Multi-metal associated pyrolusite hydrogen-based ore phase conversion system
By designing a hydrogen-based ore phase conversion system for polymetallic soft manganese ore and using hydrogen reduction technology to accurately regulate the ore phase structure, the problems of inefficient resource development, environmental pollution and energy consumption in traditional metallurgical processes have been solved, and efficient and green manganese resource development has been achieved.
Patent Information
- Application Number
- CN202510106254.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-23
- Publication Date
- 2025-04-25
AI Technical Summary
When dealing with polymetallic soft manganese ore, traditional hydrometallurgy and pyrometallurgy processes have problems such as high reagent consumption, high cost, serious environmental pollution, and large energy consumption and carbon emissions, which are difficult to meet the needs of green and efficient resource development.
A hydrogen-based ore phase conversion system of polymetallic soft manganese ore is designed, including a preheating oxidation subsystem, a hydrogen-based ore phase conversion subsystem, a cooling subsystem and a hot air circulation subsystem. The ore phase structure is accurately regulated through hydrogen reduction technology to achieve efficient conversion of manganese elements and green resource development.
By accurately controlling the mineral phase structure, the system improves resource utilization, reduces the negative impact on the environment, achieves efficient conversion of low temperature and low carbon, and reduces energy consumption and carbon emissions.
Smart Images
Figure CN119876580A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of pyrolusite reduction roasting, and in particular relates to a hydrogen-based ore phase conversion system for polymetallic associated pyrolusite. Background Art
[0002] Pyrolusite occupies a pivotal position in today's mining industry. It is one of the key sources of manganese, and manganese has indispensable applications in many industries. In the steel industry, manganese, as an important alloying element, can significantly improve the strength, toughness, wear resistance and corrosion resistance of steel. It is an essential raw material for the production of high-quality steel, and provides solid support for the vigorous development of many fields such as modern construction, machinery manufacturing, and the automobile industry. In the field of battery manufacturing, the processed products of pyrolusite are often used to prepare various battery electrode materials, help the development of new energy industries, and meet the growing demand for energy storage. In addition, it also plays a unique role in other industries such as chemical industry, widely participates in the synthesis of various manganese compounds, and promotes the diversification and refinement of chemical products. Pyrolusite is like the cornerstone of an industrial building, and it is of great significance to the stable operation and continuous progress of the entire industrial system. Under the current mining development pattern, pyrolusite, as an important manganese resource, has attracted much attention for its development and utilization. With the gradual reduction of high-grade and easy-to-handle manganese ore resources, the efficient development of polymetallic associated pyrolusite has become the focus of the industry. This type of ore has a complex composition. In addition to manganese, it is usually accompanied by a variety of valuable metals such as iron, cobalt, and nickel, making it difficult for traditional mineral processing technology to meet its comprehensive recovery needs.
[0003] The traditional hydrometallurgical treatment of polymetallic pyrolusite requires a large amount of strong acid and alkali leaching, which consumes a lot of reagents and is costly. It also produces acidic or alkaline wastewater containing heavy metal ions, ammonia nitrogen and other harmful substances. Direct discharge without proper treatment will pollute the surrounding water bodies and cause environmental problems such as acidification and eutrophication. The pressure and cost of environmental treatment are huge. When pyrometallurgy treats such ores, smelting and reduction at high temperatures will emit a large amount of greenhouse gases such as carbon dioxide and carbon monoxide, which is not conducive to low-carbon environmental protection. It relies on the combustion of coal and coke to maintain high temperatures, which increases energy consumption and carbon emissions. There are also problems such as uneven ore smelting and metal volatilization losses, resulting in low metal recovery and serious waste of resources. In this context, it is urgent to develop a system that can efficiently and greenly treat pyrolusite. Summary of the invention
[0004] In view of the problems existing in the prior art, the present invention provides a multi-metal associated pyrolusite hydrogen-based mineral phase conversion system. The system is mainly divided into a preheating oxidation subsystem, a hydrogen-based mineral phase conversion subsystem, and a cooling subsystem. The preheating oxidation subsystem uses the flue gas in the hydrogen-based mineral phase conversion subsystem to achieve preliminary preheating and fully recover heat resources. In the hydrogen-based mineral phase conversion subsystem, the reduction temperature, the reducing gas concentration and the reduction time are strictly controlled. Finally, manganese oxide is reduced in this order: MnO2→Mn2O3→Mn3O4→MnO. The reaction principle is: 2MnO2(s)+H2(g)=Mn2O3(s)+H2O(g), 3Mn2O3(s)+H2(g)=2Mn3O4(s)+H2O(g), Mn3O4(s)+H2(g)=3MnO(s)+H2O(g). Then the material enters the cooling subsystem, and after the protective gas nitrogen is cooled to room temperature, a cooling product is obtained.
