A method for producing titanium carbide slag and ferrovanadium alloy

Abstract

This invention relates to a method for producing titanium carbide slag and ferrovanadium alloy, comprising the following steps: a. mixing titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide, and then directly or pelletizing the mixture and charging it into an electric furnace; b. heating the furnace with electricity until all solid materials are melted, and then reducing and smelting at a predetermined temperature for a predetermined time; c. removing the slag, cooling it, and crushing the cooled product to a predetermined particle size; d. magnetic separation to obtain titanium carbide slag and ferrovanadium products. This invention converts titanium in titanium-containing slag and vanadium-containing tailings into titanium carbide slag that can be chlorinated at a lower temperature, while calcium and magnesium do not participate in the chlorination process. This effectively utilizes the titanium resources in the slag and recovers the vanadium resources from the slag, while also reducing the iron content in the overall slag, ensuring the product quality and stable operation of the entire process. Improving the comprehensive utilization rate of vanadium and titanium resources is of great significance.

Description

Technical Field

[0001] This invention belongs to the field of metallurgy, specifically relating to a method for producing titanium carbide slag and ferrovanadium alloy. Background Technology

[0002] The Panxi region is rich in vanadium-titanium magnetite resources, with titanium reserves accounting for over 90% of the national total. However, this mine is a typical polymetallic associated mineral resource of iron, vanadium, and titanium. While developing and utilizing iron, half of the titanium resources are enriched in the slag (with a TiO2 content as high as 15-45 wt%) after iron concentrate is smelted in blast furnaces or non-blast furnaces. The stockpiling of this titanium-containing slag not only causes environmental problems but also results in a significant waste of resources (currently, the utilization rate of titanium resources in the Panxi region is only 28%).

[0003] TiO2 in this type of titanium-containing slag can be converted into TiC by carbothermal reduction at high temperature, and then further chlorinated at low temperature to prepare titanium tetrachloride, thereby realizing the recycling of titanium resources in this type of slag. This is also the only titanium extraction technology route that has achieved industrial application at present.

[0004] Because slag and iron cannot be completely separated during the ironmaking process, this type of titanium-containing slag often contains 1% to 8% iron. In the further carbothermic reduction and low-temperature chlorination titanium extraction process, this part of the Fe will react with chlorine to generate ferric chloride. Ferric chloride entering titanium tetrachloride will not only affect the product quality, but also cause blockage of the chlorination system and affect the stable operation of the process. Therefore, it is necessary to control the iron content in this type of slag to a low level before chlorination.

[0005] Industrially, magnetic separation is used to remove iron after carbothermic reduction of titanium-containing slag. However, since the generated titanium carbide tends to accumulate on the surface of metallic iron and encapsulates it, the effect of direct magnetic separation for iron removal is not ideal.

[0006] On the other hand, since the Panzhihua vanadium-titanium magnetite is a co-existing mineral resource, the slag in this type of furnace also contains a certain amount of vanadium. The crude titanium tetrachloride obtained after high-temperature carbothermal reduction and low-temperature chlorination has a high vanadium content and must be removed through refining processes; otherwise, it will affect the subsequent production of sponge titanium and titanium dioxide. After vanadium removal in titanium tetrachloride refining, vanadium is enriched in the refining tailings. This vanadium-containing tailings contains approximately 10-20% vanadium and 12-25% titanium. Its stockpiling not only causes environmental pollution but also wastes vanadium and titanium resources.

[0007] Therefore, existing technologies still need improvement. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention proposes a method involving the carbothermic reduction of the aforementioned titanium-containing slag and vanadium-containing tailings at high temperatures. This process converts the titanium in both slags into titanium carbide, which can be chlorinated at low temperatures, thus extracting titanium resources from the slag. Simultaneously, the iron and vanadium in the slag combine to form a ferrovanadium alloy, which, after enrichment and growth, is more easily separated from the titanium carbide slag. This method not only recovers vanadium and titanium resources from the slag but also reduces the iron content, ensuring the product quality and stable operation of the entire process.

