Fluidized hydrogen-based ore phase inversion treatment method for multi-metal associated pyrolusite

Abstract

A multi-metal associated pyrolusite fluidization hydrogen-based ore phase conversion treatment method belongs to the technical field of pyrolusite reduction roasting, and comprises the following steps: refining raw ore to a required particle size standard to obtain an ore grinding product, drying the ore grinding product, scattering the ore grinding product to a uniform and loose state, and discharging the ore grinding product; the scattered pyrolusite product enters an ore phase conversion roasting furnace of a fluidized reduction roasting system and is preheated in advance in the air atmosphere, adsorbed water is removed, then N2 gas is introduced to empty air in the furnace, mixed gas of N2 and H2 is introduced, fluidized hydrogen group reduction is conducted, and a reduced product is obtained; and cooling the reduced product to normal temperature in N2 atmosphere to obtain a cooled product. According to the fluidized roasting technology adopted by the method, the high-purity bipartite ore can be obtained through efficient reduction, the reduction rate is greatly increased, accurate regulation and control of the reduced phase can be achieved by introducing nitrogen in the cooling stage, and compared with a traditional technology, the method has the environment-friendly advantage and application value.

Description

Technical Field

[0001] The invention belongs to the technical field of pyrolusite reduction roasting, and in particular relates to a fluidized hydrogen-based ore phase conversion treatment method for polymetallic associated pyrolusite. Background Art

[0002] As a complex mineral resource, polymetallic pyrolusite is widely distributed around the world and has considerable reserves. It has important economic value and strategic significance. However, the existing treatment process faces a series of severe challenges. When traditional hydrometallurgical treatment of polymetallic pyrolusite usually requires the use of a large amount of strong acid, strong alkali and other chemical reagents for leaching operations. This not only leads to a large consumption of chemical reagents, significantly increases production costs, but also produces a large amount of acidic or alkaline wastewater during the leaching process. These wastewaters contain high concentrations of heavy metal ions, ammonia nitrogen and other harmful substances. If they are directly discharged without proper treatment, they will cause extremely serious pollution to the surrounding water environment, causing a series of environmental problems such as water acidification, eutrophication and poisoning of aquatic organisms. At the same time, they also face huge environmental treatment pressure and high treatment costs. When treating polymetallic pyrolusite, the pyrometallurgical process generally smelts and reduces the ore under high temperature conditions. This process is often accompanied by the emission of a large amount of greenhouse gases such as carbon dioxide (CO2) and carbon monoxide (CO), which has a negative impact on global warming and is not in line with the current low-carbon and environmentally friendly development concept. Moreover, the high temperature environment required by pyrometallurgy usually relies on the combustion of large amounts of fossil fuels such as coal and coke, which further exacerbates energy consumption and carbon emissions. In addition, problems such as uneven smelting of ore and volatilization loss of metals at high temperatures during pyrometallurgy also lead to low metal recovery rates and serious waste of resources.

[0003] In terms of phase regulation, it is difficult for traditional processes, whether wet or pyrometallurgical, to accurately control the phase transformation of pyrolusite in key processes such as dehydration and reduction. Various metal elements are intertwined in pyrolusite, and its phase changes are complex and diverse. Traditional processes lack precise control methods, making subsequent separation and purification processes more difficult. For example, in some traditional reduction processes, the inability to accurately control the degree of reduction and phase structure leads to uneven particle size and many crystal structure defects in the generated metal minerals, which affects the effect of subsequent separation processes such as magnetic separation and flotation, and reduces the grade and recovery rate of manganese concentrate and other associated metal concentrates. With the increasing prominence of global resource shortages and increasingly stringent environmental regulations, it is urgent to develop an efficient, green, and phase-controlled multi-metallic associated pyrolusite treatment process, which is of great significance for improving resource utilization, reducing environmental pollution, and promoting the sustainable development of the mining industry. Summary of the invention

[0004] In view of the problems existing in the prior art for treating polymetallic associated pyrolusite, the present invention provides a fluidized hydrogen-based ore phase transformation treatment method for polymetallic associated pyrolusite, which adopts fluidized hydrogen-based ore phase transformation technology of air preheating and H2 reduction to enable the polymetallic associated pyrolusite to achieve precise phase transformation in the dehydration and reduction process.

