CN114293014A - Silicon carbide-free thermal reduction magnesium metallurgy device and method - Google Patents
Silicon carbide-free thermal reduction magnesium metallurgy device and method Download PDFInfo
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Abstract
A silicon carbide-free thermal reduction magnesium metallurgy device and a method. Aiming at the heavy pressure of double carbon and double control targets of the iron alloy industry and the magnesium metallurgy industry, the aim of non-carbonization of magnesium metallurgy is fulfilled by cooperatively connecting material flow and energy flow between the two industries and using a silicon alloy superheated energy as a magnesium metallurgy reduction energy. Namely, the invention adopts molten silicon alloy to reduce MgO, and finishes the MgO reduction process when excessive (the silicon/oxygen ratio is more than or equal to 1.5) silicon alloy is overheated (the temperature is higher than 1300 ℃ melting point temperature of 75FeSi and is more than 300 ℃) by adjusting the MgO reaction amount; the molten state of the silicon alloy is kept, the magnesium metallurgy process is facilitated to replace the reaction between a Pidgeon process solid phase (silicon alloy) and a solid phase (MgO) through the reaction between a liquid phase (silicon alloy) and the solid phase (MgO), particularly, a liquid phase wrapping solid phase reaction structure is formed through molten metal atomization, the heat transfer, mass transfer and energy transfer between the two phases are enhanced, the reduction efficiency is improved, the energy consumption of the magnesium metallurgy is greatly reduced, and meanwhile, the carbonization-free process is realized.
Description
Technical Field
The invention relates to a magnesium metallurgy preparation method, in particular to a silicon carbide-free thermal reduction magnesium metallurgy device and a method.
Background
The magnesium metal and the magnesium alloy have the advantages of high specific strength, good heat conduction and electric conductivity, damping and shock absorption, electromagnetic external shielding, easy machining, easy recovery and the like, are widely applied and become the third metal engineering material second to steel and aluminum. The world production of magnesium metal in 2017 has exceeded 120 ten thousand tons. China is a world-wide magnesium-producing country, and the yield accounts for more than 85% of the total world yield. The Chinese original magnesium is produced by Pidgeon process. The Pidgeon process is a vacuum thermal reduction magnesium-smelting technique which takes dolomite as raw material and takes ferrosilicon alloy (75# ferrosilicon) containing 75 percent of silicon as a reducing agent. The Pidgeon method has been in history for over 70 years since birth, and has been industrially applied in China for over 40 years. After decades of development, particularly application of heat accumulating type reduction furnaces in recent decades, energy consumption is reduced from 10t of standard coal for producing 1t of magnesium to 4-5 t. If the energy consumption of the ferrosilicon alloy as a reducing agent is added, the comprehensive energy consumption of the technology for smelting magnesium by the Pidgeon process is still higher than 8-9t standard coal, and the unit energy consumption even exceeds that of metal aluminum, so that the method is one of nonferrous metallurgy industries with the highest unit energy consumption. The magnesium metallurgy industry mainly using petrochemical energy is one of the main forces of carbon dioxide emission. According to the statistics of the China nonferrous metals industry Association, the national magnesium yield in 2019 is over 84 ten thousand tons, the emission of carbon dioxide is about 1375-. With the compelling push of the national 'double carbon' target and the general requirement for the energy consumption double control target, the magnesium metallurgy and 'two high' industry represented by the ferrosilicon alloy and CO2The big households are facing serious survival crisis. How to greatly save energy and reduce carbon is the key for determining whether Pidgeon magnesium metallurgy can survive and develop.
Pidgeon magnesium metallurgy is to reduce the pellet made by roasting white jade, 75 ferrosilicon alloy, fluorite and calcium oxide at about 1200 ℃ and 10pa of vacuum degree. Because the heat-conducting property of the pellets is poor, the self efficiency of the solidification reaction is low, and the efficiency is continuously reduced along with the overflow of magnesium vapor, the reduction time reaches 8-12h, the energy consumption is high, and the MgO reduction rate is less than 80%. Similarly, as a reducing agent for magnesium metallurgy, silicon alloys are smelted by reducing a mixture of a carbon source, quartz and an iron source in a molten state in a submerged arc furnace by arc heating at a temperature of about 1800 ℃ or higher and a molten iron outlet at 1700 ℃ or higher. All iron alloys, including silicon-based alloys, are mainly cast in a pit due to the forming process. The heat of solution and solidification can not be recovered, which causes high energy consumption of the iron alloy industry.
In pijiang magnesium metallurgy, silicon-based alloys are used only as a reducing agent for magnesium metallurgy. The temperature of magnesium metallurgy is above 900 ℃, the melting point of silicon is 1410 ℃, the melting point of the silicon-iron alloy is 1200-1400 ℃, and the melting point of the mainly adopted 75FeSi is 1300 ℃. If the silicon alloy is used as the heat source of magnesium metallurgy, the energy cost of magnesium metallurgy is obviously reduced. Specifically, the heat of the molten silicon alloy outlet reduced to 1750 ℃ to 1300 ℃ is used as a heat source for magnesium metallurgy reduction, so that the heat of the silicon alloy is greatly recycled, and the double control and double carbon targets of the silicon alloy industry and the magnesium metallurgy industry are realized.
