CN110395734B - Method for producing granular metal and titanium carbide by using red mud as raw material - Google Patents
Method for producing granular metal and titanium carbide by using red mud as raw material Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
A method for producing granular metal and titanium carbide by using red mud as a raw material. Belongs to the field of smelting. The method comprises the steps of mixing red mud and low-volatile solid carbon, placing the mixture in a molten salt bath, constructing a reducing molten salt bath reaction system, reducing iron and gallium in the red mud into elemental iron and gallium step by matching with a staged heating system, and converting a titanium mineral into titanium carbide or titanium oxycarbide. The highest heat preservation temperature of the molten salt bath is 1148-1199 ℃, and the products after reaction exist in the forms of simple substance iron, gallium-iron alloy, titanium carbide or titanium oxycarbide particles. The product has high particle density and is easy to sink to the bottom of the reactor. The lower layer molten salt containing reactants is pressed out by an air pressure adjusting mechanism of the reactor, then solid product particles and liquid molten salt are separated by a porous plate, iron, titanium carbide and gallium-iron alloy are separated from the solid product by magnetic separation, and finally titanium carbide particles are separated from residues by an eddy current separation mode. The method has the advantages of short production flow, wide raw material source and low production cost.
Description
Technical Field
The invention belongs to the field of mineral processing, and relates to a method for producing granular metal and titanium carbide by using red mud as a raw material.
Technical Field
Titanium carbide has excellent properties such as high temperature resistance, high strength, corrosion resistance, high heat conductivity and the like, and is widely applied to the fields of metal ceramics, cutting tool materials, wear-resistant and fireproof materials, heat-resistant gallium-iron alloys and the like. Meanwhile, the red mud is the most important titanium-containing resource in China, but the red mud cannot be used for producing titanium carbide at present. The invention takes the red mud as the main raw material, can directly produce high-quality titanium carbide powder by heating for 1 time, and simultaneously produces gallium slag, granular simple substance iron and steel, thereby realizing the comprehensive utilization of iron, titanium and gallium elements in the red mud.
The Chinese patent CN108441636A discloses a method for treating red mud by two-stage vacuum reduction, which comprises the following steps: (1) respectively grinding the red mud and the carbonaceous reducing agent, mixing the ground red mud and the carbonaceous reducing agent with additive sodium sulfate, and pressing the mixture into blocks; (2) carrying out reduction reaction under the conditions of vacuum and 700-1200 ℃; (3) carrying out magnetic separation after levigating to obtain a Fe-FeS alloy ball product and magnetic separation tailings; (4) mixing the magnetic separation tailings, aluminum powder and additives and pressing into secondary agglomerates; (5) and (3) carrying out a two-stage reduction reaction under the conditions of vacuum and 700-1200 ℃, and crystallizing the steam into solid sodium metal. The method provided by the invention realizes the thorough separation of sodium element in the red mud, and creates favorable conditions for the utilization of subsequent residues and the extraction of rare elements in the subsequent residues.
The invention Chinese patent CN108950180A discloses a method for extracting iron by reducing roasting of red mud by a Bayer process, wherein red mud is added with chloride as a segregation agent, a sodium-containing compound as an accelerant, an iron-containing compound as a nucleating agent, a calcium-containing compound as a sulfur-fixing agent and a carbonaceous reducing agent, and according to the mass of the red mud, the addition amount of the chloride is 3-10 wt%, the addition amount of the sodium-containing compound is 5-15%, the addition amount of the iron-containing compound is 3-8%, the addition amount of the calcium-containing compound is 5-12%, and the addition amount of the carbonaceous reducing agent is 5-15%. The invention adopts a method of reducing and roasting red mud to reduce iron in the red mud into low-price magnetic substances, and the low-price magnetic substances are gathered together under the action of a nucleating agent to form large-particle crystal grains which are separated out by weak magnetic separation. The method can obviously improve the metal conversion rate and the segregation effect in the red mud reduction roasting, thereby achieving the effect of improving the iron recovery rate or grade.
