from 1 to 120 minutes.

[0016] As a preferred solution, the microwave power ranges from 200 to 700W.

[0017] As a preferred solution, during the water leaching process, the factors affecting the metal leaching rate in the vanadium ore include: the water leaching temperature range is 60-95° C. and the water leaching time is 30-150 min.

[0018] As a preferred embodiment, the aging product is ground into powder with a particle size ranging from 10 to 200 meshes.

[0019] The beneficial effects of the microwave anhydrous aging and upgrading method of a primary polymetallic vanadium ore disclosed in the present invention are as follows: sulfuric acid aging can convert metals such as vanadium into soluble sulfates, and has natural advantages in treating mica minerals. In particular, sulfuric acid has a high microwave absorption capacity, which can quickly absorb microwaves in a microwave field to form a local high-temperature domain to accelerate vanadium oxidation and dissolution, thereby improving the aging efficiency and vanadium leaching rate, thereby effectively utilizing vanadium ore resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a schematic diagram of the effect of water addition on the leaching rate of various metals in microwave-ripened shale vanadium ore.

[0021] Figure 2 This is a schematic diagram of the effect of sulfuric acid dosage on the metal leaching rate of microwave-ripened shale vanadium ore.

[0022] Figure 3 This is a schematic diagram of the effect of maturation temperature on the metal leaching rate of microwave-maturing shale vanadium ore.

[0023] Figure 4This is a schematic diagram of the effect of holding time on the metal leaching rate of microwave-ripened shale vanadium ore.

[0024] Figure 5 This is a schematic diagram of the effect of microwave power on the metal leaching rate of microwave-ripened shale vanadium ore.

[0025] Figure 6 This is a schematic diagram of the effect of water immersion temperature on the metal leaching rate of microwave-ripened shale vanadium ore.

[0026] Figure 7 This is a schematic diagram of the effect of liquid-to-solid ratio on the metal leaching rate of microwave-ripened shale vanadium ore.

[0027] Figure 8 This is a schematic diagram of the effect of immersion time on the metal leaching rate of microwave-ripened shale vanadium ore.

[0028] Fig. 9 This is a schematic diagram of the effect of particle size on the metal leaching rate of microwave-ripened shale vanadium ore. DETAILED DESCRIPTION

[0029] The present invention will be further described and illustrated below in conjunction with specific embodiments and accompanying drawings:

[0030] A method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous aging, comprising the following steps: S1, microwave aging: weighing vanadium ore powder, adding sulfuric acid and water, stirring evenly, heating in a microwave field and keeping warm for a period of time, and after aging, grinding the aging product into powder using a vibration mill;

[0031] S2, leaching and filtration: weigh the microwave-cured powder in S1 and soak it in deionized water at 80-90°C. The liquid-to-solid ratio during leaching is 0.5-2. After the immersion is completed, use a vacuum filter to filter it, wash it with hot water, and finally take a dried sample.

[0032] The calculation formula of leaching rate η is:

[0033] In the formula: m0, m1, m2—mass of raw materials, clinker and leaching residue (g); m*1—mass of clinker used in the leaching process (g); ω0, ω1, ω2—metal content in raw materials, clinker and leaching residue (wt.% or g / t).

[0034] On the basis of microwave sulfuric acid ripening, the effects of leaching temperature, liquid-to-solid ratio, leaching time and particle size on the leaching rates of vanadium, niobium, molybdenum, aluminum, gallium, indium and germanium in the ore were explored to obtain economically reasonable process parameters.

[0035] The effect of microwave ripening on the metal leaching rate in shale vanadium ore was further determined:

[0036] (1) Effect of water addition on leaching rate

[0037] Under the conditions of 40wt.% sulfuric acid, microwave power of 300W, aging temperature of 225℃, and holding time of 60min, the effect of water addition (0, 5, 10, 15, 20ml, i.e. 0, 5, 10, 15, 20% of vanadium ore) on the leaching rate of each metal is shown in the figure. Figure 1 shown.