[0009] Specifically, according to the present invention, a method for producing titanium carbide slag and ferrovanadium alloy is provided, comprising the following steps: a. mixing titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide, and then directly or pelletizing the mixture and charging it into an electric furnace; b. heating the furnace with electricity until all solid materials are melted, and then reducing and smelting the mixture at a predetermined temperature for a predetermined time; c. removing the slag, cooling the mixture, and crushing the cooled product to a predetermined particle size; d. magnetic separation to obtain titanium carbide slag and ferrovanadium product, wherein the titanium carbide slag can be directly used in a low-temperature chlorination process for further chlorination to prepare titanium tetrachloride, and the ferrovanadium product can be used as an alloying additive or catalyst.

[0010] In an embodiment of the present invention, the titanium-containing slag is a by-product obtained from blast furnace or non-blast furnace ironmaking of vanadium-titanium magnetite, and its main components include: 9-25% Ti, 1-10% Fe, 3-12% Mg, 2-20% Ca, 7-14% Si, 6-8% Al, and 0.1-1% TV.

[0011] In an embodiment of the present invention, the vanadium-containing tailings are the tailings remaining after vanadium removal from titanium tetrachloride, and its main components include: 10-20% TV, 12-25% Ti, 2-5% Cl, 4-7% Si, 1-6% Fe, 2-4% Al, 5-10% Ca, and 1-3% Mg.

[0012] In an embodiment of the present invention, in step a, the amounts of titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide added by weight are: 100: 5-40: 10-30: 0.1-1.5.

[0013] In an embodiment of the present invention, in step a, the carbonaceous reducing agent includes at least one of anthracite, coke, petroleum coke or graphite, and the fixed carbon content in the carbonaceous reducing agent is not less than 75%, and the particle size is not greater than 3 mm.

[0014] In an embodiment of the present invention, in step b, the predetermined temperature is 1550℃~1750℃, the predetermined time is 1~6h, and the reduction temperature is 1350℃~1800℃.

[0015] In an embodiment of the present invention, in step c, the predetermined particle size is 80 mesh or less.

[0016] In an embodiment of the present invention, in step c, the predetermined particle size is between 100 mesh and 240 mesh.

[0017] In an embodiment of the present invention, during step d, the magnetic field strength is controlled to be 500-3000 Gs.

[0018] In an embodiment of the present invention, during step d, the magnetic field strength is controlled to be 500 Gs to 1500 Gs during magnetic separation.

[0019] This invention provides a method for converting titanium in titanium-containing slag and vanadium-containing tailings into titanium carbide. The resulting titanium carbide slag can be used as a raw material for the production of titanium tetrachloride. Furthermore, by introducing vanadium-containing tailings and manganese oxide, this invention allows the iron in the titanium-containing slag to combine with vanadium and manganese to form a vanadium-iron alloy. This not only recovers the vanadium resources from the tailings but also reduces the iron content in the titanium carbide slag, ensuring the quality of the titanium tetrachloride product and the stable and smooth operation of the subsequent chlorination process. Attached Figure Description

[0020] Figure 1 A schematic flow diagram of a method for producing titanium carbide slag and ferrovanadium alloy provided by the present invention is shown. Detailed Implementation

[0021] It should be understood that the embodiments of the invention shown in the exemplary embodiments are merely illustrative. Although only a few embodiments have been described in detail in this invention, those skilled in the art will readily recognize that various modifications are possible without substantially departing from the teachings of the invention. Accordingly, all such modifications should be included within the scope of the invention. Other substitutions, modifications, variations, and deletions can be made to the design, operating conditions, and parameters of the following exemplary embodiments without departing from the spirit of the invention.

[0022] This invention provides a production method for preparing titanium carbide slag and ferrovanadium alloy. The method uses titanium-containing slag from vanadium-titanium magnetite ironmaking and tailings from titanium tetrachloride refining to remove vanadium as raw materials. It can recover titanium resources from these two types of slag to prepare titanium carbide, which can be further chlorinated to prepare titanium tetrachloride. It can also reduce the iron content in the slag while recovering vanadium through the combination of vanadium and iron, thus ensuring the product quality and stable operation of the entire process.