[0005] A multi-metal associated pyrolusite hydrogen-based mineral phase conversion system, specifically comprising a preheating oxidation subsystem, a hydrogen-based mineral phase conversion subsystem, a cooling subsystem, a hot air circulation subsystem and a product collection pool;
[0006] The gas outlet of the preheating oxidation subsystem is connected to the gas inlet of the hydrogen-based mineral phase conversion subsystem, the discharge port of the hydrogen-based mineral phase conversion subsystem is connected to the feed port of the cooling subsystem, and the discharge port of the cooling subsystem is connected to the product collection pool;
[0007] The air inlet of the preheating oxidation subsystem is divided into two input paths, the first path is connected to the air outlet of the hydrogen-based mineral phase conversion subsystem, and the second path is connected to the air outlet of the cooling subsystem; the air outlet of the preheating oxidation subsystem is connected to the air inlet of the hot air circulation subsystem, and the hot air circulation subsystem is provided with an exhaust port.
[0008] The preheating oxidation subsystem includes a silo, a loss-in-weight scale, a ball mill, a material dryer, a material disperser, a primary cyclone separator, a primary sealing valve, a preheating oxidation reactor, a secondary cyclone separator, a burner and a fan; the silo, the loss-in-weight scale, the ball mill, the material dryer and the material disperser are connected in sequence, the feed port of the primary cyclone separator is connected to the discharge port of the material disperser, the discharge port of the primary cyclone separator is connected to the feed port of the primary sealing valve, the primary sealing valve is provided with an air inlet, and the discharge port of the primary sealing valve is connected to the feed port of the preheating oxidation reactor; three air inlets and one air inlet are provided at the bottom of the preheating oxidation reactor, the first air inlet is connected to the air outlet of the burner, the air inlet is connected to the fan, the gas outlet of the preheating oxidation reactor is connected to the gas inlet of the secondary cyclone separator; the air outlet of the secondary cyclone separator is connected to the air inlet of the primary cyclone separator.
[0009] The hydrogen-based mineral phase conversion subsystem includes a secondary sealing valve, a hydrogen-based mineral phase conversion reactor and a tertiary cyclone separator. The discharge port of the secondary cyclone separator in the preheating oxidation subsystem is connected to the feed port of the secondary sealing valve, the discharge port of the secondary sealing valve is connected to the feed port of the hydrogen-based mineral phase conversion reactor, and the secondary sealing valve is also provided with a nitrogen inlet; the gas outlet of the hydrogen-based mineral phase conversion reactor is connected to the gas inlet of the tertiary cyclone separator, the discharge port of the hydrogen-based mineral phase conversion reactor is connected to the cooling subsystem, the discharge port of the tertiary cyclone separator is connected to the ash return port of the hydrogen-based mineral phase conversion reactor, and a reducing gas inlet is also provided at the bottom of the hydrogen-based mineral phase conversion reactor; the gas outlet of the tertiary cyclone separator is connected to the second gas inlet of the preheating oxidation reactor in the preheating oxidation subsystem.
[0010] The cooling subsystem includes a four-stage cyclone separator and a cooling sealing valve, the air outlet of the four-stage cyclone separator is connected to the third air inlet of the preheating oxidation reactor in the preheating oxidation subsystem, the gas inlet of the four-stage cyclone separator is connected to the air outlet of the cooling sealing valve, and the discharge port of the four-stage cyclone separator is connected to the ash return port of the cooling sealing valve; the discharge port of the hydrogen-based mineral phase conversion reactor in the hydrogen-based mineral phase conversion subsystem is connected to the feed port of the cooling sealing valve, the discharge port of the cooling sealing valve is connected to the product collection pool, and the cooling sealing valve is also provided with a nitrogen inlet.