[0038] Depend on Figure 1 It can be seen that the leaching rates of vanadium and molybdenum increase with the increase of water addition, reaching the maximum at 5%; as the amount of water added continues to increase, the leaching rates of vanadium and molybdenum decrease with the increase of water. Therefore, when the amount of water added during microwave aging is 5%, the corresponding leaching rates of vanadium, molybdenum, gallium, and germanium are 62.5%, 78.38%, 52.48%, and 86.63%, respectively.

[0039] (2) Effect of sulfuric acid dosage on leaching rate

[0040] Under the conditions of 5% water addition, 300W microwave power, 225℃ aging temperature and 60min holding time, the effect of sulfuric acid dosage (40, 50, 60, 70, 75wt.%) on the leaching rate of each metal is shown in the figure. Figure 2 shown.

[0041] Depend on Figure 2 It can be seen that the leaching rates of vanadium, niobium and aluminum all increase with the increase of sulfuric acid dosage; when the sulfuric acid dosage increases to 60%, the leaching rates of vanadium and niobium are 90.69% and 89.26% respectively. Continuing to increase the amount of sulfuric acid, the growth rate of vanadium and niobium leaching rates slows down. Considering the cost of subsequent production and sulfuric acid, it is advisable to control the amount of sulfuric acid at 60%, and the corresponding leaching rates of vanadium, molybdenum, aluminum, niobium, gallium and germanium are 90.69%, 68.83%, 79.21%, 89.26%, 50.52% and 83.2% respectively.

[0042] (3) Effect of aging temperature on leaching rate

[0043] Under the conditions of 5% water addition, 60wt.% sulfuric acid dosage, 300W microwave power and 60min holding time, the effects of aging temperature (175, 200, 225, 250, 275℃) on the leaching rate of each metal are shown in the figure. Figure 3 shown.

[0044] Depend on Figure 3It can be seen that when the temperature is less than 225°C, the leaching rates of vanadium, niobium, aluminum, and indium increase with the increase of microwave insulation temperature. However, when the temperature is higher than 225°C, the leaching rates of vanadium and niobium remain basically unchanged, and the leaching rate of aluminum decreases slightly with the increase of temperature. This may be due to the fact that the concentrated sulfuric acid gradually decomposes due to excessive temperature, affecting the leaching rates of vanadium, niobium, and aluminum. Therefore, the microwave roasting temperature should be controlled at around 225°C, and the corresponding leaching rates of vanadium, molybdenum, aluminum, niobium, gallium, germanium, and indium are 92.2%, 64.12%, 87.08%, 89.94%, >62.22%, 79.89%, and 79.47%.

[0045] (4) Effect of holding time on leaching rate

[0046] Under the conditions of 5% water addition, 60wt.% sulfuric acid, 225℃ aging temperature and 300W microwave power, the effects of holding time (0, 30, 60, 90 and 120min) on the leaching rate of each metal are shown in the figure. Figure 4 shown.

[0047] Depend on Figure 4 It can be seen that microwave roasting time has little effect on the leaching rate of vanadium, niobium, aluminum and germanium in shale vanadium ore. Taking comprehensive consideration, the holding time is selected as 30min, and the corresponding leaching rates of vanadium, molybdenum, aluminum, niobium, gallium, germanium and indium are 92.13%, 69.15%, 84.78%, 91.07%, >62.22%, 84.96% and 78.42%.

[0048] (5) Effect of microwave power on leaching rate

[0049] Under the conditions of 5% water addition, 60wt.% sulfuric acid, 225℃ aging temperature and 30min holding time, the effect of microwave power (200, 300, 400, 500, 700W) on the leaching rate of each metal is shown in the figure. Figure 5 shown.

[0050] Depend on Figure 5 It can be seen that the leaching rate of vanadium increases with the increase of microwave power, while the leaching rates of niobium and aluminum remain basically unchanged. When the microwave power is 200, 300, 400, 500, 600, and 700 W, the total roasting time is 61, 48, 46, 44, and 41 min, respectively. Considering the energy consumption and time cost, the microwave power is selected as 300 W, and the corresponding leaching rates of vanadium, molybdenum, aluminum, niobium, gallium, germanium, and indium are 92.13%, 69.15%, 84.78%, 91.07%, >62.22%, 84.96%, and 78.42%.