The Chinese invention patent CN109160744A discloses a red mud magnetizing roasting comprehensive utilization system and a process, relating to the technical field of mineral resource utilization, and the key point of the technical scheme is that the system comprises the following steps: detecting, analyzing and batching: sampling the red mud, detecting and analyzing, and adding an additive for inhibiting the high-temperature combination of silicon, titanium and aluminum and iron into the red mud in proportion; stirring and drying: stirring the proportioned red mud for 30-60 min to uniformly mix the materials, and then drying at the drying temperature of 180-200 ℃; roasting and reducing: roasting and reducing the dried material, wherein the reduction temperature is controlled to be 750-1150 ℃, and the reduction time is 15-60 min; magnetic separation: and cooling and grinding the roasted and reduced product, and then sequentially screening through a two-stage magnetic field to separate magnetic iron ore powder and nonmagnetic tailings. The method solves the problem of low reaction efficiency caused by high ash content in the conventional magnetic roasting method for reducing the red mud by using the lignite, and improves the comprehensive utilization rate of the red mud by optimizing and improving the magnetic roasting equipment.
Chinese invention patent CN108085446A discloses a system and a method for treating red mud, the system comprising: the mixing device is provided with a red mud inlet, a reducing agent inlet, a fluxing agent inlet, a binder inlet and a mixed material outlet; the pelletizing device is provided with a mixed material inlet and a mixed pellet outlet, and the mixed material inlet is connected with the mixed material outlet; the smelting device is provided with a smelting space, a smelting pool is limited at the bottom of the smelting space, the smelting space sequentially forms a charging area along the flow direction of a melt, a reduction area, a smelting area and a clarification area, the charging area is positioned at one end of the smelting device, the clarification area is positioned at the other end of the smelting device, a mixed pellet inlet is arranged on the side wall of the charging area, the mixed pellet inlet is connected with a mixed pellet outlet, a molten iron outlet and a slag outlet are arranged on the side wall of the clarification area, at least one pair of heat accumulating type burners are correspondingly arranged on the side walls of the charging area, the reduction area, the smelting area and the clarification area, and each pair of heat accumulating type burners are.
Therefore, no report of preparing titanium carbide by using titanium-containing minerals in red mud exists at present.
Disclosure of Invention
The invention provides a method for producing granular iron and titanium carbide by using red mud as a raw material and utilizing a reducing molten salt bath, which comprises the steps of mixing the red mud and low-volatile solid carbon (graphite powder and petroleum coke), putting the mixture into the molten salt bath, utilizing molten salt to dissolve iron, gallium and titanium components in the red mud, reducing iron and gallium ions into metal on the surfaces of solid carbon granules, and combining the titanium ions with the carbon to form titanium carbide. After the reaction is finished, separating solid product particles and liquid molten salt by using a porous plate, separating iron, titanium carbide and gallium-iron alloy from the solid product by magnetic separation, and finally separating titanium carbide particles from the residue in a vortex current separation mode.
A method for producing granular metal and titanium carbide by using red mud as a raw material is characterized by comprising the following steps: mixing red mud and low-volatile solid carbon, putting the mixture into a molten salt bath, and dissolving iron, gallium and titanium in the red mud by using molten salt to enable the red mud to enter the molten salt in a free ion form; iron and gallium ions are reduced to metal on the surface of the solid carbon particles, and titanium ions are combined with carbon to form titanium carbide or titanium oxycarbide; after the reaction is finished, most of liquid molten salt is filtered from the solid product by utilizing a porous plate through gas pressure, the residual filter residue is cooled and then is subjected to magnetic separation to separate metal iron and gallium from the solid product, and finally, titanium carbide particles are separated from the residue in an eddy current separation mode.
The type of the solid carbon is graphite powder or petroleum coke, and the composition meets one of the following conditions: (1) the volatile component of the solid carbon is between 0.001 and 0.01 percent, the ash content is between 0.01 and 0.1 percent, and the sulfur content is between 0.001 and 0.01 percent; (2) the volatile component of the solid carbon is between 0.01 and 0.2 percent, the ash content is between 0.1 and 0.15 percent, and the sulfur content is between 0.01 and 0.08 percent; (3) the volatile component of the solid carbon is between 0.2 and 0.3 percent, the ash content is between 0.15 and 0.5 percent, and the sulfur content is between 0.08 and 0.2 percent; (4) the volatile component of the solid carbon is between 0.05 and 2 percent, the ash content is between 0.5 and 2 percent, and the sulfur content is between 0.2 and 0.9 percent.
