Device and method for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride

Abstract

The invention relates to the field of comprehensive smelting of titanium metal and vanadium metal, in particular to a device and a method for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride. The method comprises the following steps: adding organic matter naphthenic oil in a refining process of crude titanium tetrachloride, and reducing VOCl3 in crude titanium into VOCl2 to enter refined slurry; the method comprises the following steps: firstly recovering TiCl4 in the refined vanadium-containing slurry, and then introducing chlorine gas for heating, so that VOCl2 is converted into VOCl3 gas again; condensing the VOCl3 gas to obtain a VOCl3 liquid; and finally, evaporating the VOCl3, and condensing and recovering the gas VOCl3 to obtain pure liquid VOCl3. The method is continuous in production operation, high in production efficiency, large in capacity, safe, economical and environmentally friendly, two products are creatively produced in a joint mode, the products are diversified through rigorous reaction steps, and a production line does not need to be independently developed.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of comprehensive smelting of titanium metal and vanadium metal, and particularly relates to a device and method for extracting and converting vanadyl chloride from crude titanium tetrachloride. BACKGROUND

[0002] The production process of crude titanium tetrachloride is a complex and delicate process flow, which mainly includes key steps such as raw material processing, chlorination reaction, gas condensation and impurity separation. In these steps, the core process is mainly divided into two kinds of boiling chlorination method and molten salt chlorination method, each of which has its unique operation process and technical requirements, and the specific process is as follows:

[0003] In the production of crude titanium tetrachloride, the boiling chlorination method is a mainstream process method, which is particularly suitable for processing high-grade titanium-rich materials. The TiO2 content of these titanium-rich materials usually exceeds 86%, and the total amount of calcium and magnesium oxides needs to be controlled below 2%. In the process of boiling chlorination method, the titanium-rich material (such as high-titanium slag) is first mixed uniformly with petroleum coke according to a certain mass ratio, and the mixing ratio is about 10:3. The mixed material needs to be crushed to a particle size range of 0.1-1.5mm, and needs to be dried to ensure that the moisture content of the material does not exceed 0.5%.

[0004] The advantage of boiling chlorination method is the continuity of the operation process, which can significantly improve the production efficiency and is very suitable for large-scale industrial production. In the chlorination reaction stage, the mixed material is continuously added to the chlorination furnace through the screw conveyor, and chlorine gas is introduced from the bottom of the furnace. In the boiling chlorination furnace, the material presents a fluidized state, and the main chemical reaction is as follows:

[0005] TiO2 + Cl2 + C → TiCl4 + CO + CO2.

[0006] In the collection process of crude titanium tetrachloride, the condensed liquid needs to go through the steps of sedimentation and filtration to remove suspended solids and dissolved impurities. After these treatments, red-brown or light yellow crude TiCl4 can be obtained, which contains suspended solids (such as TiO2, SiO2) and dissolved impurities (such as VOCl3, AlCl3, etc.).

[0007] It is worth noting that in the production process of crude titanium tetrachloride, VOCl3 is not effectively utilized and is wasted.

[0008] Vanadium oxytrichloride (VOCl3) is an important chemical intermediate, and its downstream application demand is growing steadily, especially in the fields of ethylene-propylene rubber catalyst, high-purity vanadium pentoxide preparation, and pharmaceutical intermediates. With the development of new energy materials, the demand for high-purity VOCl3 products is also rising.

[0009] Currently, the mainstream production method of VOCl3 is to use vanadium oxide (V2O5) and chlorine gas (Cl2) as raw materials to prepare crude vanadium oxytrichloride through high-temperature chlorination reaction, and then to improve its purity through distillation purification method. In this process, one of the key technologies is how to effectively remove impurities, especially those with similar boiling points to VOCl3, such as POCl3. In order to improve the separation efficiency, it is usually necessary to use multi-stage distillation or patented purification process, such as hydrolysis separation method, to ensure the high purity of VOCl3.

