• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: A method of producing metal sulfides directly from metal and sulfur by mechanothermal operation is provided to reduce waste byproduct generation as well as improve process efficiency. CONSTITUTION: The production method of metal sulfides includes the steps of charging a sealed jar with sulfur to be alloyed, at least one particulate/granular metal species, together with steel balls; rotating the sealed jar for preparing a mutually diffused compound or a chemically connected metal sulfide through a series of crush-conjunction-crush process in the sealed jar; and thermal treatment of above mutually diffused compound or chemically connected metal sulfide in a separated heating device for chemical stabilization.
    公开号:KR20020066863A
    申请号:KR1020010007298
    申请日:2001-02-14
    公开日:2002-08-21
    发明作者:안인섭；이강률；박동규
    申请人:가야에이엠에이 주식회사；대한민국 (경상대학교 총장)；
    IPC主号:
    专利说明:

    METHODS OF PRODUCING METAL SULFIDES
    [17] Metal sulfide is a generic term for a compound formed by combining metal and sulfur, and representative examples thereof include FeS, MnS, MoS 2 , Cu 2 S, and WS 2 . Such metal sulfides are widely used in various fields including metal and mechanical fields because of their nonmetallic properties and lubricity.
    [18] Since most natural minerals are present as oxides or sulfides, metal sulfides are obtained as by-products produced during smelting or refining, or as chemical methods for obtaining sulfides by reacting oxides or hydrates and then purifying them. Alternatively, a pyrolysis method for pyrolyzing sulfur oxides to obtain sulfides may be used. However, such conventional manufacturing methods inevitably generate pollutants that must be treated separately such as waste liquid and waste gas during the manufacturing process, and there are many difficulties in the purification process to increase the purity, and the manufacturing process is long and complicated. As it becomes longer, it is manufactured very economically.
    [19] In addition, efforts have been made to prepare metal sulfides by mechanical alloying methods. This is the name given to supplying the necessary driving force as mechanical energy from the outside, and was first attempted in the manufacture of super heat resistant alloy in 1970. The mechanical alloying method is a method capable of finely and uniformly alloying two or more metals or non-metallic components with a solid phase reaction rather than a liquid phase reaction in a molten state. It is a novel production method that is effective as an alloying method that can be used when a base metal and a metal-to-metal bond are required.
    [20] However, the mechanical alloying method has a small one-time charge amount due to the method of supplying the energy necessary for the reaction only with mechanical energy, and the time required for the completion of the reaction is also increased from tens to hundreds of hours, so that the equipment is large in mass production. This leads to higher initial capital investment and higher product prices.
    [21] In the present invention, to solve the above-mentioned difficulties of the prior art, to simply produce a metal sulfide in a shorter time.
    [22] That is, the present invention is widely used throughout the fields of electronics, ceramics and industrial equipment, including metal and mechanical fields as lubricants and release agents, by means of a mechanical-mechanothermal approach, unlike conventional chemical and mechano-metallic approaches. The technical problem is to provide a method for efficiently producing a metal sulfide.
    [1] 1 is a schematic perspective view of a mechanized alloying apparatus according to the present invention.
    [2] 2 is a schematic diagram of a process in which the powder of the A and B components are alloyed according to the mechanical alloying time.
    [3] 3 is a graph showing the degree of alloying according to the mechanical alloying time and heat treatment of the iron-sulfur component system of an embodiment of the present invention.
    [4] Figure 4 is an X-ray diffraction analysis of the alloying process according to the mechanical alloying time of the iron-sulfur component system of an embodiment of the present invention.
    [5] 5 is a schematic perspective view showing a horizontal ball milling apparatus used in the present invention.
    [6] Figure 6 is a graph showing the degree of alloying according to the mechanical alloying time and heat treatment of the manganese-sulfur component system of an embodiment of the present invention.
    [7] 7 is a schematic diagram of a heating apparatus used in the present invention.
    [8] 8 is a manufacturing process chart of the metal sulfide according to the present invention.
    [9] Figure 9 is an X-ray diffraction analysis before and after heat treatment of the manganese-sulfur component system of an embodiment of the present invention.
    [10] <Explanation of symbols for the main parts of the drawings>
    [11] 1 ---- Atelier 2 ---- Steel ball
    [12] 3 ---- Alloy Components 4 ---- Rotating Body
    [13] 5 ---- Motor 6 ---- Rotary shaft
    [14] 7 ---- Ball mill 8 ---- Preheater
    [15] 9 ---- Main part 10 ---- Cooling part
    [16] 11 ---- Gas Supply Device 12 ---- Mesh Belt
    [23] The present invention provides a method for producing a metal sulfide, by using a mechanical alloying method and heat treatment, to produce a metal sulfide directly from the metal and sulfur as raw materials to reduce the production of waste by-products, and to increase the efficiency of the production The purpose.