[0051] Effect of water leaching on metal leaching rate in shale vanadium ore:

[0052] Based on the microwave aging experiment (water addition amount 5%, sulfuric acid dosage 60%, aging temperature 225℃, insulation time 30min, microwave power 300W), the effects of immersion temperature, liquid-solid ratio, immersion time and particle size on the leaching rates of vanadium, niobium, molybdenum, aluminum, gallium, indium and germanium were explored.

[0053] (1) Effect of water immersion temperature on leaching rate

[0054] The effects of immersion time of 60 min, liquid-to-solid ratio of 1.5 (ml / g), and immersion temperature (60, 70, 80, 90, 95°C) on the leaching rates of various metals are shown in the figure. Figure 6 shown.

[0055] Depend on Figure 6 It can be seen that the leaching temperature has a great influence on the leaching rate of each element. The leaching temperature has little effect on the leaching rate of vanadium. The leaching rates of Nb and Ge increase with the increase of leaching temperature. When the leaching temperature is 90℃, the leaching rates of V, Nb and Ge are 92.13%, 91.07% and 84.96% respectively. The leaching temperature has a great influence on Mo. As the leaching temperature increases from 60℃ to 95℃, the leaching rate of Mo increases from 61.27% to 69.83%. However, a higher leaching temperature will inhibit the dissolution of aluminum. Considering comprehensively, the optimal leaching temperature is 90℃.

[0056] (2) Effect of liquid-solid ratio on leaching rate

[0057] The effects of the liquid-to-solid ratio (0.5, 1, 1.5, 2) on the leaching rates of various metals at a water immersion temperature of 90°C and a water immersion time of 60 min are shown in the figure. Figure 7 shown.

[0058] Depend on Figure 7 It can be seen that the liquid-solid ratio has little effect on the leaching rates of V, Nb, Mo, Ga, and Ge, but with the increase of the solid-liquid ratio, the leaching rates of Mo and Al show an overall downward trend, especially Mo. As the liquid-solid ratio increases from 0.5 to 2.0, the leaching rate of Mo decreases from 75.51% to 65.83%. A low solid-liquid ratio is prone to dry leaching. Considering the actual production of the enterprise, the preferred liquid-solid ratio is 1.

[0059] (3) Effect of immersion time on leaching rate

[0060] The effects of immersion temperature of 90°C, liquid-to-solid ratio of 1, and immersion time (30, 60, 90, 120, 150 min) on the leaching rates of various metals are shown in the figure. Figure 8 shown.

[0061] Depend on Figure 8It can be seen that the leaching time has little effect on the leaching rate of V and Nb. The leaching rates of Ge and Al increase with the extension of leaching time. As the leaching time increases from 30min to 120min, the leaching rates of Ge and Al increase from 81.39% and 78.49% to 85.66% and 83.74%, respectively. The leaching rate of Ga decreases significantly with the extension of leaching time. Considering comprehensively, the appropriate leaching time is 30min.

[0062] (4) Effect of particle size on leaching rate

[0063] Under the conditions of immersion temperature of 90℃, liquid-to-solid ratio of 1, and leaching time of 30min, the effect of particle size (10, 60, 80, 120, 200 mesh) on the leaching rate of each metal is as follows: Fig. 9 shown.

[0064] Depend on Fig. 9 It can be seen that the particle size in the range of 10-200 mesh has little effect on the leaching rate of V, Nb, Al, and Ge. However, the leaching rate of Mo and Ga increases with the increase of particle size, especially Ga. As the particle size increases from 10 mesh to 200 mesh, the leaching rate of Ga increases from 55.31% to >62.22%. Taking all factors into consideration, the appropriate particle size is 200 mesh.

[0065] In summary, the best aging process conditions for improving the quality of shale vanadium ore by microwave aging-water leaching are: water addition 5%, sulfuric acid dosage 60%, aging temperature 225℃, insulation time 30min, microwave power 300W; the best water leaching process is water leaching temperature 90℃, liquid-solid ratio 1, leaching time 30min, particle size 200 mesh. Under these conditions, the leaching rates of vanadium, molybdenum, aluminum, niobium, gallium, and germanium are 91.56%, 78.49%, 78.82%, 90.29%, >62.22%, and 81.39%.