The silicon alloy belongs to the ferroalloy industry, and is troubled by the qualitative industry of high energy consumption and high pollution for a long time. The industry also continuously does a great deal of work in the aspects of equipment maximization, industrial process automation and production lean, and the productivity and the continuous and automatic control level of a single device are obviously improved. In the aspect of energy saving, the method makes a breakthrough in the aspects of flue gas waste heat, combustible gas recovery in flue gas, waste residue waste heat utilization and the like, and the energy consumption is obviously reduced. However, because the forming of the iron alloy is mainly static forming, the existing forming technology cannot meet the requirements of planned production, and almost all the solidification heat of the iron alloy is consumed. This is the largest portion of the ferroalloy heat energy lost. But since the advent of ferroalloys, no critical change has been achieved.
The Pidgeon magnesium smelting process has the obvious advantages of small investment, convenient operation, large-scale production and the like in the prior magnesium metallurgy technology, is popular with Chinese people, and enables Chinese to rapidly develop into the biggest world Pidgeon magnesium smelting country. Its significant cost advantage also becomes a profit for Chinese magnesium to occupy 85% of world markets. And a solid economic foundation is laid for the wide-range use of the magnesium alloy in the world. Around the problems existing in the Pidgeon magnesium smelting process, various researches are carried out by domestic related academies, for example, a magnesium metallurgy integration technology carried out by Yangtian team of northeast university integrates the calcination and the reduction of dolomite; the Wang Xiao gang of the university of the Xian industry invents a multi-heat-source internal-heating magnesium-smelting device, and establishes a new process for smelting magnesium by a large-scale vertical furnace; shaanxi fu gu is based on the development idea of 'centralized layout, green production, project grouping, industrial circulation and garden load bearing', but the essence of Pidgeon reduction is not changed. Other people have carried out certain work on the magnesium reduction vertical furnace, have made certain progress, have not broken through the technical category of Pidgeon process magnesium smelting either. Because of this, with the mandatory implementation of the "dual carbon" goal, the pidgeon magnesium metallurgy industry featuring "high energy consumption, high pollution, high emission" will certainly become the primary control goal, and the survival of the chinese magnesium industry and the world magnesium metal supply will face serious challenges.
The Pidgeon process for magnesium production has several problems. Firstly, the energy consumption is high, 4-5 tons of standard coal are required for smelting 1 ton of metal magnesium, and in addition, the energy consumption for smelting the ferrosilicon alloy is increased, and the energy consumption of each ton of primary magnesium reaches 8-9 tons of standard coal; secondly, the reduction rate is low, and the reduction rate of the MgO is less than 80 percent at present; thirdly, the efficiency is low, and the reduction time is as long as 8-12 h; thirdly, the waste residue generated by reduction and the fluorite added in the reaction are pollution sources; and the influence of short service life of the reduction tank on production and the like.
In fact, there are two fundamental reasons for the above problems in the Pidgeon process for magnesium production. Firstly, the reduction pellets are in solid-phase reaction, the contact of reactants is insufficient, and particularly, the mass transfer efficiency is further reduced along with the overflow of magnesium vapor, so that complete reaction cannot be realized; secondly, the heat transfer efficiency is low. The reaction pellet contains mainly calcined dolomite, ferrosilicon alloy, fluorite, calcium oxide, etc. whether internally heated or externally heated. These components are poor conductors, and have low heat conduction efficiency, which causes difficulty in heat transfer between the inside and outside of the pellets and between the pellets, thereby causing problems of long reduction time, low reaction efficiency, and volume and capacity of the reduction tank. In this context, the addition of the mineralizer fluorite contributes to the acceleration of the reduction efficiency, but causes contamination with hydrogen fluoride gas. Therefore, the key point for realizing the energy saving of magnesium metallurgy is to improve the heat transfer and reaction efficiency of reactants. It is well known that, from the viewpoint of reaction efficiency, gas-solid > liquid-solid > solid-solid. Therefore, if the solid-solid reaction in the magnesium reduction process can be converted into the liquid-solid reaction, the heat transfer and the reaction efficiency can be greatly enhanced. According to the idea, the aim can be achieved by enabling the reducing agent-silicon series alloy in the magnesium reduction process to participate in MgO reduction in a liquid phase.
The silicon alloy is in a liquid phase state when smelting and tapping, and the tapping temperature is generally required to be more than 1600 ℃ and is far higher than the reduction reaction temperature of 900-. The reaction of the high-temperature liquid-phase silicon ferroalloy and the solid MgO obviously enhances the heat transfer efficiency, obviously improves the reduction efficiency of the MgO, does not need to adopt a vacuum method to improve the reaction efficiency and reduce the reduction temperature, and further creates process conditions for normal-pressure or negative-pressure magnesium metallurgy. After magnesium vapor reduced by silicon thermal reduction overflows, the silicon alloy solution can timely supplement gas to overflow reserved gaps, the close contact state between the silicon alloy solution and the residual MgO particles is always kept, and the continuous heat transfer and reduction efficiency is kept. Therefore, it is also not necessary to add fluorite as a mineralizer. Eliminating HF gas pollution.
Disclosure of Invention
The invention aims to provide a silicon carbide-free thermal reduction magnesium metallurgy device and a method, which can realize high efficiency, low carbon, energy saving and greening of a magnesium metallurgy process.