[0010] The difficulty of purifying VOCl3 lies in the fact that the boiling points of POCl3 and VOCl3 are very close, about 126℃, which makes the traditional distillation separation method less efficient. Therefore, chemical treatment methods such as selective hydrolysis must be combined to improve the separation effect. In addition, due to the need for high-temperature and corrosion-resistant equipment during the reaction process, and the need for full sealing during the entire operation process to avoid environmental pollution, the investment and maintenance cost of the equipment is relatively high.

[0011] If the production of crude titanium tetrachloride and vanadium oxytrichloride can be combined, a more intensive production process can be formed.

[0012] On April 15, 2025, a search was conducted in the China Patent Publication Database with "TiCl4 and VOCl3 and chlorine gas and naphthenic oil" as the abstract keyword, and the synonym expansion option was checked. No relevant literature was found.

[0013] On April 15, 2025, an abstract search was conducted on China National Knowledge Network with "TiCl4 and VOCl3 and chlorine gas and naphthenic oil". No relevant literature was found.

[0014] On April 15, 2025, a search was conducted on the United States Patent and Trademark Office website with "TiCl4 with VOCl3 with chlorine gas with naphthenic oil". No relevant literature was found; the search website is https: / / ppubs.uspto.gov / pubwebapp / .

[0015] No relevant document was found by searching with "TiCl4 and VOCl3 and chlorine gas and naphthenic oil" on WIPO's https: / / patentscope2.wipo.int / on April 15, 2025.

[0016] No relevant document was found by searching with "TiCl4 and VOCl3 and chlorine gas and naphthenic oil" on Japan's https: / / www.j-platpat.inpit.go.jp / on April 15, 2025. SUMMARY

[0017] The purpose of the application is to provide a device and method for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride with better effects, and the specific purposes are shown in the multiple substantial technical effects in the specific implementation part.

[0018] To achieve the above purpose, the application adopts the following technical solutions:

[0019] The method for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride comprises the following steps:

[0020] During the refining process of crude titanium tetrachloride, organic naphthenic oil is added, and VOCl3 in the crude titanium is reduced to VOCl2 and enters the refining slurry;

[0021] TiCl4 is recovered from the vanadium-containing slurry, and then chlorine gas is introduced and heated to make VOCl2 reconvert into VOCl3 gas;

[0022] VOCl3 gas is condensed to obtain VOCl3 liquid;

[0023] Finally, after evaporation, gas VOCl3 is condensed and recovered to obtain pure liquid VOCl3.

[0024] The further technical solution of the application is that the crude titanium tetrachloride is obtained by mixing titanium-rich material with petroleum coke, adding it into a chlorination furnace, and performing chlorination reaction with chlorine gas in a fluidized state;

[0025] Since the titanium-rich material contains V2O5, V2O5 reacts with chlorine gas and petroleum coke at high temperature in the chlorination furnace to generate VOCl3, which enters the crude titanium tetrachloride through the condensation system with the furnace gas;

[0026] Chemical equation: V2O5 + 2C + 3Cl2 = 2VOCl3 + CO + CO2;

[0027] In the refining production, the crude titanium tetrachloride enters the vanadium removal distillation kettle 1, is mixed with the vanadium removal agent uniformly, is heated and is warmed through the vanadium removal heater, the vanadium removal agent is carbonized and is cracked into nascent carbon under high temperature, reacts with vanadyl trichloride, reduces vanadyl trichloride into vanadyl dichloride and is precipitated into the refining slurry and is discharged from the vanadium removal distillation kettle 1, and vanadyl trichloride is removed in turn;

[0028] Chemical equation: 2VOCl3+C=2VOCl2+COCl2;

[0029] The refining slurry enters the settling tank one 6 from the vanadium removal distillation kettle 1, the slurry in the settling tank one 6 is thickened through the thickener one 7, the bottom slurry enters the centrifuge one 9 below the thickener, the supernatant returns to the crude titanium storage tank 17, the centrifuge one 9 is separated under the centrifugal force through rotation and thickens the slurry again, the separated clear liquid returns to the settling tank one 6, the slurry separated from the centrifuge one 9 enters the pyrolysis furnace one 10 and is continuously dried, the evaporated titanium tetrachloride gas passes through the direct condenser one 11 and the first-stage indirect condenser in turn, the titanium tetrachloride condensed in the direct condenser one 11 enters the direct cooling collection tank one 12, and the high liquid level overflows into the settling tank one 6; the titanium tetrachloride condensed in the first-stage indirect condenser flows into the crude titanium storage tank 17 in turn;