Further, the inorganic salt exists in a liquid state in the reaction process, and the quality of the molten salt meets the following conditions: 2.97 (the mass of the red mud plus the mass of the solid carbon) or more and the mass of the molten salt is more than or equal to 0.86 (the mass of the red mud plus the mass of the solid carbon); the molten salt is used for dissolving the red mud and converting iron, gallium and titanium minerals in the red mud into free ions; the conversion reaction of the ions needs to use molten salt as a medium; wherein, iron and gallium ions are diffused to the surface of the solid carbon particles by the medium action of molten salt, and are reduced to metal from free ions, so as to form particles; titanium ions diffuse to the surface of the solid carbon particles and are converted into titanium carbide or titanium oxycarbide, and then the particles are formed.
Further, a staged heating and heat preservation system is adopted; wherein the heating rate from room temperature to 575 ℃ is between 2.81 ℃/min and 8.53 ℃/min, the heating rate from 575 ℃ to 998 ℃ is between 1.91 ℃/min and 6.25 ℃/min, and the heating rate from 999 ℃ to 1198 ℃ is between 0.81 ℃/min and 6.13 ℃/min; the temperature is required to be preserved after the temperature is raised to reach the preset temperature, and the temperature preservation temperature range is 1-4 of the following ranges, namely 651-699 ℃, 951-998 ℃, 1101-1148 ℃ and 1151-1198 ℃.
Further, a molten salt bath having reducibility is used as a reaction medium, and the reducibility of the molten salt bath is provided by solid carbon particles insoluble in molten salt; compounding of solid carbonThe quantitative ratio is (0.19 α)Fe+0.6αTi+0.42αGa) × (1-V) × 100%, wherein, αFe、αTi、αGaThe mass fractions of Fe, Ti and Ga in the red mud are respectively, and V is the volatile content of the solid carbon.
Further, the red mud and the solid carbon are used as raw materials, and the proportion of the solid carbon is (0.19 α)Fe+0.6αTi+0.35αGa) × (1-V) × 100%, wherein, αFe、αTi、αGaThe mass fractions of iron, gallium and titanium in the red mud are respectively, and V is the volatile content of the solid carbon.
Further, the solid carbon is graphite powder or petroleum coke, and the selection and the heat preservation temperature of the molten salt are related to the components of the solid carbon. Selecting a single component of inorganic salt sodium chloride when the volatile content of the solid carbon is between 0.001 and 0.01 percent, the ash content is between 0.01 and 0.1 percent and the sulfur content is between 0.001 and 0.01 percent, and keeping the temperature at 1149 ℃ to 1199 ℃; when the volatile content of the solid carbon is between 0.01 and 0.2 percent, the ash content is between 0.1 and 0.15 percent and the sulfur content is between 0.01 and 0.08 percent, selecting a single-component inorganic salt calcium chloride, and keeping the temperature at 1100 ℃ to 1148 ℃; selecting single-component inorganic salt sodium chloride or calcium chloride when the volatile content of the solid carbon is between 0.2 and 0.3 percent, the ash content is between 0.15 and 0.5 percent and the sulfur content is between 0.08 and 0.2 percent, and keeping the temperature at 999-1099 ℃; when the volatile content of the solid carbon is between 0.05 and 2 percent, the ash content is between 0.5 and 2 percent, and the sulfur content is between 0.2 and 0.9 percent, selecting sodium chloride-calcium chloride binary molten salt, and keeping the temperature at 949 to 998 ℃.
Further, most of the liquid molten salt is filtered from the solid product at high temperature by using a porous plate; after the molten salt is cooled, the solid product is removed and water is added to adjust the concentration of the slurry to 45-65%; and (3) stirring or simply grinding the slurry (the grinding time is less than 5min), and then separating metallic iron and gallium particles from solid product particles by adopting a magnetic separation mode. Wherein the magnetic separation field strength is between 4kA/m and 15 kA/m. And purifying the magnetic separation tailings in a flotation (or eddy current separation) mode to obtain titanium carbide or titanium oxycarbide particles, and simultaneously removing the tailings.
Further, the composition of the solid carbon is utilized to control the grade and the application of the product, and when the composition of the solid carbon meets the condition (1), the titanium carbide particles can be produced by matching with the type and the temperature of the molten salt to produce a high-quality wear-resistant material; when the solid carbon component meets the condition (2), titanium carbide particles are produced by matching with the type of molten salt and the temperature condition and are used for manufacturing a high-temperature-resistant instrument; when the composition of the solid carbon meets the condition (3), titanium carbide particles can be produced by matching with the type and temperature of the molten salt, and the purified and modified titanium carbide particles can be used as a production raw material of titanium carbide; when the solid carbon composition satisfies the condition (4), a mixture of titanium carbide and titanium oxycarbide can be produced for producing electrolytic titanium.