In order to achieve the aim, the invention relates to a carbonless silicon thermal reduction magnesium metallurgical device, which comprises an upper molten state silicon ferroalloy furnace, a middle reduction furnace and a lower slag refining furnace which are communicated in sequence;
the upper end of the molten silicon ferroalloy furnace is provided with a molten silicon ferroalloy feeding pipeline, a heating wire is arranged in the molten silicon ferroalloy feeding pipeline, the lower end of the molten silicon ferroalloy feeding pipeline is provided with a molten silicon ferroalloy outlet communicated with the middle reduction furnace, a lifting rod penetrates through the molten silicon ferroalloy furnace, the lower end of the lifting rod penetrates through the molten silicon ferroalloy outlet, atomizing nozzles communicated with the reduction furnace are arranged around the molten silicon ferroalloy outlet, the atomizing nozzles are communicated with a fluidized bed containing calcined dolomite powder through a pipeline, and a high-pressure argon inlet is also formed in the fluidized bed;
the middle reduction furnace comprises a shell and a reduction furnace sleeved in the shell, the upper end of the reduction furnace is communicated with a molten silicon ferroalloy outlet and an atomizing nozzle, a gap is reserved between the lower end of the reduction furnace and the lower end of the shell, a magnesium vapor area is formed in a cavity between the shell and the reduction furnace, a condensation crystallization device is arranged outside the shell, and a slag outlet at the lower end of the shell is communicated with a lower slag refining furnace;
the lower part slag refining furnace is installed on a supporting material, the upper end of the slag refining furnace is communicated with a slag outlet at the lower end of the shell, a taphole pipeline communicated with a pouring treatment device is arranged on the side wall of the bottom end, a slag outlet pipeline is arranged on the side wall of the upper end, an exhaust pipeline and a rotary blowing device are arranged at the top end, an inlet of the rotary blowing device is connected with an argon inlet pipeline, the lower end of the rotary blowing device extends into the bottom of the slag refining furnace, and a graphite rotor is installed at the lower end of the rotary blowing device.
The molten silicon series ferroalloy furnace is made of heat insulating materials, the lower end of the molten silicon series ferroalloy furnace is of a conical structure, and a molten silicon series ferroalloy feeding pipeline valve is arranged on a molten silicon series ferroalloy feeding pipeline.
And a heater is arranged on a pipeline connecting the atomizing nozzle and the fluidized bed.
The heating wire device is installed in the shell, the high-temperature thermocouple is arranged in the reduction furnace, the upper ends of the shell and the reduction furnace are both in a horn mouth-shaped structure, and the lower end of the shell is provided with a conical structure formed by refractory materials.
And the inner wall of the shell is provided with a suspension fixing device, and the reduction furnace is suspended in the shell through the suspension fixing device.
And a slag outlet valve is arranged on the slag outlet.
The slag refining furnace is composed of an outer heat insulation material and an inner fireproof material, and a heating wire device is arranged between the heat insulation material and the inner fireproof material.
And the exhaust pipeline and the argon inlet pipeline are respectively provided with an exhaust pipeline valve and an argon inlet pipeline valve.
The tapping hole pipeline and the slag hole pipeline are respectively provided with a tapping hole pipeline valve and a slag hole pipeline valve, and the tapping hole siphon device and the slag hole siphon device are respectively arranged on the pipelines at the rear ends of the tapping hole pipeline valve and the slag hole pipeline valve.
The invention relates to a method for reducing magnesium metallurgy by using silicon carbide-free heat, which comprises the following steps:
1) the high-temperature molten silicon ferroalloy enters a molten silicon ferroalloy furnace through a feeding pipeline, and is kept at 1700-1800 ℃ under the combined action of a heating wire device and a wrapped heat-insulating material;
2) controlling the molten-state silicon-based ferroalloy to enter an intermediate reduction furnace area through the up-and-down operation of a lifting rod, simultaneously, fully mixing the high-temperature calcined dolomite, namely calcined powder with high-pressure argon entering from a high-pressure argon inlet in a fluidized bed, enabling the mixed gas-solid powder to reach the required high-temperature condition through a heater, performing cross mixed flow with two flows of the molten-state silicon-based ferroalloy under the action of argon pressure, forming molten-state silicon-based ferroalloy coated solid calcined powder under the impact action of the high-pressure argon, and generating a large amount of sprayed liquid-phase silicon-based alloy coated solid-phase powder liquid drops to enter an intermediate high-temperature reduction area for magnesium metal reduction metallurgy;
3) the liquid phase silicon series alloy coated solid phase powder liquid drop reacts at 1450-1800 ℃, wherein the heating wire device regulates and controls the reaction temperature, and the reaction formula is as follows:
2MgO(s)+Si(Fe)(l)＝2Mg(g)+SiO2(s)
SiO2(s)+2CaO(s)＝2CaO·SiO2(l)
the generated high-temperature magnesium vapor moves downwards under the combined action of gravity and the pressure of argon at the upper end and magnesium vapor generated in the reaction. Because of low density, the magnesium powder overflows from the lower edge of the reduction bin and turns back upwards to form a magnesium vapor area, and finally enters a condensation crystallization device to be condensed and sublimated into crystallized magnesium;
4) SiO2 and the like generated in the reaction process are wrapped in the silicon alloy liquid, and under the action of gravity, together with 2 CaO. SiO2 and unreacted iron, the slag of the high-temperature product falls into a slag refining furnace from a slag outlet through a slag outlet valve;
5) under the protection of internal refractory materials, a heating wire device is arranged on the outer layer of the lower refining furnace to ensure that the temperature of the refining furnace is above 1350, ferroalloy is positioned at the lower part of the refining furnace, oxide slag is positioned at the upper part of the refining furnace, a graphite rotor at the end of a rotary blowing purification device is arranged at the bottom of a refining furnace molten pool, argon is blown in from an argon inlet pipeline under the control of an argon inlet pipeline valve, and generated fine argon bubbles play a role in stirring a melt in the floating process to drive oxide impurities with light weight to float upwards and promote impurity separation, namely, the slag melt is purified and uniformly mixed with various components;
6) opening a slag hole pipeline valve after the molten slag in the refining furnace is accumulated to the set depth of the refining furnace, discharging oxide molten slag in the refining furnace to the outside of the furnace through the slag hole pipeline under the action of a siphon, opening an iron outlet pipeline valve after the height of the silicon-containing ferroalloy solution in the refining furnace reaches 40-50% of the capacity of the refining furnace, discharging the solution to pouring treatment equipment through the iron outlet pipeline under the action of the siphon for subsequent ferroalloy treatment and utilization, still keeping a molten iron bath with the furnace capacity of 10-20% in the refining furnace, and designing an overpressure protection valve at the top end of the smelting furnace to control the pressure in the furnace.