[0023] like Figure 1 As shown, the method for producing titanium carbide slag and ferrovanadium alloy provided by the present invention includes the following steps:

[0024] a. Mix titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide, and then directly or pelletize them and charge them into the electric furnace;

[0025] b. Power is supplied to raise the temperature until all the solid material has melted, and then the material is reduced and smelted at a predetermined temperature for a predetermined time.

[0026] c. Remove slag, cool, and crush the cooled product to the predetermined particle size;

[0027] d. Magnetic separation yields titanium carbide slag and ferrovanadium products. The titanium carbide slag can be directly used in a low-temperature chlorination process to further chlorinate and prepare titanium tetrachloride, while the ferrovanadium products can be used as alloying additives or catalysts.

[0028] In an embodiment of the present invention, the titanium-containing slag is a by-product obtained from blast furnace or non-blast furnace ironmaking of vanadium-titanium magnetite, and its main components include: 9-25% Ti, 1-10% Fe, 3-12% Mg, 2-20% Ca, 7-14% Si, 6-8% Al, and 0.1-1% TV.

[0029] In an embodiment of the present invention, the vanadium-containing tailings are the tailings remaining after vanadium removal from titanium tetrachloride, and their main components include: 10-20% TV, 12-25% Ti, 2-5% Cl, 4-7% Si, 1-6% Fe, 2-4% Al, 5-10% Ca, and 1-3% Mg. That is, the amounts of titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide added, by weight, are: 100 parts titanium-containing slag, 5-40 parts vanadium-containing tailings, 10-30 parts carbonaceous reducing agent, and 0.1-1.5 parts manganese oxide.

[0030] In an embodiment of the present invention, in step a, the amounts of titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide added by weight are: 100: 5-40: 10-30: 0.1-1.5.

[0031] In an embodiment of the present invention, in step a, the carbonaceous reducing agent includes at least one of anthracite, coke, petroleum coke or graphite, and the fixed carbon content in the carbonaceous reducing agent is not less than 75%, and the particle size is not greater than 3 mm.

[0032] In an embodiment of the present invention, in step b, the predetermined temperature is 1550℃~1750℃, the predetermined time is 1~6h, and the reduction temperature is 1350℃~1800℃.

[0033] In an embodiment of the present invention, in step c, the predetermined particle size is 80 mesh or less.

[0034] In an embodiment of the present invention, in step c, the predetermined particle size is between 100 mesh and 240 mesh.

[0035] In an embodiment of the present invention, during step d, the magnetic field strength is controlled to be 500-3000 Gs.

[0036] In an embodiment of the present invention, during step d, the magnetic field strength is controlled to be 500 Gs to 1500 Gs to achieve a better separation effect.

[0037] The specific embodiments of the present invention will be further described below with reference to examples, but the present invention is not limited to the scope of the embodiments described herein.

[0038] Example 1

[0039] The titanium-containing slag processed in this embodiment mainly comprises (by mass fraction): 9% Ti, 1.5% Fe, 3.8% Mg, 19.7% Ca, 13.6% Si, 8% Al, and 0.23% V. The vanadium-containing tailings mainly comprise (by mass fraction): 10.9% V, 13.2% Ti, 3.8% Cl, 6.2% Si, 5.6% Fe, 9.2% Ca, 2.4% Mg, and 3.8% Al. The carbonaceous reducing agent is a graphite carburizing agent with a fixed carbon content of 75% and a particle size of less than 3 mm. The method for producing titanium carbide slag and ferrovanadium alloy according to this invention includes the following steps:

[0040] A. Mix 10t of titanium-containing slag, 1.3t of vanadium-containing tailings, 1.25t of graphite recarburizer, and 20kg of manganese oxide and then directly load them into the electric furnace.

[0041] B. Power on and heat up until all solid materials are melted, then reduce and melt at a high temperature of 1550℃~1750℃ for 1.5 hours;

[0042] C. Remove slag, cool, and crush the cooled product to below 80 mesh;

[0043] D. Control the magnetic field strength to 3000 Gs, perform magnetic separation, and obtain titanium carbide slag and ferrovanadium products.