    [24] Means of the present invention for achieving the above object is as follows.
    [25] The method for producing a metal sulfide of the present invention includes a powdery or granular material of sulfur and at least one metal component to be alloyed with steel balls in a sealed container; Rotating the vessel or rotating the rotor inside the vessel to produce a dispersedly mixed mixture, or a partly chemically bonded metal sulfide, in the process of shock absorption and pulverization-bonding-pulverization; It is characterized in that the heat treatment in a separate heating furnace to chemically stabilize.
    [26] The present invention will be described in more detail with reference to the accompanying drawings as follows.
    [27] The basic process for the preparation of metal sulfides according to the invention consists of the steps of mixed dispersion-heating-grinding-classification as shown in FIG.
    [28] The process of mixed dispersion is as shown in FIG. 1 is a schematic perspective view of a mechanical alloying apparatus according to the present invention, in which one or more metal components 3 in the form of sulfur and powder or granules of alloys are formed into an attrile ruler 1 which is a rigid container. ) Together. Then, the atliter ruler 1 is rotated or the rotating body 4 inside the atliter is rotated to transmit the rotational force, which is mechanical energy, to the alloying component 3 as the impact energy of the steel ball 2, thereby absorbing the shock. And the pulverization-bonding-pulverization process is repeated to form a mixture or partial compound of uniform composition (hereinafter referred to as mixed dispersion). This method can reduce the time to 1/10 to 1/3 or less and increase the input amount several times than forming a complete intermetallic compound by the conventional mechanical alloying method.
    [29] As shown in FIG. 7, the mixed dispersion obtained by the mixing-dispersion process is charged to the heating furnace in which the protective atmosphere is maintained by the gas supply apparatus 11, and is heated. This not only produces stable sulfides, but also allows removal of excess sulfur components and sulfur oxides formed by contact with air in the previous process, making it possible to produce pure metal sulfides.
    [30] In FIG. 7, reference numeral 12 denotes a preheating part, 9 a main heat part, 10 a cooling part, and 12 a mesh belt.
    [31] The obtained intermetallic compound is pulverized by a ball mill or stamp mill or the like in the horizontal ball milling apparatus of FIG. 5, and powder-treated using a sieve to produce a metal sulfide having a desired composition and particles. In FIG. 5, 3 is a component to be alloyed, 5 is a drive motor, 6 is a rotating shaft, and 7 is a ball mill.
    [32] The raw material used in the present invention is preferably in the form of a powder. This is because the larger the initial particle size of the raw material, the longer the time required for mixing and dispersing. Suitable raw material particle sizes are preferably 60 mesh or less for metals and 150 mesh or less for sulfur.
    [33] In addition, the raw metal may be a pure metal or a metal alloy. Therefore, not only the metal sulfide of a 1 metal component but also the metal sulfide of a composite composition can be prepared. In addition, in the conventional chemical process, it is impossible to produce a metal sulfide with a specific component ratio or an additional process is required, but the production method according to the present invention does not have any probability of interalloy such as alloy solidity, specific gravity difference and difference in melting point. In any case, the desired component ratio can be adjusted by precise metering and dosing without further processing. However, in the case of the compounds according to the invention, it is preferred that the metal-sulfur mixture or compound is adjusted to at least 50% of the total. If less than 50%, due to the influence of other impurities, it may be impossible to exhibit the original function, such as lubricity.
    [34] Figure 2 of the accompanying drawings shows a schematic diagram of a process of alloying the powder of the A and B components according to the mechanical alloying time.
    [35] Hereinafter, the present invention will be described in more detail with reference to Examples.
    [36] Example
    [37] Iron sulfide manufacturers
    [38] In the atrit ruler 1 as shown in FIG. 1, 57.4 g of elemental sulfur corresponding to 100 g of iron of -100 mesh size and 1: 1 in atomic weight are 1/4 inch corresponding to 50% of the atliter capacity. It was put together with 3 kg of iron steel balls (2) of size, covered with a lid, and filled with an inert gas. Samples were taken at each hour after holding the rotating shaft 4 at 600 rpm for up to 30 minutes to apply mechanical energy. The collected sample was heated and cooled at 750 ° C. for 30 minutes in a heating furnace in which a protective atmosphere was maintained to obtain a result as in FIG. 3. 3 is a graph showing the mechanical alloying time of the iron-sulfur component system and the degree of alloying according to heat treatment.