Further, most of the liquid molten salt is filtered from the solid product by using a porous plate at high temperature so as to be recycled; after the molten salt is cooled, metal Fe and Ga particles are separated from solid product particles by magnetic separation, nonmagnetic TiC is enriched in a nonmagnetic product, and finally titanium carbide particles are separated from the nonmagnetic product in an eddy current separation mode.
Further, iron and gallium in the red mud are reduced into metallic iron, gallium or iron-gallium alloy step by adopting a step heating system above the melting temperature of the salt, and titanium is converted into titanium carbide or titanium oxycarbide.
The invention takes the red mud as the main raw material, can directly produce high-quality titanium carbide powder by heating for 1 time, and can also produce granular metallic iron, metallic gallium or gallium-iron alloy, thereby realizing the comprehensive utilization of iron, titanium and gallium elements in the red mud. The method has the advantages of short production process, wide raw material source and low production cost. The differences from the prior art are reflected in:
(1) raw materials. In the prior art, titanium carbide can be produced only by using raw materials such as metallic titanium, titanium slag, ilmenite, titanium dioxide and the like, and red mud with wider sources and lower price cannot be used;
(2) the treatment temperature. In the prior art, carbonization is completed through solid-phase reaction between titanium-containing minerals and solid carbon, the reaction temperature is generally above 1500 ℃, and the treatment temperature of the method is less than 1200 ℃;
(3) diffusion conditions. The solid phase reaction diffusion condition is not sufficient, the obtained titanium carbide has uneven properties, and the improvement of the application performance is limited. The invention introduces the molten salt bath with excellent diffusion performance, and the reaction efficiency and the product quality are obviously improved;
in conclusion, compared with the existing red mud and titanium carbide production technology, the method provided by the invention is different in raw materials, process parameters and product performance, and is a brand-new production technology.
Drawings
FIG. 1 is a process flow of flotation of enriched red mud-based titanium carbide;
FIG. 2 is a process flow of the eddy current enriched red mud-based titanium carbide.
Detailed Description
The following examples are provided to illustrate the practice of the present invention, but are not intended to limit the scope of the invention.
Example 1:
the red mud concentrate and the high-purity graphite powder with the purity of 99 percent in Xinjiang comprise the following main components (the range values tested for multiple times and the same below): TFe 45.17% -45.21%, SiO29.21％～9.24％，TiO25.16％～5.19％Ga2O30.001 to 0.0011 percent of the total weight, and 81.03 to 81.22 percent of the particle size composition with the particle size of-0.074 mm; graphite powder ash 0.5% -0.65%, water 0.13% -0.15%, volatile 0.02% -0.3%, and particle size composition 0.074mm accounting for 44.5% -45%; industrial sodium chloride is used as the molten salt.
The use process comprises the following steps:
(1) and (4) preparing raw materials. Taking 10kg of red mud, mixing the red mud, graphite powder and sodium chloride according to a mass ratio of 1: 0.15: 2.5, mixing uniformly, and placing the mixture in a 10L high-purity graphite crucible in a well type furnace;
(2) and (5) heating and preserving heat. The heating rate from room temperature to 575 ℃ is between 2.81 ℃/min and 2.9 ℃/min, the heating rate is 2.1 ℃/min from 575 ℃ to 670 ℃, and the temperature is kept for 10min at 670 ℃; the heating rate between 670 ℃ and 1198 ℃ is between 1.96 ℃/min and 1.98 ℃/min, and the temperature is kept for 60min after the temperature is raised to 1198 ℃;
(3) molten salt extraction and filtration. High-pressure gas is blown into a quartz tube suspended above the molten salt, so that the molten salt is forced to flow out of a quartz conduit inserted into the molten salt and is extruded out of the reactor. During which the solid product is isolated by a porous medium plate; after separating the liquid molten salt, cooling the device to room temperature, and taking out product particles; adding water into the product particles to adjust the concentration of the slurry to 60%;
(4) stirring and magnetic separation. Simply stirring the slurry and then sorting by a roller magnetic separator, wherein the field intensity is between 6.1kA/m and 6.5kA/m, and separating metallic iron, gallium and iron gallium ferro-gallium alloy particles;
(5) and (4) carrying out flotation. And (3) carrying out flotation and enrichment on the residual titanium carbide-rich tailings after magnetic separation by 3 sections to prepare titanium carbide powder with the titanium carbide content of 98.28%.