[0030] The high-temperature vanadium slag after evaporation enters the small chlorination furnace 20, heating chlorine is introduced and reacts with vanadyl dichloride in the vanadium slag to generate vanadyl trichloride: chemical equation: 2VOCl2+Cl2=2VOCl3.

[0031] The vanadyl trichloride gas from the chlorination furnace 20 is condensed into vanadyl trichloride liquid through the direct condenser two 22 and the indirect condenser, the vanadyl trichloride condensed in the direct condenser two 22 enters the vanadyl trichloride direct cooling collection tank two 23, and the vanadyl trichloride condensed in the indirect condenser flows into the vanadyl trichloride storage tank 29 in turn;

[0032] The vanadyl trichloride in the storage tank is transported to the vanadyl trichloride distillation kettle 30 through the magnetic pump 10, is heated and distilled, the vanadyl trichloride gas passes through the vanadyl trichloride distillation column 31, enters the vanadyl trichloride condenser 32 through the top, is condensed and enters the vanadyl trichloride reflux tank 33, part of the vanadyl trichloride in the vanadyl trichloride reflux tank 33 refluxes into the vanadyl trichloride distillation column 31, and part of the vanadyl trichloride is transported to the tank area vanadyl trichloride storage tank for storage and sale through the vanadyl trichloride reflux pump 34.

[0033] The direct condenser one 11 for titanium tetrachloride recovery in the application, the titanium tetrachloride in the direct cooling collection tank one 12 is transported to the spiral plate heat exchanger one 14 through the direct cooling pump one 13, is cooled and enters the direct condenser one 11, the titanium tetrachloride liquid is directly contacted with the titanium tetrachloride gas from bottom to top through the tray and from top to bottom, mass transfer and heat transfer are carried out, and the titanium tetrachloride gas is condensed into the titanium tetrachloride liquid;

[0034] The titanium tetrachloride gas not cooled into liquid enters an indirect condenser for further condensation; the cooling medium in the spiral plate heat exchanger 14 is circulating water; the indirect condensation is two-stage condensation in series, namely, a first-stage indirect condenser 15 and a second-stage indirect condenser 16, and the cooling medium in the two stages is refrigerated brine.

[0035] The further technical solution of the present application is that the direct condenser for vanadium oxytrichloride is a direct condenser two 22, the vanadium oxytrichloride in a direct cooling collection tank two 23 is transported to a spiral plate heat exchanger two 25 by a direct cooling pump two 24, and then enters the direct condenser two 22 after being cooled, the vanadium oxytrichloride liquid passes through the tower plate from top to bottom and directly contacts with the vanadium oxytrichloride gas from bottom to top to transfer mass and heat, so that the vanadium oxytrichloride gas is condensed into vanadium oxytrichloride liquid; the vanadium oxytrichloride gas not cooled into liquid enters an indirect condenser for further condensation; the cooling medium in the spiral plate heat exchanger two 25 is circulating water; the indirect condensation is two-stage condensation in series, namely, a first-stage indirect condenser two 26 and a second-stage indirect condenser two 27, and the cooling medium in the two stages is refrigerated brine.

[0036] The further technical solution of the present application is that the vanadium oxytrichloride system: when the solid content in the vanadium oxytrichloride distillation kettle 30 reaches the control standard, the slurry is discharged to a sedimentation tank two 35, the slurry in the sedimentation tank two 35 is thickened by a thickener two 36, the slurry at the bottom is introduced into a centrifuge two 37 below the thickener two 36, and the supernatant flows into a vanadium oxytrichloride second-stage storage tank 39 by itself, and then is transported into the vanadium oxytrichloride distillation kettle 30 by a magnetic pump; the centrifuge two 37 separates the solid and liquid under the centrifugal force by rotation to further thicken the slurry, the separated supernatant is returned to the sedimentation tank two 35, and the slurry separated by the centrifuge two 37 is introduced into a pyrolysis furnace two 38 for continuous drying, and the evaporated vanadium oxytrichloride gas is sequentially recycled by the direct condenser two 22 and the indirect condenser.