Aiming at the heavy pressure of the double-carbon and double-control targets of the iron alloy industry and the magnesium metallurgy industry, the invention realizes the energy recovery of silicon alloy and the energy utilization of magnesium metallurgy by the cooperative connection of materials and energy between the two industries, and realizes the energy-saving and carbon-reducing targets of the two high-energy-consumption industries. Namely, the invention adopts molten silicon alloy to reduce MgO, and finishes the MgO reduction process when excessive (the silicon/oxygen ratio is more than or equal to 1.5) silicon alloy is overheated (the temperature is higher than 1300 ℃ melting point temperature of 75FeSi and is more than 300 ℃) by adjusting the MgO reaction amount;
the molten state of the silicon-based alloy is maintained, and the magnesium metallurgy process is facilitated to replace the reaction between the solid phase (silicon-based alloy) and the solid phase (MgO) in the Pidgeon process through the reaction between the liquid phase (silicon-based alloy) and the solid phase (MgO). Has less influence on the production of the silicon series alloy. The material flow and the energy flow in the two process flows of the silicon alloy and the magnesium metallurgy are closely connected, the molten state of the silicon alloy is kept, and particularly, a liquid-phase wrapped solid-phase reaction structure is formed through atomization of molten metal, so that heat transfer, mass transfer and energy transfer between two phases are enhanced, the reduction efficiency is improved, the energy consumption of the magnesium metallurgy is greatly reduced, meanwhile, a carbonization-free process is realized, and the efficient, low-carbon, energy-saving and green preparation of the magnesium metallurgy process is realized.
The technical effects brought by adopting the scheme are as follows:
1. energy is saved. Energy consumption in the magnesium metallurgy process is basically eliminated, namely 4-5 tons of standard coal per ton of raw magnesium, and energy is saved by more than 90%;
2. and no carbon. The innovative non-carbomorphism reduction metallurgy technology can effectively reduce the carbon emission of the magnesium metallurgy industry, and the magnesium metallurgy as the largest carbon dioxide emission industry in China occupies more than 12 percent of the carbon emission in China;
3. high efficiency. The Pidgeon process generally requires 8-12h for reducing magnesium. The invention strengthens heat transfer and mass transfer by virtue of high temperature and liquid-solid wrapping form, and realizes the conversion of the magnesium metallurgy reaction process from long time to instant time;
4. high reduction rate. The Pidgeon process adopts solid-solid reaction between low heat-conducting materials, and the reduction rate of MgO is less than 80%. According to the invention, the solid MgO form is coated with excessive high-temperature liquid phase reducing agent, so that the reduction rate is improved to more than 95%;
5. eliminating HF pollution. Fluorite is used as a mineralizer fluorite for smelting magnesium by Pidgeon process, and the addition amount is generally about 3%. The fluorite forms HF gas at high temperature to be discharged, thereby causing environmental pollution. The invention does not need to add fluorite raw materials.
6. Realizes the large-scale, continuous and large-scale production of magnesium metallurgy. The Pidgeon process is used as a main process of magnesium metallurgy in China, is always multi-layer multi-row small-sized reduction tank intermittent production, and has low efficiency, high energy consumption and poor environment. The invention can realize continuous, large-scale and low-carbon manufacturing by high-temperature reduction and high-efficiency reaction under normal pressure.
Drawings
FIG. 1 is a schematic structural diagram of a carbonless silicon thermal reduction magnesium metallurgy device according to the present invention.