    [39] In the case of alloying with mechanical energy in the attrit, the time taken for 100% alloying was 30 hours or more. However, when the heat treatment was performed in parallel, 100% alloying was obtained in 10 hours or more. In this case, as confirmed in FIG. 4, the X-ray diffraction method also proved to be FeS, so that the degree of alloying could be easily confirmed.
    [40] Manganese Sulfate Manufacturing
    [41] In a horizontal ball milling apparatus as shown in FIG. 5, a high chromium-based φ 15 mm steel ball was prepared using 3.500 kg of manganese powder equivalent to 40% of the capacity of the atrit ruler 1 and 2.043 kg of elemental sulfur corresponding to 1: 1 by atomic weight. It was put together with 55 kg and rotated at a speed of 120 rpm to apply mechanical energy. The holding time was up to 300 hours, and the sample was taken each time. The sample collected was heated at 800 ° C. for 30 minutes while maintaining a protective atmosphere, and then cooled. The result obtained by measuring the alloying degree before and after heating is shown in FIG.
    [42] 6 is a graph showing the degree of alloying according to the mechanical alloying time and heat treatment of the manganese-sulfur component system.
    [43] The degree of 100% alloying was obtained in the mechanical energy treatment of 300 hours or more before the heat treatment, but the heat treatment time was shown from 30 hours, indicating that the treatment time was reduced by about 1/10. In the manganese-sulfur component system shown in FIG. 9, the X-ray diffractograms before and after the heat treatment showed that the complete metal sulfide was formed after the heat treatment.
    [44] According to the above embodiments, the method of the present invention facilitates the formation of sulfides in the case of manganese having high affinity as well as iron having low affinity with oxygen, and shortening the treatment time by 1/3 to 1/10. I can see that I can. It is inferred by this invention that it is possible to produce metal sulfides in most metals, such as Mo, Cu and W, with similar or low affinity to oxygen.
    [45] In the case of preparing the metal sulfide through the mechanical energy and heat treatment according to the present invention, not only a complete metal sulfide can be prepared, but also unreacted sulfide which may be present in the case of manufacturing by mechanical energy is completely removed in the heat treatment process. The corrosion damage by unreacted sulfur was able to be minimized. In addition, since it is possible to remove the sulfur oxide that may occur during the mechanical alloying process by the heat treatment, there is an advantage that even if the maintenance level of the required protective atmosphere during the mechanical process is lowered.
    [46] The advantages of producing metal sulfides by the process according to the invention are as follows.
    [47] 1. It can make high purity metal sulfide economically. The purification effort is reduced as compared to the conventional method, making it economical in producing high purity sulfides.
    [48] 2. It is possible to make single or complex metal sulfides. Existing methods have made it difficult to produce complex metal sulfides except when mixed with impurities. However, using the present invention, the combination of raw material powders provides the possibility of alloy alloying, such as the degree of solid solution, specific gravity difference, and melting point difference. In any case without them, it is possible to easily make complex sulphides without additional processes.
    [49] 3. The stabilization process is conducted by inducing a chemical reaction in a protective atmosphere using a separate heating furnace, so that not only all the reactants form a uniform metal sulfide, but also no sulfur oxides are formed on the surface, and completely removes unreacted sulfur components. This can eliminate the damage such as corrosion caused by this.
    [50] 4. The productivity of the dispersion mixing process, which is an expensive process, can be increased, and mass production can be performed by a heating furnace, thereby improving economic efficiency.
    权利要求:
    Claims (3)
    [1" claim-type="Currently amended] A method of producing metal sulfides, in which a powdered or granular raw material of sulfur and at least one metal component is added together with steel balls in a sealed vessel, and the vessel is rotated or the rotating body inside the vessel is absorbed and crushed. Through the process of bonding-milling, the metal sulfides, which are dispersed and mixed, or partly chemically bonded metal sulfides, are heat-treated in separate furnaces to be chemically stabilized, and then pulverized and classified. Manufacturing method.
    [2" claim-type="Currently amended] The method of claim 1, wherein the pure metal is a pure metal or a composite metal.
    [3" claim-type="Currently amended] The method of claim 1 wherein the metal sulfide comprises at least 50% of a compound of metal and sulfur or a mixture of metal and sulfur.
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    同族专利:
    公开号 | 公开日
    KR100407194B1|2003-11-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-02-14|Application filed by 가야에이엠에이 주식회사, 대한민국 (경상대학교 총장)
    2001-02-14|Priority to KR10-2001-0007298A
    2002-08-21|Publication of KR20020066863A
    2003-11-28|Application granted
    2003-11-28|Publication of KR100407194B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-2001-0007298A|KR100407194B1|2001-02-14|2001-02-14|Method of producing metal sulfides|
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