[0066] Leaching residue composition report

[0067] The composition of the leached residue is reported in Tables 1 and 2. The compass test results

[0068] Table 1 Composition analysis of leached residue (wt.%)

[0069]

[0070] Table 2 Component analysis of the leachate (mg\l) (full test)

[0071]

[0072] Alkali dissolution experiment of leaching residue

[0073] The silicon dioxide content in the leached residue is 83.39%. After direct alkali dissolution, ultrasonic assisted alkali dissolution, alkali roasting-water leaching, and pressurized alkali dissolution, the residual rate of the leached residue is shown in Table 3.

[0074] Table 3 Effect of different alkaline dissolution processes on the dissolution of leaching residue

[0075]

[0076]

[0077] Experiment to reduce acid consumption

[0078] The acid consumption during the aging process was reduced by extending the treatment time and increasing the microwave power. The results are shown in Table 4.

[0079] Table 4 Effect of extending treatment time on reducing acid consumption

[0080]

[0081] The present invention provides a method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous aging. Sulfuric acid aging can convert metals such as vanadium into soluble sulfates, and has natural advantages in treating mica minerals. In particular, sulfuric acid has a high microwave absorption capacity, and can quickly absorb microwaves in a microwave field to form a local high-temperature domain to accelerate vanadium oxidation and dissolution, thereby improving the aging efficiency and vanadium leaching rate, thereby effectively utilizing vanadium ore resources.

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous ripening, characterized in that: The following steps are involved: S1, microwave aging: weigh vanadium ore powder, add sulfuric acid, stir evenly, heat in a microwave field and keep warm for a period of time. After aging, use a vibration mill to grind the aging product into powder; S2, leaching and filtration: weigh the microwave-cured powder in S1 and soak it in deionized water at 80-90°C. The liquid-to-solid ratio during leaching is 0.5-2. After the immersion is completed, use a vacuum filter to filter it, wash it with hot water, and finally take a dried sample.

2. A method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous maturation as claimed in claim 1, characterized in that: The calculation formula of the leaching rate η is: In the formula: m0, m1, m2—mass of raw materials, clinker and leaching residue (g); m*1—mass of clinker used in the leaching process (g); ω0, ω1, ω2—metal content in raw materials, clinker and leaching residue (wt.% or g / t).

3. A method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous maturation as claimed in claim 1, characterized in that: In step S1, water may be added, and water and sulfuric acid may be added together and stirred uniformly.

4. A method for improving the quality of primary polymetallic vanadium ore by microwave anhydrous maturation as claimed in claim 4, characterized in that: The amount of water added is 1-20% of the mass of the vanadium ore.

5. The microwave anhydrous maturation and upgrading method of primary polymetallic vanadium ore according to claim 1, characterized in that: The amount of sulfuric acid used is in the range of 40-75 wt.%.

6. The microwave anhydrous ripening and upgrading method of primary polymetallic vanadium ore according to claim 1, characterized in that: The microwave field ripening temperature ranges from 175°C to 275°C.

7. The microwave anhydrous ripening and upgrading method of primary polymetallic vanadium ore according to claim 1, characterized in that: The insulation time ranges from 1 to 120 minutes.

8. The microwave anhydrous ripening and upgrading method of primary polymetallic vanadium ore according to claim 1, characterized in that: The microwave power ranges from 200 to 700W.

9. The microwave anhydrous ripening and upgrading method of primary polymetallic vanadium ore according to claim 1, characterized in that: During the water leaching process, the factors affecting the metal leaching rate in the vanadium ore include: the water leaching temperature range is 60-95° C. and the water leaching time is 30-150 min.

10. The microwave anhydrous ripening and upgrading method of primary polymetallic vanadium ore according to claim 1, characterized in that: The granularity range of the aging product ground into powder is 10-200 meshes.

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