[0044] Example 2

[0045] The titanium-containing slag processed in this embodiment mainly comprises (by mass fraction): 15% Ti, 3.5% Fe, 6.1% Mg, 15% Ca, 10.3% Si, 7.2% Al, and 0.18% V. The vanadium-containing tailings mainly comprise (by mass fraction): 13% V, 21.2% Ti, 2.8% Cl, 4.6% Si, 3.4% Fe, 7.2% Ca, 1.7% Mg, and 2.8% Al. The carbonaceous reducing agent is coke powder with a fixed carbon content of 85% and a particle size of less than 1 mm. The method for producing titanium carbide slag and ferrovanadium alloy according to this invention includes the following steps:

[0046] A. Mix 10t of titanium-containing slag, 2.7t of vanadium-containing tailings, 1.8t of coke powder, and 50kg of manganese oxide and then directly load them into the electric furnace.

[0047] B. Power on and heat up until all solid materials are melted, then reduce and melt at a high temperature of 1550℃~1750℃ for 3 hours.

[0048] C. Remove slag, cool, and crush the cooled product to below 80 mesh;

[0049] D. Control the magnetic field strength to 2000 Gs, perform magnetic separation, and obtain titanium carbide slag and ferrovanadium products.

[0050] Example 3

[0051] The titanium-containing slag processed in this embodiment mainly comprises (by mass fraction): 19% Ti, 10% Fe, 11.2% Mg, 2.5% Ca, 7.8% Si, 6.4% Al, and 0.92% V. The vanadium-containing tailings mainly comprise (by mass fraction): 15.4% V, 20.6% Ti, 4.7% Cl, 5.1% Si, 2.8% Fe, 5.6% Ca, 1.6% Mg, and 2.6% Al. The carbonaceous reducing agent is semi-coke with a fixed carbon content of 80% and a particle size of less than 3 mm. The method for producing titanium carbide slag and ferrovanadium alloy according to this invention includes the following steps:

[0052] A. Mix 10t of titanium-containing slag, 4t of vanadium-containing tailings, 2.6t of semi-coke, and 150kg of manganese oxide, then pelletize and load the mixture into the electric furnace.

[0053] B. Power on and heat up until all solid materials are melted, then reduce and melt at a high temperature of 1550℃~1750℃ for 4.5 hours;

[0054] C. Remove slag, cool, and crush the cooled product to below 80 mesh;

[0055] D. Control the magnetic field strength to 1000 Gs, perform magnetic separation, and obtain titanium carbide slag and ferrovanadium products.

[0056] Example 4

[0057] The titanium-containing slag processed in this embodiment mainly comprises (by mass fraction): 23% Ti, 6.6% Fe, 10% Mg, 2.6% Ca, 7% Si, 7.6% Al, and 0.67% V. The vanadium-containing tailings mainly comprise (by mass fraction): 20% V, 16.1% Ti, 2.7% Cl, 4.5% Si, 2.3% Fe, 6.7% Ca, 1.6% Mg, and 2.7% Al. The carbonaceous reducing agent is anthracite with a fixed carbon content of 90% and a particle size of less than 2 mm. The method for producing titanium carbide slag and ferrovanadium alloy according to this invention includes the following steps:

[0058] A. Mix 10t of titanium-containing slag, 3.3t of vanadium-containing tailings, 2.9t of anthracite, and 90kg of manganese oxide, then pelletize and load the mixture into the electric furnace.

[0059] B. Power on and heat up until all solid materials are melted, then reduce and melt at a high temperature of 1550℃~1750℃ for 6 hours.

[0060] C. Remove slag, cool, and crush the cooled product to below 80 mesh;

[0061] D. Control the magnetic field strength to 500 Gs, perform magnetic separation, and obtain titanium carbide slag and ferrovanadium products.

[0062] The titanium carbide slag obtained in the above embodiments contains 10% to 30% titanium carbide, and the titanium recovery rate can reach more than 90%; the vanadium-iron product contains 5% to 75% vanadium and iron, and the vanadium and iron recovery rate is 30% to 80%.