[0037] The further technical solution of the present application is that the pyrolysis furnace is a horizontal roller design and uses electric heating; the vanadium oxytrichloride distillation kettle is an electromagnetic induction heating design.

[0038] Main process control parameters

[0039]

[0040] The device for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride is characterized in that,

[0041] The vanadium removal distillation kettle 1 is connected with a vanadium removal distillation tower 2, the vanadium removal distillation tower 2 is connected with a vanadium removal condenser 3, the vanadium removal condenser 3 is connected with a vanadium removal reflux tank 4, and the vanadium removal reflux tank 4 is connected with the vanadium removal distillation tower 2 through a vanadium removal reflux pump 5.

[0042] The vanadium removal distillation kettle 1 is connected with a thickener one 7, and the thickener one 7 and a sedimentation tank 6 are arranged integrally; the sedimentation tank 6 is connected with a titanium tetrachloride storage tank 8.

[0043] The thickener 7 is connected with the centrifuge 9, and the centrifuge 9 is connected with the pyrolysis furnace 10;

[0044] The thickener 7 is connected with the direct cooling collecting tank 12, and the direct cooling collecting tank 12 is connected with the spiral plate heat exchanger 14 through the direct cooling pump 13; the spiral plate heat exchanger 14 is connected with the direct condenser 11;

[0045] The direct condenser 11 is connected with the first-stage indirect condenser 15 and the second-stage indirect condenser 16;

[0046] The first-stage indirect condenser 15 and the second-stage indirect condenser 16 are connected with the crude titanium storage tank 17, and the crude titanium storage tank 17 is connected with the crude titanium pump 18 and the gas-liquid separator 19;

[0047] The pyrolysis furnace 10 is connected with the chlorination furnace 20.

[0048] The further technical scheme of the present application is that the chlorination furnace 20 is connected with the cyclone dust collector 21, the cyclone dust collector 21 is connected with the direct condenser 22, the direct condenser 22 is connected with the direct cooling collecting tank 23, and the direct cooling collecting tank 23 is connected with the spiral plate heat exchanger 25 through the direct cooling pump 24;

[0049] The direct cooling collecting tank 23 is connected with the vanadyl trichloride storage tank 29;

[0050] The vanadyl trichloride storage tank 29 is connected with the first-stage indirect condenser 26, the second-stage indirect condenser 27 and the gas-liquid separator 28.

[0051] The further technical scheme of the present application is that the vanadyl trichloride storage tank 29 is connected with the vanadyl trichloride distillation kettle 30, the vanadyl trichloride distillation kettle 30 is connected with the vanadyl trichloride distillation column 31, the vanadyl trichloride distillation column 31 is connected with the vanadyl trichloride condenser 32, the vanadyl trichloride condenser 32 and the vanadyl trichloride reflux tank 33, the vanadyl trichloride reflux tank 33 is connected with the reflux pump 34, and the reflux pump 34 is connected with the vanadyl trichloride distillation column 31;

[0052] The vanadyl trichloride distillation kettle 30 is connected with the settling tank 35, and the settling tank 35 is arranged with the thickener 36; the thickener 36 is connected with the vanadyl trichloride second-stage storage tank 39 and the magnetic pump 40, and the magnetic pump 40 is connected with the vanadyl trichloride distillation kettle 30;

[0053] The settling tank 35 is connected with the centrifuge 37, and the centrifuge 37 is connected with the pyrolysis furnace 38.