Example 2:
concentrate of certain red mud in Hebei and 99 percent of high-purity graphite powder, wherein the red mud mainly comprises the following components: 58.61% -58.65% of TFe and SiO22.23％～2.26％，TiO28.92％～8.95％，Ga2O30.00077-0.00081 percent, and 89.61-89.67 percent of granularity composition of-0.074 mm; graphite powder ash 0.5% -0.65%, water 0.13% -0.15%, volatile 0.02% -0.3%, and particle size composition 0.074mm accounting for 44.5% -45%; industrial sodium chloride is used as the molten salt.
The use process comprises the following steps:
(1) and (4) preparing raw materials. Taking 10kg of red mud, mixing the red mud, graphite powder and sodium chloride according to a mass ratio of 1: 0.12: 2.4, mixing uniformly, and placing in a high-purity graphite crucible in a 50kg induction furnace;
(2) and (5) heating and preserving heat. The heating rate from room temperature to 575 ℃ is between 2.79 ℃/min and 2.95 ℃/min, the heating rate is 5 ℃/min from 575 ℃ to 670 ℃, and the temperature is kept for 10min at 670 ℃; the heating rate between 670 ℃ and 1198 ℃ is between 5.11 ℃/min and 5.42 ℃/min, and the temperature is kept for 35min to 40min after the temperature is raised to 1198 ℃;
(3) molten salt extraction and filtration. High-pressure gas is blown into a quartz tube suspended above the molten salt, so that the molten salt is forced to flow out of a quartz conduit inserted into the molten salt and is extruded out of the reactor. During which the solid product is isolated by a porous medium plate; after separating the liquid molten salt, cooling the device to room temperature, and taking out product particles; adding water into the product particles to adjust the concentration of the slurry to 55-56%;
(4) stirring and magnetic separation. After the slurry is simply stirred, a roller magnetic separator is adopted for separation, the field intensity is between 4.8kA/m and 5.2kA/m, and metal iron, gallium and iron gallium ferro-gallium alloy particles are separated;
(5) and (4) carrying out flotation. And further enriching the titanium carbide-rich tailings left after magnetic separation by adopting a self-made eddy current separator. And 2-section eddy current sorting and enriching to prepare titanium carbide powder with the titanium carbide content of 97.28%.
Example 3:
red mud concentrate and fixed carbon 95.09% petroleum coke in the west of Sichuan, the red mud mainly comprises the following components: TFe 54.19% -54.35%, SiO21.97％～1.98％，TiO210.97％～10.98％，Ga2O30.0092-0.0093%, and 80.2-80.7% of grain size composition-0.074 mm; 3.85-3.91% of petroleum coke ash, 0.13-0.15% of water, 0.8-0.9% of volatile component and 49.3-49.6% of granularity composition of 0.074 mm; industrial sodium chloride-calcium chloride is used as molten salt.
The use process comprises the following steps:
(1) and (4) preparing raw materials. Taking 10kg of red mud, mixing the red mud, graphite powder and sodium chloride according to a mass ratio of 1: 0.18: 2.5, mixing uniformly, and placing the mixture in a 10L high-purity graphite crucible in a well type furnace;
(2) and (5) heating and preserving heat. The heating rate from room temperature to 575 ℃ is between 2.81 ℃/min and 2.9 ℃/min, the heating rate from 575 ℃ to 670 ℃ is 1.9 ℃/min to 1.95 ℃/min, and the temperature is kept at 670 ℃ for 10 min; the heating rate between 670 ℃ and 998 ℃ is between 2.1 ℃/min and 2.2 ℃/min, and the temperature is kept for 30min after the temperature is raised to 998 ℃;
(3) molten salt extraction and filtration. High-pressure gas is blown into a quartz tube suspended above the molten salt, so that the molten salt is forced to flow out of a quartz conduit inserted into the molten salt and is extruded out of the reactor. During the process, a porous medium plate is used for intercepting solid products; after separating the liquid molten salt, cooling the device to room temperature, and taking out product particles; adding water into the product particles to adjust the concentration of the slurry to 65%;
(4) stirring and magnetic separation. Simply stirring the slurry and then sorting by a roller magnetic separator, wherein the field intensity is between 4.5kA/m and 4.6kA/m, and separating metallic iron, gallium and iron gallium iron alloy particles;
(5) and (4) carrying out flotation. And (3) carrying out flotation and enrichment on the titanium carbide-rich tailings remaining after the magnetic separation by 3 sections to obtain titanium carbide powder with the titanium carbide content of 83.64%.