Wherein, 1, melting silicon ferroalloy charging pipeline valve; 2. a molten silicon ferroalloy feed line; 3. lifting a pull rod; 4. a furnace for melting a silicon-based ferroalloy; 5. a heater wire device; 6. melting a silicon-based iron alloy; 7. a heater; 8. calcined dolomite powder (including MgO and CaO); 9. a fluidized bed; 10. a high pressure argon inlet; 11. a condensation crystallization device; 12. a suspension fixture; 13. a high temperature thermocouple; 14. an argon inlet pipe; 15. an argon inlet pipeline valve; 16. a rotary blowing device; 17. a slag hole pipeline valve; 18. a siphon; 19. a slag outlet conduit; 20. slag; 21. pouring treatment equipment; 22. a siphon device; 23. a taphole pipe; 24. a taphole pipe valve; 25. silicon-containing ferrous alloy water; 26. a support material; 27. a refractory material; 28. a heater wire device; 29. a thermal insulation material; 30. a slag outlet valve; 31. an exhaust pipe valve; 32. an exhaust duct; 33. a slag outlet; 34. a refractory material; 35. a reduction furnace; 36. a magnesium vapor zone; 37. a heater wire device; 38. a housing; 39. a suspension fixture; 40. liquid phase silicon series alloy wraps the solid phase powder drop; 41. an atomizing nozzle.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Referring to fig. 1, the manufacturing apparatus of the present invention includes an upper molten silicon-based ferroalloy furnace, a middle reduction furnace, and a lower slag refining furnace, which are sequentially communicated;
the molten silicon ferroalloy furnace 4 is made of heat-insulating materials, the upper end of the molten silicon ferroalloy furnace is provided with a molten silicon ferroalloy feeding pipeline 2 with a molten silicon ferroalloy feeding pipeline valve 1, a heating wire 5 is installed inside the molten silicon ferroalloy furnace 4, the lower end of the molten silicon ferroalloy furnace is of a conical structure, the lower end of the molten silicon ferroalloy furnace is provided with a molten silicon ferroalloy outlet communicated with a middle reduction furnace 35, a lifting rod 3 penetrates through the molten silicon ferroalloy furnace 4, the lower end of the lifting rod 3 penetrates through the molten silicon ferroalloy outlet, atomizing nozzles 41 communicated with the reduction furnace 35 are installed around the molten silicon ferroalloy outlet, the atomizing nozzles 41 are communicated with a fluidized bed 9 provided with calcined white powder 8 through a pipeline and a heater 7 installed on the pipeline, and the fluidized bed 9 is also provided with a high-pressure argon inlet 10;
the middle reduction furnace comprises a shell 38 and a reduction furnace 35 sleeved in the shell 38, wherein suspension fixing devices 12 and 39 are arranged on the inner wall of the shell 38, the reduction furnace 35 is suspended in the shell 38 through the suspension fixing devices 12 and 39, a heating wire device 37 is arranged in the shell 38, a high-temperature thermocouple 13 is arranged in the reduction furnace 35, the upper ends of the shell 38 and the reduction furnace 35 are both in a bell mouth-shaped structure, the upper end of the reduction furnace 35 is communicated with a molten silicon series ferroalloy outlet and an atomizing nozzle 41, a gap is reserved between the lower end of the reduction furnace 35 and the lower end of the shell 38, a conical structure formed by refractory materials 34 is arranged at the lower end of the shell 38, a magnesium vapor area 36 is formed in a cavity between the shell 38 and the reduction furnace 35, a condensation crystallization device 11 is arranged outside the shell 38, and a slag outlet 33 at the lower end of the shell is communicated with a lower slag refining furnace;
the lower slag refining furnace is arranged on a supporting material 26 and consists of an outer heat insulating material 29 and an inner refractory material 27, a heating wire device 28 is arranged between the heat insulating material 29 and the inner refractory material 27, the upper end of the slag refining furnace is communicated with a slag outlet 33 of a slag outlet valve 30 at the lower end of the shell, an iron outlet pipeline 23 communicated with a pouring treatment device 21 is arranged on the side wall at the bottom end, a slag outlet pipeline 19 is arranged on the side wall at the upper end, an exhaust pipeline 32 with an exhaust pipeline valve 31 and a rotary blowing device 16 are arranged at the top end, an iron outlet pipeline valve 24 and a slag outlet pipeline valve 17 are respectively arranged on the iron outlet pipeline 23 and the slag outlet pipeline 19, an iron outlet siphon device 22 and a slag outlet siphon device 18 are respectively arranged on pipelines at the rear ends of the iron outlet pipeline valve 24 and the slag outlet pipeline valve 17, the inlet of the rotary blowing device 16 is connected with an argon inlet pipeline 14 with an argon inlet pipeline valve 15, the lower end of the rotary blowing device 16 extends into the bottom of the slag refining furnace, and a graphite rotor is arranged at the lower end of the rotary blowing device 16.
The invention relates to a silicon carbide-free thermal reduction magnesium metallurgy method, which comprises the following steps:
an upper partial area: the high-temperature molten silicon ferroalloy 6 enters the upper molten silicon ferroalloy furnace 4 from the molten silicon ferroalloy feeding pipeline 2 under the control of the molten silicon ferroalloy feeding pipeline valve 1, and the high-temperature condition meeting the reduction reaction is kept at 1800 ℃ under the combined action of the heating wire device 5 and the wrapped heat-insulating material. The molten silicon ferroalloy can be controlled to enter an intermediate reduction furnace area by the up-and-down operation of the lifting rod 3, meanwhile, dolomite which is calcined at high temperature, namely calcined dolomite powder 8 is fully mixed with high-pressure argon gas entering from a high-pressure argon gas inlet 10 in a fluidized bed 9, the mixed gas-solid powder reaches the required high-temperature condition through a heater 7, under the action of an atomizing nozzle 41, the molten silicon ferroalloy 6 metal enters an atomizing area through a guide pipe in the middle of the atomizing nozzle 41 and interacts with the core calcined dolomite powder 8 and the atomizing gas argon gas high-speed two-phase flow, the molten metal forms an equal-thickness liquid film on the powder surface and is rapidly solidified to obtain the metal coated powder, namely, a large amount of sprayed liquid phase silicon ferroalloy coated solid phase powder droplets 40 are generated. Entering a middle high-temperature reduction area for magnesium metal reduction metallurgy.