[0054] The present application has the following beneficial effects compared with the prior art: the present application is a continuous production operation, has high production efficiency, large capacity, safety, economy, environmental protection, and initiatively produces two products in combination, and through strict reaction steps, the product is diversified, and a separate production line is not needed. BRIEF DESCRIPTION OF DRAWINGS

[0055] In order to further illustrate the present application, further description is made below in combination with the drawings:

[0056] Figure 1 is a structural diagram;

[0057] Figure 2 is Figure 1 a partial structural diagram of;

[0058] Figure 3 is Figure 1 a partial structural diagram of;

[0059] 1. Vanadium removal distillation kettle; 2, vanadium removal distillation column; 3, vanadium removal condenser; 4, vanadium removal reflux tank; 5, vanadium removal reflux pump; 6, settling tank one; 7, thickener one; 8. Titanium tetrachloride storage tank; 9. Centrifuge one; 10 pyrolysis furnace one; 11. Direct condenser one; 12. Direct cooling tank one; 13 direct cooling pump one; 14. Spiral plate heat exchanger one; 15. First stage indirect condenser one; 16. Second stage indirect condenser one; 17. Coarse titanium storage tank; 18. Coarse titanium pump; 19. Gas-liquid separator one; 20. Chlorination furnace; 21. Cyclone dust collector; 22. Direct condenser two; 23. Direct cooling tank two; 24. Direct cooling pump two; 25. Spiral plate heat exchanger two; 26. First stage indirect condenser two; 27. Second stage indirect condenser two; 28. Gas-liquid separator two; 29. Vanadyl trichloride storage tank; 30. Vanadyl trichloride distillation kettle; 31. Vanadyl trichloride distillation column; 32. Vanadyl trichloride condenser; 33. Vanadyl trichloride reflux tank; 34. Vanadyl trichloride reflux pump; 35. Settling tank two; 36. Thickener two; 37. Centrifuge two; 38. Pyrolysis furnace two; 39. Vanadyl trichloride secondary storage tank; 40. Magnetic pump. DETAILED DESCRIPTION

[0060] The present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. In the description of the present invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," "outer," "top," and "bottom," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the present invention. In addition, unless otherwise expressly specified and limited, the terms "installed," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication of two components. For those skilled in the art, the specific meaning of the above terms in the present invention can be understood according to the specific circumstances.

[0061] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0062] This patent provides multiple parallel solutions; the different descriptions represent improved solutions or parallel solutions based on the basic solution. Each solution has its own unique characteristics. Furthermore, the technical features involved in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other. Fixing methods not described herein can be any type of fixing, such as threaded fixing, bolt fixing, or adhesive bonding.

[0063] A method for extracting and converting vanadium oxychloride from crude titanium tetrachloride, characterized by comprising the following steps:

[0064] During the refining process of crude titanium tetrachloride, an organic naphthenic oil is added to reduce VOCl3 in the crude titanium to VOCl2, which then enters the refining slurry.

[0065] TiCl4 is first recovered from the refined vanadium-containing slurry, and then chlorine gas is introduced and heated to convert VOCl2 back into VOCl3 gas.

[0066] The VOCI3 gas is condensed to obtain VOCI3 liquid;

[0067] Finally, the VOCI3 gas is evaporated and condensed to obtain pure VOCI3 liquid.

[0068] More specifically, referring to all the drawings, especially Figure 1 The crude titanium tetrachloride is obtained by mixing the titanium-rich material with petroleum coke and adding the mixture into a chlorination furnace to perform chlorination reaction with chlorine gas in a fluidized state;

[0069] Since the titanium-rich material contains V2O5, the V2O5 reacts with chlorine gas and petroleum coke at high temperature in the chlorination furnace to generate VOCI3, which enters the crude titanium tetrachloride through the condensing system with the furnace gas;

[0070] Chemical equation: V2O5+2C+3Cl2=2VOCI3+CO+CO2;

[0071] In the refining production, the crude titanium tetrachloride enters the vanadium removal distillation kettle 1, is uniformly mixed with the vanadium removal agent, is heated by the vanadium removal heater, and is carbonized and cracked into nascent carbon at high temperature. The nascent carbon reacts with vanadyl trichloride to reduce the vanadyl trichloride into vanadyl dichloride, which is precipitated into the refined slurry and discharged from the vanadium removal distillation kettle 1, so as to remove the vanadyl trichloride;