[0005] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0006] (1) grinding the raw ore to obtain a desired particle size to obtain a pyrolusite grinding product;

[0007] (2) preliminarily drying the obtained pyrolusite grinding product, and then breaking it into a uniform and loose state and discharging it;

[0008] (3) The broken up pyrolusite product enters into a mineral phase conversion roasting furnace of a fluidized reduction roasting system, where the pyrolusite is preheated in advance and adsorbed water is removed under an air atmosphere, and then N2 gas is introduced to exhaust the air in the furnace, and then a mixed gas of N2 and H2 is introduced, and fluidized hydrogen-based reduction is performed under this atmosphere to obtain a reduced product;

[0009] (4) The reduced product is cooled to room temperature under a N2 atmosphere to obtain a cooled product.

[0010] in:

[0011] In the step (1), the raw ore is ground to a particle size of -0.074 mm ≥ 60%.

[0012] In the step (2), the temperature of the preliminary drying is 100° C. to 200° C., and the time is 25 min to 45 min.

[0013] In the step (3), the preheating temperature of the pyrolusite is 200° C. to 400° C., and the preheating time is 1 min to 5 min.

[0014] In the step (3), the volume concentration of H2 in the mixed gas of N2 and H2 is 15% to 30%.

[0015] In the step (3), the temperature of the fluidized hydrogen-based reduction is 500° C. to 700° C., and the reduction time is 15 min to 35 min.

[0016] In the step (4), the cooling product (Mn 2+ ) / (TMn)≥90%.

[0017] The key technical principle of the fluidized hydrogen-based ore phase transformation treatment method of a polymetallic associated pyrolusite of the present invention is as follows:

[0018] 1. In the reduction stage of the present invention, H2 is used as the reducing gas to transform the polymetallic associated pyrolusite into a hydrogen-based ore phase, and pyrolusite (MnO2) is accurately converted into harzburgite (MnO) for leaching in the next stage. The reduction sequence is MnO2→Mn2O3→Mn3O4→MnO, and the high-valent MnO2 is gradually reduced to the low-valent MnO.

[0019] Among them, the mineral phase transformation principle involved is:

[0020] 2MnO2(s)+H2(g)=Mn2O3(s)+H2O(g)

[0021] 3Mn2O3(s)+H2(g)=2Mn3O4(s)+H2O(g)

[0022] Mn3O4(s)+H2(g)=3MnO(s)+H2O(g)

[0023] 2. In the cooling stage of the present invention, nitrogen is used to cool the reduction product, and protective gas cooling is used to prevent harzburgite (MnO) from being gradually oxidized to hausmannite (Mn3O4), francone (Mn2O3), etc. in the order of MnO→Mn3O4→Mn2O3, thereby affecting the subsequent leaching efficiency.

[0024] Among them, the oxidation reaction principle involved is:

[0025] 6MnO(s)+O2(g)=2Mn3O4(s)

[0026] 4Mn3O4(s)+O2(g)=6Mn2O3(s)

[0027] The mineral phase transformation process achieves accurate control of the newly formed sylvite (MnO), greatly reducing the oxidation rate of sylvite during the cooling process, and further improving the leaching efficiency in the subsequent stages.

[0028] 3. The present invention adopts a fluidized hydrogen-based reduction roasting technology in which H2 is introduced in the reduction stage to achieve ore phase transformation of the difficult-to-select pyrolusite, accurately transforming pyrolusite (MnO2) into harzburgite (MnO), and transforming a small amount into hausmannite (Mn3O4) and fusantite (Mn2O3), thereby increasing its acid solubility and being more conducive to subsequent leaching operations.

[0029] Compared with the prior art, the invention has the following innovative features and beneficial effects:

[0030] 1. The process of using H2 to reduce polymetallic pyrolusite has emerged, bringing innovative breakthroughs in the field of manganese concentrate preparation. Compared with traditional chemical reduction and metallurgical processes, this process shows significant advantages in the reduction reaction stage, and does not produce greenhouse gases such as carbon dioxide (CO2) and carbon monoxide (CO) and acidic wastewater, effectively curbing pollution from the source and greatly reducing the negative impact on the ecological environment. Therefore, this technology has achieved remarkable results in low-carbon emission reduction, and has great environmental advantages and application value.

[0031] 2. The present invention innovatively introduces fluidized roasting technology into the roasting process of polymetallic associated pyrolusite. Compared with other conventional processes, fluidized roasting technology allows the reducing gas to contact the solid particles more fully, and has outstanding advantages in energy consumption. Pyrolusite needs to undergo three phase changes during the reduction process. Fluidized roasting technology can efficiently reduce and obtain high-purity pyrolusite, greatly increasing the reduction rate.