Intermediate reducing part area: the liquid-solid coated droplets start to react in a high-temperature environment, wherein the temperature range is 1450-. Wherein, the heating wire device is used for ensuring the temperature to be in a proper range. The reduction furnace 35 is suspended in the intermediate reaction device under the combined action of the suspension fixing devices 12.39 on the left and right sides. Wherein the reaction formula is:
2MgO(s)+Si(Fe)(l)＝2Mg(g)+SiO2(s)
SiO2(s)+2CaO(s)＝2CaO·SiO2(l)
the generated high-temperature magnesium vapor moves downwards under the upper end pressure, the periphery of the reduction furnace 35 is sealed, and the lower part of the reduction furnace is not sealed. After leaving the reducing furnace 35 from the lower part, the magnesium is turned back upwards to enter the condensing and crystallizing devices 11 at the two sides of the device from the magnesium vapor zone 36 due to the action of low density and high temperature, and crystallized magnesium is formed by condensation.
The middle area and the lower area are provided with refractory material 34 in the middle, which plays a role of fire-proof safety and a certain supporting effect.
Lower part area: SiO2 and the like generated in the reaction process are wrapped in the silicon-based alloy liquid, and under the action of gravity, together with 2 CaO. SiO2 and unreacted iron, the slag of a high-temperature product is controlled by a slag outlet valve and falls into a slag refining furnace from a slag outlet 33.
The outer layer of the lower refining furnace is provided with a heating wire device 28 under the protection of the internal refractory material 27, and the temperature in the furnace is ensured to be about 1500. The lower support material 26 ensures the stability and safety of the overall equipment. Segregation occurs because the density of the iron alloy and the above-mentioned oxide impurities differ considerably. The ferroalloy is positioned at the lower part of the refining furnace, and the oxide slag is positioned at the upper part of the molten pool. Utilize the graphite rotor of 16 tip of rotatory jetting purifier at the molten bath bottom, under the control of argon gas inlet pipeline valve 15, blow in argon gas by argon gas inlet pipeline 14, tiny argon gas bubble that produces plays the stirring effect to the fuse-element at the come-up in-process, drives the light oxide impurity come-up of quality, promotes the impurity separation, carries out purification treatment to the slag fuse-element promptly to make wherein various composition misce bene, make things convenient for standing and layering on next step. When the slag 20 in the furnace is accumulated to a certain depth in the furnace, a slag outlet pipeline valve is opened, and the oxide slag in the furnace is discharged out of the furnace through a slag outlet pipeline 19 under the action of a siphon 18. According to calculation, after the content of Si in the silicon-containing iron alloy water 25 in the furnace is reduced to below 20 percent and the furnace capacity is accumulated to 40-50 percent in the furnace, a tap hole pipeline valve 24 is opened, the silicon-containing iron alloy water is discharged to the pouring treatment equipment 21 through a tap hole pipeline 23 under the action of a siphon 22 for subsequent iron alloy treatment and utilization, a molten iron pool which accounts for about 10-20 percent of the furnace capacity is still kept in the furnace, and the heat conductivity of the heating wire device 28 is facilitated. Wherein, for safety reasons, an exhaust duct 32 controlled by an exhaust duct valve 31 is designed at the top end of the smelting furnace for discharging excess gas in the furnace.
According to the invention, the materials flow and the energy flow in the two process flows of silicon alloy and magnesium metallurgy are closely connected, especially the technical innovation of MgO reduction mode and mechanism is combined with a carbon-free innovative smelting method, and the efficient, low-carbon, energy-saving and green preparation of the magnesium metallurgy process is realized. The key point of the connection of the two metallurgical processes of silicon alloy and magnesium metallurgy is that the MgO reduction process needs to be completed when the temperature of the silicon alloy is from 1410 (melting point of silicon) to 1700 ℃ or above (tapping temperature point), and simultaneously, the silicon alloy is ensured to be refinedThe range impact is minimal. The core of the method is to realize the high-efficiency operation of the magnesium metallurgy process on the basis of keeping the energy balance, the material balance and the reaction speed balance in the reaction process. It is known from the foregoing that silicon-based alloys and MgO take part in reactions in molten and solid forms, respectively. There are two reactant contact-reaction-separation processes in this process. The reaction process needs to be completed in a short time, and a high-speed reaction must be achieved. That is, high-speed approach of the two phases of reaction-high-speed overflow is required. This is not possible in a static solution with solid reactant systems. Therefore, a core-shell structure in which a solid phase is wrapped in a liquid phase must be adopted. Because the requirements of refining the silicon alloy on components and temperature need to be ensured, the amount of the silicon alloy is far larger than that of a solid phase, and therefore, the material condition of a core-shell structure is also ensured. The core-shell structure has a sufficient reaction interface, and the high-speed rate requirement of magnesium reduction can be ensured by the sufficient reaction power formed at high temperature and the rapid overflow of the shell layer condition. In addition to the first time, the problem of subsequent treatment of the product needs to be solved. Wherein the generated magnesium vapor can overflow the core-shell structure and is discharged out of the reaction system in a gas phase; wherein the solid phase product SiO is produced2And SiO carried with MgO addition2、Al2O3、Fe2O3And CaO and other impurities enter the molten pool again along with the liquid-phase silicon ferroalloy which does not participate in the reaction, so that the slag-iron separation process is completed.