[0072] Chemical equation: 2VOCI3+C=2VOCI2+COCl2;

[0073] The refined slurry enters the settling tank 6 from the vanadium removal distillation kettle 1. The slurry in the settling tank 6 is thickened by the thickener 7, and the bottom slurry enters the centrifuge 9 below the thickener. The supernatant returns to the crude titanium storage tank 17. The centrifuge 9 separates the solid and liquid under the action of centrifugal force by rotation to further thicken the slurry. The separated clear liquid returns to the settling tank 6. The slurry separated by the centrifuge 9 enters the pyrolysis furnace 10 for continuous drying. The evaporated titanium tetrachloride gas passes through the direct condenser 11 and the first-stage indirect condenser in sequence. The titanium tetrachloride condensed by the direct condenser 11 enters the direct cooling collection tank 12, and overflows at a high liquid level to the settling tank 6. The titanium tetrachloride condensed by the first-stage indirect condenser flows into the crude titanium storage tank 17.

[0074] The high-temperature vanadium slag after evaporation enters the small chlorination furnace 20, and heated chlorine gas is introduced to react with vanadyl dichloride in the vanadium slag to generate vanadyl trichloride: Chemical equation: 2VOCI2+Cl2=2VOCI3.

[0075] The vanadyl trichloride gas from the chlorination furnace 20 is condensed into vanadyl trichloride liquid by the direct condenser two 22 and the indirect condenser. The vanadyl trichloride condensed by the direct condenser two 22 enters the direct condenser collection tank two 23, and the vanadyl trichloride condensed by the indirect condenser flows into the vanadyl trichloride storage tank 29. The vanadyl trichloride in the storage tank is transported to the vanadyl trichloride distillation kettle 30 by the magnetic pump 10, and after heating and distillation, the vanadyl trichloride gas enters the vanadyl trichloride condenser 32 through the top of the vanadyl trichloride distillation column 31, and then enters the vanadyl trichloride reflux tank 33. Part of the vanadyl trichloride in the vanadyl trichloride reflux tank 33 refluxes into the vanadyl trichloride distillation column 31, and part of the vanadyl trichloride is transported to the tank area vanadyl trichloride storage tank by the vanadyl trichloride reflux pump 34 for storage and sale. The direct condenser one 11 of the titanium tetrachloride recovery system, through the direct condenser pump one 13, transports the titanium tetrachloride in the direct condenser collection tank one 12 to the spiral plate heat exchanger one 14 for cooling, and then enters the direct condenser one 11. The titanium tetrachloride liquid passes through the tower plate from top to bottom and directly contacts with the titanium tetrachloride gas from bottom to top for mass transfer and heat transfer, so that the titanium tetrachloride gas is condensed into titanium tetrachloride liquid. The titanium tetrachloride gas that is not cooled into liquid enters the indirect condenser for further condensation. The cooling medium in the spiral plate heat exchanger one 14 is circulating water. The indirect condensation is two-stage condensation in series, that is, the first-stage indirect condenser one 15 and the second-stage indirect condenser one 16. The cooling medium of the two-stage indirect condensation is refrigerated brine.