[0011] The hot air circulation subsystem includes a dust collector and a chimney. The air outlet of the primary cyclone separator in the preheating oxidation subsystem is connected to the air inlet of the dust collector, the air outlet of the dust collector is connected to the air inlet of the chimney, and the chimney is provided with an exhaust port.
[0012] The primary sealing valve, the secondary sealing valve and the cooling sealing valve have the functions of ensuring the unidirectional stable flow of materials and preventing the reverse permeation of gases.
[0013] The hydrogen-based mineral phase conversion reactor is composed of four chambers, which are arranged in parallel and staggered, and the inner walls of the four chambers are provided with electric heating wires.
[0014] Compared with the prior art, the present invention has the following beneficial effects:
[0015] 1. The hydrogen-based mineral phase transformation system of polymetallic associated pyrolusite provided by the present invention is expected to accurately control the mineral phase structure through innovative hydrogen-based reduction methods, realize the precise mineral phase transformation of manganese elements, improve resource utilization, reduce negative impacts on the environment, and open up a new path for the green development of complex manganese ore resources.
[0016] 2. The system structure of the present invention is compact. Compared with the traditional carbon-based roasting technology, the preheating oxidation system can fully recover the waste heat and reduce energy consumption. The hydrogen-based mineral phase converter uses the suspended reducing gas flow to make the material fully contact with the gas, and the heat and mass transfer efficiency is better. It can achieve low-temperature, low-carbon and high-efficiency conversion, the required reaction time and reaction temperature are lower, and the carbon emission is less. The hydrogen-based mineral phase converter is more precise in temperature control and can achieve accurate conversion of quartzite. The setting of the cooling sealing valve can ensure that the obtained quartzite (MnO) product is not easily oxidized, ensuring the high efficiency of subsequent leaching. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 A schematic structural diagram of a hydrogen-based mineral phase conversion system for polymetallic associated pyrolusite of the present invention;
[0018] Among them, 1- silo, 2- loss-in-weight scale, 3- ball mill, 4- material dryer, 5- material disperser, 6- first-stage cyclone separator, 7- first-stage sealing valve, 8- preheating oxidation reactor, 9- second-stage cyclone separator, 10- second-stage sealing valve, 11- hydrogen-based mineral phase conversion reactor, 12- third-stage cyclone separator, 13- fourth-stage cyclone separator, 14- cooling sealing valve, 15- product collection pool, 16- burner, 17- dust collector, 18- chimney, 19- fan. DETAILED DESCRIPTION
[0019] Combined with Figure 1 , a clear and complete description of the technical solutions in the embodiments of the present invention is given. It should be noted that the examples described in the present invention are only used for further explanation and illustration, rather than limiting the scope of application. Based on the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the patent of the present invention.
[0020] Example 1
[0021] A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system, the structural schematic diagram of which is shown in FIG. Figure 1 As shown, it specifically includes a preheating oxidation subsystem, a hydrogen-based mineral phase conversion subsystem, a cooling subsystem, a hot air circulation subsystem and a product collection pool 15;
[0022] The gas outlet of the preheating oxidation subsystem is connected to the gas inlet of the hydrogen-based mineral phase conversion subsystem, the discharge port of the hydrogen-based mineral phase conversion subsystem is connected to the feed port of the cooling subsystem, and the discharge port of the cooling subsystem is connected to the product collection pool 15;
[0023] The air inlet of the preheating oxidation subsystem is divided into two input paths, the first path is connected to the air outlet of the hydrogen-based mineral phase conversion subsystem, and the second path is connected to the air outlet of the cooling subsystem; the air outlet of the preheating oxidation subsystem is connected to the air inlet of the hot air circulation subsystem, and the hot air circulation subsystem is provided with an exhaust port.