[0032] 3. The present invention adopts the fluidized reduction roasting technology of introducing H2 in the reduction stage and the cooling technology of introducing nitrogen in the cooling stage, so that the polymetallic associated pyrolusite can achieve precise control of the physical phase of reduction. Under this precise control, pyrolusite (MnO2) can be accurately converted into harzburgite (MnO), and the generation of high-valent manganese oxides (Mn3O4, Mn2O3) is effectively suppressed, thereby minimizing the adverse effects on the subsequent manganese mineral leaching process. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 A process flow chart of fluidized hydrogen-based ore phase conversion treatment of polymetallic associated pyrolusite of the present invention. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the implementation of the present invention in conjunction with the embodiments and the accompanying drawings. It should be noted that the embodiments described in the present invention are only used to further explain and illustrate, rather than to limit the scope of application. Based on the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

[0035] Example 1

[0036] A method for fluidizing hydrogen-based ore phase conversion treatment of polymetallic associated pyrolusite, the process flow chart of which is as follows: Figure 1 As shown, the specific steps include:

[0037] (1) Using a local pyrolusite ore with a TMn grade of 34.2% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 70%, obtaining a pyrolusite grinding product, which is then dried and dispersed;

[0038] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 150° C. for 30 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0039] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 300°C and the preheating time is 3 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 500°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion, and the volume concentration of the reducing gas H2 is controlled at 25%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 30 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0040] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 95%.

[0041] Example 2

[0042] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0043] (1) Using a local pyrolusite ore with a TMn grade of 19.71% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 75%, obtaining a pyrolusite grinding product, which is then dried and dispersed;

[0044] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 170° C. for 25 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0045] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 350°C and the preheating time is 5 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 550°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion, and the volume concentration of the reducing gas H2 is controlled at 20%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 20 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0046] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 90%.

[0047] Example 3

[0048] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0049] (1) Using a local pyrolusite ore with a TMn grade of 30.7% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 70%, and a pyrolusite grinding product is obtained, which is then dried and dispersed;

[0050] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 200° C. for 35 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0051] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 250°C and the preheating time is 4 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 570°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion. The volume concentration of the reducing gas H2 is controlled at 30%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 15 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0052] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 92%.

[0053] Example 4

[0054] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0055] (1) Using a local pyrolusite ore with a TMn grade of 20.1% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 75%, and a pyrolusite grinding product is obtained, which is then dried and dispersed;

[0056] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 100° C. for 45 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0057] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 200°C and the preheating time is 4 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 600°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion, and the volume concentration of the reducing gas H2 is controlled at 20%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 25 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0058] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 98%.

[0059] Example 5

[0060] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0061] (1) Using a local pyrolusite ore with a TMn grade of 17.48% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 70%, obtaining a pyrolusite grinding product, which is then dried and dispersed;

[0062] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 200° C. for 25 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0063] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 400°C and the preheating time is 4 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 700°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion, and the volume concentration of the reducing gas H2 is controlled at 15%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 25 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0064] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 94%.

[0065] Example 6

[0066] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0067] (1) Using a local pyrolusite ore with a TMn grade of 18.12% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 65%, obtaining a pyrolusite grinding product, which is then dried and dispersed;

[0068] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 150° C. for 40 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0069] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 300°C and the preheating time is 2 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 525°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion, and the volume concentration of the reducing gas H2 is controlled at 25%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 35 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0070] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 96%.

[0071] Comparative Example 1

[0072] A fluidized hydrogen-based mineral phase conversion treatment method for polymetallic associated pyrolusite, specifically comprising the following steps:

[0073] (1) Using a local pyrolusite ore with a TMn grade of 34.2% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 70%, obtaining a pyrolusite grinding product, which is then dried and dispersed;

[0074] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 150° C. for 30 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0075] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 300°C and the preheating time is 3 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace needs to be accurately controlled to 500°C. Subsequently, N2 gas is continuously introduced into the furnace chamber for 5 minutes to ensure that the residual air in the furnace is completely emptied. Then, a mixed gas of N2 and H2 is introduced in proportion, and the volume concentration of the reducing gas H2 is controlled at 25%. The reducing gas flow at the bottom of the furnace chamber allows the pyrolusite material to fully roll and contact under the airflow, and fluidized hydrogen-based reduction is carried out. The reduction time is controlled at 30 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a stable reduced product, quartzite, is obtained.