Example 4:
the red mud concentrate and the high-purity graphite powder with the purity of 99 percent in Xinjiang comprise the following main components (the range values tested for multiple times and the same below): TFe 55.17% -55.21%, SiO22.23％～2.26％，TiO2 10.16％～10.19％，Ga2O30.00103-0.00107 percent of grain size composition, and 81.2-81.3 percent of grain size composition with the grain size of-0.074 mm; graphite powder ash 0.5% -0.65%, water 0.13% -0.15%, volatile 0.02% -0.3%, and particle size composition 0.074mm accounting for 44.5% -45%; industrial calcium chloride is used as molten salt.
The use process comprises the following steps:
(1) and (4) preparing raw materials. Taking 10kg of red mud, mixing the red mud, graphite powder and sodium chloride according to a mass ratio of 1: 0.15: 3, uniformly mixing, and placing the mixture in a 10L high-purity graphite crucible in a well type furnace;
(2) and (5) heating and preserving heat. The heating rate from room temperature to 575 ℃ is between 2.8 ℃/min and 2.85 ℃/min, the heating rate from 575 ℃ to 670 ℃ is 1.9 ℃/min to 2.1 ℃/min, and the temperature is kept at 670 ℃ for 20 min; the heating rate between 670 ℃ and 998 ℃ is between 1.9 ℃/min and 2.1 ℃/min, and the temperature is kept for 30min after the temperature is increased to 1198 ℃;
(3) molten salt extraction and filtration. High-pressure gas is blown into a quartz tube suspended above the molten salt, so that the molten salt is forced to flow out of a quartz conduit inserted into the molten salt and is extruded out of the reactor. During the process, a porous medium plate is used for intercepting solid products; after separating the liquid molten salt, cooling the device to room temperature, and taking out product particles; adding water into the product particles to adjust the concentration of the slurry to 55 percent;
(4) stirring and magnetic separation. Simply stirring the slurry and then sorting by a roller magnetic separator, wherein the field intensity is between 5.1kA/m and 5.2kA/m, and separating metallic iron, gallium and iron gallium iron alloy particles;
(5) and (4) carrying out flotation. And (3) carrying out flotation and enrichment on the titanium carbide-rich tailings remaining after the magnetic separation by 3 sections to obtain titanium carbide powder with the titanium carbide content of 94.26%.
Claims (7)
1. A method for producing granular metal and titanium carbide by using red mud as a raw material is characterized by comprising the following steps: mixing red mud and low-volatile solid carbon, putting the mixture into a molten salt bath, and dissolving iron, gallium and titanium in the red mud by using molten salt to enable the red mud to enter the molten salt in a free ion form; iron and gallium ions are reduced to metal on the surface of the solid carbon particles, and titanium ions are combined with carbon to form titanium carbide or titanium oxycarbide; after the reaction is finished, filtering most of liquid molten salt from the solid product by using a porous plate, cooling the residual filter residue, separating metallic iron and gallium from the solid product by magnetic separation, and finally separating titanium carbide particles from the magnetic separation tailings in a vortex current separation mode;
the type of the solid carbon is graphite powder or petroleum coke, and the composition meets one of the following conditions: (1) the volatile component of the solid carbon is between 0.001 and 0.01 percent, the ash content is between 0.01 and 0.1 percent, and the sulfur content is between 0.001 and 0.01 percent; (2) the volatile component of the solid carbon is between 0.01 and 0.2 percent, the ash content is between 0.1 and 0.15 percent, and the sulfur content is between 0.01 and 0.08 percent; (3) the volatile component of the solid carbon is between 0.2 and 0.3 percent, the ash content is between 0.15 and 0.5 percent, and the sulfur content is between 0.08 and 0.2 percent; (4) the volatile component of the solid carbon is between 0.05 and 2 percent, the ash content is between 0.5 and 2 percent, and the sulfur content is between 0.2 and 0.9 percent;
inorganic salt exists in a liquid state in the reaction process, and the quality of the molten salt meets the following conditions: 2.97 (the mass of the red mud plus the mass of the solid carbon) or more and the mass of the molten salt is more than or equal to 0.86 (the mass of the red mud plus the mass of the solid carbon); the molten salt is used for dissolving the red mud and converting iron, gallium and titanium minerals in the red mud into free ions; the conversion reaction of the ions needs to use molten salt as a medium; wherein, iron and gallium ions are diffused to the surface of the solid carbon particles by the medium action of molten salt, and are reduced to metal from free ions, so as to form particles; diffusing titanium ions to the surface of the solid carbon particles to convert the titanium ions into titanium carbide or titanium oxycarbide, and further forming particles;
a step-by-step heating and heat preservation system is adopted; wherein the heating rate from room temperature to 575 ℃ is between 2.81 ℃/min and 8.53 ℃/min, the heating rate from 575 ℃ to 998 ℃ is between 1.91 ℃/min and 6.25 ℃/min, and the heating rate from 999 ℃ to 1198 ℃ is between 0.81 ℃/min and 6.13 ℃/min; the temperature is required to be preserved after the temperature is raised to reach the preset temperature, and the temperature preservation temperature range is 1-4 of the following ranges, namely 651-699 ℃, 951-998 ℃, 1101-1148 ℃ and 1151-1198 ℃.