[0024] The preheating oxidation subsystem includes a silo 1, a weight loss scale 2, a ball mill 3, a material dryer 4, a material disperser 5, a primary cyclone separator 6, a primary sealing valve 7, a preheating oxidation reactor 8, a secondary cyclone separator 9, a burner 16 and a fan 19; the discharge port of the silo 1 is connected to the feed port of the weight loss scale 2, the discharge port of the weight loss scale 2 is connected to the feed port of the ball mill 3, the discharge port of the ball mill 3 is connected to the feed port of the material dryer 4, the discharge port of the material dryer 4 is connected to the feed port of the material disperser 5, the feed port of the primary cyclone separator 6 is connected to the feed port of the material disperser 5, and the feed port of the primary cyclone separator 6 is connected to the feed port of the material disperser 5. The discharge port is connected, the discharge port of the primary cyclone separator 6 is connected to the feed port of the primary sealing valve 7, the primary sealing valve 7 is provided with an air inlet, and the discharge port of the primary sealing valve 7 is connected to the feed port of the preheating oxidation reactor 8; the preheating oxidation reactor 8 is provided with three air inlets and one air inlet at the bottom, the first air inlet is connected to the air outlet of the burner 16, the air inlet is connected to the fan 19, the gas outlet of the preheating oxidation reactor 8 is connected to the gas inlet of the secondary cyclone separator 9; the air outlet of the secondary cyclone separator 9 is connected to the air inlet of the primary cyclone separator 6. Among them, the primary sealing valve 7 has the function of ensuring the unidirectional stable flow of materials and blocking the reverse permeation of gases.
[0025] In the preheating oxidation subsystem, polymetallic associated pyrolusite is used as the raw ore, which is sent from the silo 1 to the ball mill 3 through the weight loss scale 2. Under the grinding action of the ball mill 3, the particle size of the raw ore is gradually refined until it reaches the feeding particle size standard required by the subsequent process. After grinding, the material is dried by the material dryer 4 and dispersed by the material disperser 5, and then sent to the primary cyclone separator 6. Driven by wind power, the pyrolusite and the hot flue gas enter the primary cyclone separator 6 together to achieve efficient gas-solid separation. After separation, the flue gas is discharged from the top outlet of the primary cyclone separator 6, and the material enters the bottom feed port of the preheating oxidation reactor 8 through the primary sealing valve 7 from the bottom outlet. The pyrolusite in the preheating oxidation reactor 8 moves slowly from bottom to top with the hot flue gas until it reaches the secondary cyclone separator 9. During this period, the preheating oxidation reactor 8 and the interior of the secondary cyclone separator 9 create an ideal environment for the material, prompting the material to complete the preheating and oxidation reaction.
[0026] The hydrogen-based mineral phase conversion subsystem includes a secondary sealing valve 10, a hydrogen-based mineral phase conversion reactor 11 and a tertiary cyclone separator 12. The discharge port of the secondary cyclone separator 9 in the preheating oxidation subsystem is connected to the feed port of the secondary sealing valve 10, and the discharge port of the secondary sealing valve 10 is connected to the feed port of the hydrogen-based mineral phase conversion reactor 11. The secondary sealing valve 10 is also provided with a nitrogen inlet; the gas outlet of the hydrogen-based mineral phase conversion reactor 11 is connected to the gas inlet of the tertiary cyclone separator 12, and the discharge port of the hydrogen-based mineral phase conversion reactor 11 is connected to the cooling subsystem. The discharge port of the first-stage cyclone separator 12 is connected to the ash return port of the hydrogen-based mineral phase conversion reactor 11. The bottom of the hydrogen-based mineral phase conversion reactor 11 is also provided with a reducing gas inlet, into which a mixed gas of reducing gas and nitrogen is introduced; the gas outlet of the third-stage cyclone separator 12 is connected to the second gas inlet of the preheating oxidation reactor 8 in the preheating oxidation subsystem; the hydrogen-based mineral phase conversion reactor 11 is composed of four chambers, which are arranged in parallel and staggered. From the outlet to the inlet, they are the first chamber, the second chamber, the third chamber, and the fourth chamber, and the inner wall thereof is provided with a heating wire. Among them, the secondary sealing valve 10 has the function of ensuring the unidirectional stable flow of materials and blocking the reverse permeation of gases.