[0063] The resulting titanium carbide slag can be directly transported to a low-temperature chlorination process for further chlorination to prepare titanium tetrachloride. The resulting ferrovanadium product can be used as an alloying additive or catalyst.

[0064] This invention transforms titanium from titanium-containing slag and vanadium-containing tailings into a titanium carbide slag that can undergo chlorination at a relatively low temperature (500℃), while calcium and magnesium do not participate in the chlorination process. On one hand, it converts the titanium in both types of slag into titanium tetrachloride, an indispensable raw material for the titanium industry, effectively utilizing the titanium resources in the slag. On the other hand, by introducing vanadium-containing tailings and manganese oxide, the iron in the titanium-containing slag combines with vanadium and manganese to form a vanadium-iron alloy. This not only recovers the vanadium resources from the slag but also reduces the overall iron content of the slag, ensuring the product quality and stable operation of the entire process. This is of great significance for alleviating environmental pressures on enterprises and improving the comprehensive utilization rate of vanadium and titanium resources.

[0065] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Any modifications or equivalent substitutions made to the present invention without departing from the spirit and scope thereof should be covered within the protection scope of the claims of the present invention.

Claims

1. A method for producing titanium carbide slag and ferrovanadium alloy, characterized in that, Includes the following steps: a. A mixture of titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide is directly or pelletized and charged into an electric furnace to recover vanadium and titanium resources from the slag and reduce the iron content. The titanium-containing slag is a byproduct obtained from blast furnace or non-blast furnace ironmaking of vanadium-titanium magnetite, and its composition by mass fraction includes: 9-25% Ti, 1-10% Fe, 3-12% Mg, 2-20% Ca, 7-14% Si, 6-8% Al, and 0.1-1% Fe. The vanadium-containing tailings are the tailings remaining after vanadium removal from titanium tetrachloride, and their composition by mass fraction includes: 10~20% TV, 12~25% Ti, 2~5% Cl, 4~7% Si, 1~6% Fe, 2~4% Al, 5~10% Ca, and 1~3% Mg; the amount of titanium-containing slag, vanadium-containing tailings, carbonaceous reducing agent, and manganese oxide added by weight is: 100: 5~40: 10~30: 0.1~1.5; b. Power is supplied to heat the material until all solid material has melted, and then the material is reduced and smelted at a predetermined temperature for a predetermined time; c. Remove slag, cool, and crush the cooled product to the predetermined particle size; d. Magnetic separation yields titanium carbide slag and ferrovanadium products. The titanium carbide slag can be directly used in a low-temperature chlorination process to further chlorinate and prepare titanium tetrachloride, while the ferrovanadium products can be used as alloying additives or catalysts.

2. The method for producing titanium carbide slag and ferrovanadium alloy according to claim 1, characterized in that, In step a, the carbonaceous reducing agent includes at least one of anthracite, coke, petroleum coke or graphite, and the fixed carbon content in the carbonaceous reducing agent is not less than 75%, and the particle size is not greater than 3 mm.

3. The method for producing titanium carbide slag and ferrovanadium alloy according to claim 1, characterized in that, In step b, the predetermined temperature is 1550℃~1750℃, the predetermined time is 1~6h, and the reduction temperature is 1350℃~1800℃.

4. The method for producing titanium carbide slag and ferrovanadium alloy according to claim 1, characterized in that, In step c, the predetermined particle size is below 80 mesh.

5. The method for producing titanium carbide slag and ferrovanadium alloy according to claim 4, characterized in that, In step c, the predetermined particle size is between 100 mesh and 240 mesh.

6. The method for producing titanium carbide slag and ferrovanadium alloy according to claim 1, characterized in that, In step d, during magnetic separation, the magnetic field strength is controlled to be 500~3000 Gs.

7. The method for producing titanium carbide slag and ferrovanadium alloy according to claim 6, characterized in that, In step d, during magnetic separation, the magnetic field strength is controlled to be 500 Gs to 1500 Gs.

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