2. The method for producing granular metal and titanium carbide from red mud according to claim 1, wherein a molten salt bath having reducibility is used as a reaction medium, the reducibility of the molten salt bath is provided by solid carbon particles insoluble in molten salt, and the proportion of the solid carbon added is (0.19 α)Fe+0.6αTi+0.42αGa) × (1-V) × 100%, wherein, αFe、αTi、αGaThe mass fractions of Fe, Ti and Ga in the red mud are respectively, and V is the volatile content of the solid carbon.
3. The method for producing granular metal and titanium carbide from red mud as claimed in claim 1, wherein the red mud and solid carbon are used as raw materials, and the proportion of the solid carbon is (0.19 α)Fe+0.6αTi+0.35αGa) × (1-V) × 100%, wherein, αFe、αTi、αGaThe mass fractions of iron, titanium and gallium in the red mud are respectively, and V is the volatile content of the solid carbon.
4. The method for producing granular metal and titanium carbide by using red mud as a raw material according to claim 1, which is characterized in that: filtering most of liquid molten salt from the solid product at high temperature by using a porous plate; after the molten salt is cooled, the solid product is removed and water is added to adjust the concentration of the slurry to 45-65%; stirring or simply grinding the slurry for less than 5min, and separating metallic iron and gallium particles from solid product particles by adopting a magnetic separation mode after grinding; wherein the magnetic separation field strength is between 4kA/m and 15 kA/m; and purifying the magnetic separation tailings by adopting a flotation or eddy current separation mode to obtain titanium carbide or titanium oxycarbide particles, and simultaneously removing the tailings.
5. The method for producing granular metal and titanium carbide by using red mud as a raw material according to claim 1, which is characterized in that: the grade and the application of the product are controlled by utilizing the composition of the solid carbon, and when the composition of the solid carbon meets the condition (1), the condition of producing titanium carbide particles by matching with the variety and the temperature of molten salt is matched to produce a high-quality wear-resistant material; when the solid carbon component meets the condition (2), titanium carbide particles are produced by matching with the type of molten salt and the temperature condition and are used for manufacturing a high-temperature-resistant instrument; when the composition of the solid carbon meets the condition (3), producing titanium carbide particles by matching with the type and temperature of molten salt, and purifying and modifying the titanium carbide particles to be used as a production raw material of the titanium carbide; when the solid carbon composition satisfies the condition (4), a mixture of titanium carbide and titanium oxycarbide can be produced for producing electrolytic titanium.
6. The method for producing granular metal and titanium carbide by using red mud as a raw material according to claim 1, which is characterized in that: filtering most of liquid molten salt from the solid product by using a porous plate at high temperature so as to recycle the molten salt; after the molten salt is cooled, metal Fe and Ga particles are separated from solid product particles by magnetic separation, nonmagnetic TiC is enriched in a nonmagnetic product, and finally titanium carbide particles are separated from the nonmagnetic product in an eddy current separation mode.
7. The method for producing granular metal and titanium carbide by using red mud as a raw material according to claim 1, which is characterized in that: above the melting temperature of the salt, iron and gallium in the red mud are reduced into metallic iron, gallium or iron-gallium alloy step by adopting a staged heating system, and titanium is converted into titanium carbide or titanium oxycarbide.
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