The silicon-based alloy of the present invention comprises: various alloys containing silicon as a component, such as metallic silicon, silicon-based iron alloy, silico-calcium, silico-aluminum-iron, silico-calcium-iron, etc.; the invention can also be used in the process of reducing solid powder by using metal heat such as aluminum heat, silicon heat, calcium heat and the like.
The silicon alloy is used as a source of magnesium metallurgy reducing agent silicon and also used as a heat source of magnesium metallurgy;
the core-shell liquid drop structure formed by tightly wrapping MgO particles by the excessive high-heat liquid-phase silicon alloy eliminates gaps between solid and solid reactants, has high combination degree and large contact area, has the reaction temperature of more than 1700 ℃ (far higher than the magnesium metallurgy temperature of Pidgeon process), and more importantly, has short magnesium vapor external diffusion path, realizes quick approach between two phases, quick reaction and quick separation, and obviously improves the reduction efficiency;
4. atmospheric/negative pressure magnesium metallurgy: the Pidgeon magnesium smelting adopts a vacuum magnesium smelting process, and the vacuum degree is about 10 pa. The purpose is to reduce the temperature and improve the efficiency. The high-temperature reduction condition provided by the invention does not need vacuum condition. Can be reduced under the conditions of normal pressure, micro positive pressure and negative pressure:
5. the recovery and utilization of the solidification heat of the silicon series alloy are realized. Because the domestic ferroalloy forming process is integrally lagged behind, the ferroalloy solidification heat can not be recovered all the time. The invention realizes the recovery of the smelting and solidifying heat of the silicon series alloy by fusing two metallurgical processes, and obviously reduces the energy consumption of the silicon series alloy industry.
The invention can be used for reducing preparation of magnesium metal, and can be used for reducing materials which can be used in a molten state, if volatile products such as low-boiling-point metals and compounds can be obtained. The method can not only be used for magnesium thermal reaction, but also be used for aluminothermic, silicothermic, calthermic and other reduction reactions, and for producing ferrovanadium, metal manganese, ferrotungsten, ferronickel, rare earth ferrosilicon, silico-calcium-iron, titanium-silicon alloy, silicon-barium, silicon-strontium and other silicon composite alloys by using silicon as a reducing agent, and the like, can fully utilize reaction heat energy, increase the generation efficiency, and is a design with epoch-making significance for changing the traditional metal smelting mode.
Claims (10)
1. A silicon carbide-free thermal reduction magnesium metallurgy device is characterized in that: comprises an upper molten silicon ferroalloy furnace, a middle reduction furnace and a lower slag refining furnace which are communicated in sequence;
the device is characterized in that a molten silicon ferroalloy feeding pipeline (2) is arranged at the upper end of the molten silicon ferroalloy furnace (4), a heating wire (5) is arranged in the molten silicon ferroalloy furnace, a molten silicon ferroalloy outlet communicated with a middle reduction furnace (35) is formed in the lower end of the molten silicon ferroalloy furnace (4), a lifting rod (3) penetrates through the molten silicon ferroalloy outlet, atomizing nozzles (41) communicated with the reduction furnace (35) are arranged around the molten silicon ferroalloy outlet, the atomizing nozzles (41) are communicated with a fluidized bed (9) containing calcined dolomite powder (8) through a pipeline, and a high-pressure argon inlet (10) is formed in the fluidized bed (9);
the middle reduction furnace comprises a shell (38) and a reduction furnace (35) sleeved in the shell (38), the upper end of the reduction furnace (35) is communicated with a molten silicon ferroalloy outlet and an atomizing nozzle (41), a gap is reserved between the lower end of the reduction furnace and the lower end of the shell (38), a magnesium vapor area (36) is formed in a cavity between the shell (38) and the reduction furnace (35), a condensation crystallization device (11) is installed outside the shell (38), and a slag outlet (33) at the lower end of the shell is communicated with a lower silicon ferroalloy slag refining furnace;
the lower part silicon system ferroalloy slag refining furnace is installed on supporting material (26), the upper end of the silicon system ferroalloy slag refining furnace is communicated with an outlet (33) at the lower end of the shell, an iron outlet pipeline (23) communicated with a pouring treatment device (21) is arranged on the side wall of the bottom end, a slag outlet pipeline (19) is arranged on the side wall of the upper end, an exhaust pipeline (32) and a rotary blowing device (16) are arranged at the top end, the inlet of the rotary blowing device (16) is connected with an argon inlet pipeline (14), the lower end of the rotary blowing device (16) extends into the bottom of the slag refining furnace, and a graphite rotor is installed at the lower end of the rotary blowing device (16).
2. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: the molten-state silicon-based ferroalloy furnace (4) is made of a heat-insulating material, the lower end of the molten-state silicon-based ferroalloy furnace (4) is of a conical structure, and a molten-state silicon-based ferroalloy feeding pipeline valve (1) is arranged on the molten-state silicon-based ferroalloy feeding pipeline (2).
3. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: and a heater (7) is arranged on a pipeline connecting the atomizing nozzle (41) and the fluidized bed (9).
4. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: the heating wire device (37) is installed in the shell (38), the high-temperature thermocouple (13) is installed in the reduction furnace (35), the upper ends of the shell (38) and the reduction furnace (35) are both in a bell mouth-shaped structure, and the lower end of the shell (38) is provided with a conical structure formed by refractory materials (34).
5. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: and the inner wall of the shell (38) is provided with hanging and fixing devices (12 and 39), and the reduction furnace (35) is hung in the shell (38) through the hanging and fixing devices (12 and 39).
6. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: and a slag outlet valve (30) is arranged on the slag outlet (33).
7. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: the slag refining furnace is composed of an outer heat insulating material (29) and an inner refractory material (27), and a heating wire device (28) is arranged between the heat insulating material (29) and the inner refractory material (27).
8. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: and an exhaust pipeline valve (31) and an argon inlet pipeline valve (15) are respectively arranged on the exhaust pipeline (32) and the argon inlet pipeline (14).
9. The carbonless silicon thermal reduction magnesium metallurgy apparatus according to claim 1, wherein: and a tapping hole pipeline valve (24) and a slag hole pipeline valve (17) are respectively arranged on the tapping hole pipeline (23) and the slag hole pipeline (19), and a tapping siphon device (22) and a slag siphon device (18) are respectively arranged on the pipelines at the rear ends of the tapping hole pipeline valve (24) and the slag hole pipeline valve (17).
10. A carbonless thermal reduction magnesium metallurgy process as set forth in claim 1, characterized by the steps of:
1) the high-temperature molten-state silicon-series ferroalloy (6) enters the molten-state silicon-series ferroalloy furnace (4) from the molten-state silicon-series ferroalloy feeding pipeline (2) under the control of the molten-state silicon-series ferroalloy feeding pipeline valve (1), and the reduction reaction condition of 1500-plus 1800 ℃ is kept under the combined action of the heating wire device (5) and the wrapped heat insulation material;
2) controlling the molten-state silicon-based ferroalloy (6) to enter an intermediate reduction furnace area through the up-and-down operation of a lifting rod (3), simultaneously, fully mixing high-temperature calcined dolomite, namely calcined dolomite powder (8) with high-pressure argon entering from a high-pressure argon inlet (10) in a fluidized bed (9), enabling the mixed gas-solid powder to reach a required high-temperature condition through a heater (7), entering a reduction furnace (35) together with the molten-state silicon-based ferroalloy (6) under the action of an atomizing nozzle (41), interacting with the core calcined dolomite powder (8) and atomizing gas argon high-speed two-phase flow, forming a silicon-based ferroalloy liquid film with a certain thickness on the surface of the calcined dolomite powder (8) by the molten-state silicon-based ferroalloy (6), realizing the coating of a solid phase (MgO) by a liquid phase (molten-state silicon-based ferroalloy), namely generating a large amount of sprayed liquid-phase silicon-based alloy coated solid-phase powder droplets (40), entering a middle high-temperature reduction region for magnesium metal reduction metallurgy;
3) the liquid phase silicon series alloy coated solid phase powder liquid drop reacts at the temperature of 1450-1700 ℃, wherein, the heating wire device (37) regulates and controls the reduction reaction temperature, wherein the reaction formula is as follows:
2MgO(s)+Si(Fe)(l)＝2Mg(g)+SiO2(s)
SiO2(s)+2CaO(s)＝2CaO·SiO2(l)
high-temperature magnesium vapor generated by the reaction moves downwards under the action of upper-end pressure, and returns upwards to enter a condensation crystallizing device (11) from a magnesium vapor area (36) to be sublimated into crystallized magnesium when meeting condensation after leaving a reducing furnace (35) from the lower part under the action of low density and high temperature;
4) SiO2 generated in the reaction process and CaO. SiO2 generated in the subsequent reaction are wrapped in the silicon alloy liquid, and under the action of gravity, the silicon alloy liquid, iron and other solid impurities which do not participate in the reaction fall into a slag refining furnace from a slag outlet (33) through a slag outlet valve (30);
5) under the protection of internal refractory materials (27), a lower refining furnace is provided with a heating wire device (28) on the outer layer, the temperature of the refining furnace is ensured to be about 1400-1500 ℃, ferroalloy is positioned at the lower part of the refining furnace, oxide slag is positioned at the upper part of the refining furnace, a graphite rotor at the end part of a rotary blowing purification device (16) is utilized at the bottom of a refining furnace molten pool, argon is blown in from an argon inlet pipeline (14) under the control of an argon inlet pipeline valve (15), and generated fine argon bubbles play a role in stirring a melt in the floating-up process to drive oxide impurities with light weight to float up, so that impurity separation is promoted, namely the slag melt is purified, and various components in the slag melt are uniformly mixed;
6) after the slag (20) in the refining furnace accumulates to the set depth of the refining furnace, a slag hole pipeline valve is opened, oxide slag in the refining furnace is discharged out of the furnace through a slag hole pipeline (19) under the action of a siphon (18), after 40-50% of the capacity of the refining furnace is accumulated by silicon-containing ferroalloy water (25) in the refining furnace, an iron hole pipeline valve (24) is opened, the silicon-containing ferroalloy water is discharged into a pouring treatment device (21) under the action of a siphon (22) through an iron hole pipeline (23) for subsequent ferroalloy treatment and utilization, a molten iron bath with the furnace capacity of 10-20% in the refining furnace is still kept, and an exhaust pipeline (32) controlled by an overpressure protection valve (31) is designed at the top end of the smelting furnace and used for controlling the pressure in the furnace.
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