[0027] In the hydrogen-based mineral phase conversion subsystem, the hydrogen-based mineral phase conversion reactor 11 provides hot flue gas for the preheating oxidation reactor 8 and the secondary cyclone separator 9 in the preheating oxidation subsystem, realizing the heat utilization inside the system. The preheated and oxidized pyrolusite enters the hydrogen-based mineral phase conversion reactor 11 from the lower discharge port of the secondary cyclone separator 9 through the secondary sealing valve 10, and the reducing gas is fed from the bottom of the hydrogen-based mineral phase conversion reactor 11 in an ascending manner. Driven by the reducing gas flow, the material gradually flows from the first chamber to the fourth chamber in a W-shaped manner. In this dynamic flow process, the pyrolusite continues to undergo a reduction reaction and gradually transforms into quartzite. In the gas circulation system of the hydrogen-based mineral phase conversion reactor 11, nitrogen is introduced from the lower part of the reactor and finally discharged from the discharge port. The flue gas at the discharge port of the hydrogen-based mineral phase conversion reactor 11 carries fine particles into the three-stage cyclone separator 12, and the three-stage cyclone separator 12 is used to achieve a thorough gas-solid separation. The separated flue gas is discharged from the upper part of the three-stage cyclone separator 12 and refluxes into the preheating oxidation reactor 8, further enhancing the system's synergy and resource utilization.
[0028] The cooling subsystem includes a four-stage cyclone separator 13 and a cooling sealing valve 14. The gas outlet of the four-stage cyclone separator 13 is connected to the third gas inlet of the preheating oxidation reactor 8 in the preheating oxidation subsystem, the gas material inlet of the four-stage cyclone separator 13 is connected to the gas outlet of the cooling sealing valve 14, and the material outlet of the four-stage cyclone separator 13 is connected to the ash return port of the cooling sealing valve 14; the material outlet of the hydrogen-based mineral phase conversion reactor 11 in the hydrogen-based mineral phase conversion subsystem is connected to the material inlet of the cooling sealing valve 14, and the material outlet of the cooling sealing valve 14 is connected to the material inlet of the product collection pool 15, and the cooling sealing valve 14 is also provided with a nitrogen inlet. Among them, the cooling sealing valve 14 has the function of ensuring the unidirectional stable flow of materials and blocking the reverse permeation of gases.
[0029] In the cooling subsystem, the reduced pyrolusite is cooled to room temperature through the cooling sealing valve 14 to obtain a cooling product. In the cooling sealing valve 14, the calcined reduced product is gradually cooled to room temperature under the N2 protective atmosphere, and the flue gas at the discharge port of the cooling sealing valve 14 carries the fine particles into the four-stage cyclone separator 13, and the four-stage cyclone separator 13 is used to achieve a thorough gas-solid separation, and the separated flue gas is discharged from the upper part of the four-stage cyclone separator 13 and refluxed to the preheating oxidation reactor 8 to enhance the resource utilization of the system.
[0030] The hot air circulation subsystem includes a dust collector 17 and a chimney 18. The air outlet of the primary cyclone separator 6 in the preheating oxidation subsystem is connected to the air inlet of the dust collector 17, and the air outlet of the dust collector 17 is connected to the air inlet of the chimney 18. The chimney 18 is provided with an exhaust port.
[0031] In the hot air circulation subsystem, the flue gas separated by the primary cyclone separator 6 is dedusted by the dust collector 17 and then discharged through the chimney 18.
Claims
1. A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system, characterized in that: Specifically, it includes a preheating oxidation subsystem, a hydrogen-based mineral phase conversion subsystem, a cooling subsystem, a hot air circulation subsystem and a product collection pool; The gas outlet of the preheating oxidation subsystem is connected to the gas inlet of the hydrogen-based mineral phase conversion subsystem, the discharge port of the hydrogen-based mineral phase conversion subsystem is connected to the feed port of the cooling subsystem, and the discharge port of the cooling subsystem is connected to the product collection pool; The air inlet of the preheating oxidation subsystem is divided into two input paths, the first path is connected to the air outlet of the hydrogen-based mineral phase conversion subsystem, and the second path is connected to the air outlet of the cooling subsystem; the air outlet of the preheating oxidation subsystem is connected to the air inlet of the hot air circulation subsystem, and the hot air circulation subsystem is provided with an exhaust port.