[0076] (4) After the reduced material enters the cooling stage, it is cooled to room temperature in an air atmosphere to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 60%. Compared with Example 1, the indexes of the cooled product are decreased, which may be due to the oxidation of harzburgite to its high-valent oxide during the cooling process.

[0077] Comparative Example 2

[0078] A method for carbon thermal reduction of polymetallic associated pyrolusite, comprising the following steps:

[0079] (1) Using a local pyrolusite ore with a TMn grade of 19.71% as raw material, the raw ore is fed into a ball mill for grinding to refine it to a particle size of -0.074 mm ≥ 75%, obtaining a pyrolusite grinding product, which is then dried and dispersed;

[0080] (2) the obtained pyrolusite grinding product is preliminarily dried in a drying and dispersing machine at a temperature of 170° C. for 25 min to remove moisture from the material, and then dispersed by a dispersing device provided at the discharge port to ensure that the material is discharged in a uniform and loose state;

[0081] (3) The materials after the dispersion treatment enter the core equipment of the reduction roasting system, the mineral phase conversion roasting furnace, in an orderly manner. Under the air atmosphere, the pyrolusite is preheated in advance and the adsorbed water is removed. The preheating temperature is 350°C and the preheating time is 5 minutes. When the materials enter the main reaction zone for reduction, the temperature in the mineral phase conversion roasting furnace must be accurately controlled to 550°C, and then air is continuously introduced into the furnace cavity. Carbon thermal reduction is adopted, and the reduction time is controlled within 20 minutes to ensure that the powder ore is fully reacted in the equipment. After the reaction is completed, a reduced product, manganese ore, with stable properties is obtained.

[0082] (4) After the reduced material enters the cooling stage, N2 is introduced into the cooling furnace chamber to cool it to room temperature to obtain a cooling product. The product (Mn 2+ ) / (TMn) is 75%. Compared with Example 2, the cooling product index has decreased. The possible reason is that during the reduction process, the pyrolusite is not in sufficient contact with the reducing agent, and the pyrolusite cannot be efficiently treated. In addition, greenhouse gases such as carbon dioxide (CO2) and carbon monoxide (CO) generated by the reduction are not conducive to the green and environmentally friendly production of manganese products.

Claims

1. A fluidized hydrogen-based ore phase conversion treatment method for polymetallic associated pyrolusite, characterized in that: The specific steps include: (1) grinding the raw ore to obtain a desired particle size to obtain a pyrolusite grinding product; (2) preliminarily drying the obtained pyrolusite grinding product, and then breaking it into a uniform and loose state and discharging it; (3) The broken up pyrolusite product enters into a mineral phase conversion roasting furnace of a fluidized reduction roasting system, where the pyrolusite is preheated in advance and adsorbed water is removed under an air atmosphere, and then N2 gas is introduced to exhaust the air in the furnace, and then a mixed gas of N2 and H2 is introduced, and fluidized hydrogen-based reduction is performed under this atmosphere to obtain a reduced product; (4) The reduced product is cooled to room temperature under a N2 atmosphere to obtain a cooled product.

2. The method for fluidizing hydrogen-based ore phase transformation of polymetallic associated pyrolusite according to claim 1, characterized in that: In the step (1), the raw ore is ground to a particle size of -0.074 mm ≥ 60%.

3. The method for fluidizing hydrogen-based ore phase transformation of polymetallic associated pyrolusite according to claim 1, characterized in that: In the step (2), the temperature of the preliminary drying is 100° C. to 200° C., and the time is 25 min to 45 min.

4. The method for fluidizing hydrogen-based ore phase transformation of polymetallic associated pyrolusite according to claim 1, characterized in that: In the step (3), the preheating temperature of the pyrolusite is 200° C. to 400° C., and the preheating time is 1 min to 5 min.

5. The method for fluidizing hydrogen-based ore phase transformation of polymetallic associated pyrolusite according to claim 1, characterized in that: In the step (3), the volume concentration of H2 in the mixed gas of N2 and H2 is 15% to 30%.

6. The method for fluidizing hydrogen-based ore phase transformation of polymetallic associated pyrolusite according to claim 1, characterized in that: In the step (3), the temperature of the fluidized hydrogen-based reduction is 500° C. to 700° C., and the reduction time is 15 min to 35 min.

7. The method for fluidizing hydrogen-based ore phase transformation of polymetallic associated pyrolusite according to claim 1, characterized in that: In the step (4), the cooling product (Mn 2+ ) / (TMn)≥90%.

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