2. A multi-metallic associated pyrolusite hydrogen-based mineral phase conversion system according to claim 1, characterized in that: The preheating oxidation subsystem includes a silo, a loss-in-weight scale, a ball mill, a material dryer, a material disperser, a primary cyclone separator, a primary sealing valve, a preheating oxidation reactor, a secondary cyclone separator, a burner and a fan; the silo, the loss-in-weight scale, the ball mill, the material dryer and the material disperser are connected in sequence, the feed port of the primary cyclone separator is connected to the discharge port of the material disperser, the discharge port of the primary cyclone separator is connected to the feed port of the primary sealing valve, the primary sealing valve is provided with an air inlet, and the discharge port of the primary sealing valve is connected to the feed port of the preheating oxidation reactor; three air inlets and one air inlet are provided at the bottom of the preheating oxidation reactor, the first air inlet is connected to the air outlet of the burner, the air inlet is connected to the fan, the gas outlet of the preheating oxidation reactor is connected to the gas inlet of the secondary cyclone separator; the air outlet of the secondary cyclone separator is connected to the air inlet of the primary cyclone separator.
3. A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system according to claim 2, characterized in that: The hydrogen-based mineral phase conversion subsystem includes a secondary sealing valve, a hydrogen-based mineral phase conversion reactor and a tertiary cyclone separator. The discharge port of the secondary cyclone separator in the preheating oxidation subsystem is connected to the feed port of the secondary sealing valve, the discharge port of the secondary sealing valve is connected to the feed port of the hydrogen-based mineral phase conversion reactor, and the secondary sealing valve is also provided with a nitrogen inlet; the gas outlet of the hydrogen-based mineral phase conversion reactor is connected to the gas inlet of the tertiary cyclone separator, the discharge port of the hydrogen-based mineral phase conversion reactor is connected to the cooling subsystem, the discharge port of the tertiary cyclone separator is connected to the ash return port of the hydrogen-based mineral phase conversion reactor, and a reducing gas inlet is also provided at the bottom of the hydrogen-based mineral phase conversion reactor; the gas outlet of the tertiary cyclone separator is connected to the second gas inlet of the preheating oxidation reactor in the preheating oxidation subsystem.
4. A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system according to claim 3, characterized in that: The cooling subsystem includes a four-stage cyclone separator and a cooling sealing valve, the air outlet of the four-stage cyclone separator is connected to the third air inlet of the preheating oxidation reactor in the preheating oxidation subsystem, the gas inlet of the four-stage cyclone separator is connected to the air outlet of the cooling sealing valve, and the discharge port of the four-stage cyclone separator is connected to the ash return port of the cooling sealing valve; the discharge port of the hydrogen-based mineral phase conversion reactor in the hydrogen-based mineral phase conversion subsystem is connected to the feed port of the cooling sealing valve, the discharge port of the cooling sealing valve is connected to the product collection pool, and the cooling sealing valve is also provided with a nitrogen inlet.
5. A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system according to claim 4, characterized in that: The hot air circulation subsystem includes a dust collector and a chimney. The air outlet of the primary cyclone separator in the preheating oxidation subsystem is connected to the air inlet of the dust collector, the air outlet of the dust collector is connected to the air inlet of the chimney, and the chimney is provided with an exhaust port.
6. A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system according to claim 4, characterized in that: The primary sealing valve, the secondary sealing valve and the cooling sealing valve have the functions of ensuring the unidirectional stable flow of materials and preventing the reverse permeation of gases.
7. A polymetallic associated pyrolusite hydrogen-based mineral phase conversion system according to claim 3, characterized in that: The hydrogen-based mineral phase conversion reactor is composed of four chambers, which are arranged in parallel and staggered, and the inner walls of the four chambers are provided with electric heating wires.