[0076] The vanadyl trichloride direct condenser is the direct condenser two 22. The vanadyl trichloride in the direct condenser collection tank two 23 is transported to the spiral plate heat exchanger two 25 by the direct condenser pump two 24 for cooling, and then enters the direct condenser two 22. The vanadyl trichloride liquid passes through the tower plate from top to bottom and directly contacts with the vanadyl trichloride gas from bottom to top for mass transfer and heat transfer, so that the vanadyl trichloride gas is condensed into vanadyl trichloride liquid. The vanadyl trichloride gas that is not cooled into liquid enters the indirect condenser for further condensation. The cooling medium in the spiral plate heat exchanger two 25 is circulating water. The indirect condensation is two-stage condensation in series, that is, the first-stage indirect condenser two 26 and the second-stage indirect condenser two 27. The cooling medium of the two-stage indirect condensation is refrigerated brine. The vanadyl trichloride system: when the solid content in the vanadyl trichloride distillation kettle 30 reaches the control standard, the slurry is discharged to the sedimentation tank two 35. The slurry in the sedimentation tank two 35 is thickened by the thickener two 36, and the bottom slurry enters the centrifuge two 37 below the thickener two 36. The supernatant flows into the vanadyl trichloride secondary storage tank 39, and then is transported to the vanadyl trichloride distillation kettle 30 by the magnetic pump. The centrifuge two 37 separates the solid and liquid under the action of centrifugal force to further thicken the slurry. The separated clear liquid returns to the sedimentation tank two 35. The slurry separated by the centrifuge two 37 is continuously dried in the pyrolysis furnace two 38. The evaporated vanadyl trichloride gas is sequentially recovered by the direct condenser two 22 and the indirect condenser. The pyrolysis furnace is a horizontal drum design and uses electric heating. The vanadyl trichloride distillation kettle is designed for electromagnetic induction heating.

[0077] Main process control parameters

[0078]

[0079] The equipment used in the above process is as follows:

[0080] The device for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride is characterized in that,

[0081] The vanadium removal distillation kettle 1 is connected with the vanadium removal distillation tower 2, the vanadium removal distillation tower 2 is connected with the vanadium removal condenser 3, the vanadium removal condenser 3 is connected with the vanadium removal reflux tank 4, and the vanadium removal reflux tank 4 is connected with the vanadium removal distillation tower 2 through the vanadium removal reflux pump 5;

[0082] The vanadium removal distillation kettle 1 is connected with the thickener 7, and the thickener 7 and the settling tank 6 are integrally arranged; the settling tank 6 is connected with the titanium tetrachloride storage tank 8;

[0083] The thickener 7 is connected with the centrifuge 9, and the centrifuge 9 is connected with the pyrolysis furnace 10;

[0084] The thickener 7 is connected with the direct cooling collection tank 12, the direct cooling collection tank 12 is connected with the spiral plate heat exchanger 14 through the direct cooling pump 13; and the spiral plate heat exchanger 14 is connected with the direct condenser 11;

[0085] The direct condenser 11 is connected with the first-stage indirect condenser 15 and the second-stage indirect condenser 16;

[0086] The first-stage indirect condenser 15 and the second-stage indirect condenser 16 are connected with the crude titanium storage tank 17, and the crude titanium storage tank 17 is connected with the crude titanium pump 18 and the gas-liquid separator 19;

[0087] The pyrolysis furnace 10 is connected with the chlorination furnace 20.

[0088] The chlorination furnace 20 is connected with the cyclone dust collector 21, the cyclone dust collector 21 is connected with the direct condenser 22, the direct condenser 22 is connected with the direct cooling collection tank 23, and the direct cooling collection tank 23 is connected with the spiral plate heat exchanger 25 through the direct cooling pump 24;

[0089] The direct cooling collection tank 23 is connected with the vanadium oxytrichloride storage tank 29;

[0090] The vanadium oxytrichloride storage tank 29 is connected with the first-stage indirect condenser 26, the second-stage indirect condenser 27, and the gas-liquid separator 28.

[0091] Vanadium oxytrichloride storage tank 29 is connected with vanadium oxytrichloride distillation kettle 30, vanadium oxytrichloride distillation kettle 30 is connected with vanadium oxytrichloride distillation column 31, vanadium oxytrichloride distillation column 31 is connected with vanadium oxytrichloride condenser 32, vanadium oxytrichloride condenser 32 and vanadium oxytrichloride reflux tank 33, vanadium oxytrichloride reflux tank 33 is connected with reflux pump 34, reflux pump 34 is connected with vanadium oxytrichloride distillation column 31;

[0092] Vanadium oxytrichloride distillation kettle 30 is connected with settling tank two 35, and the thickener two 36 is arranged in the settling tank two 35, the thickener two 36 is connected with vanadium oxytrichloride secondary storage tank 39 and magnetic pump 40, magnetic pump 40 is connected with vanadium oxytrichloride distillation kettle 30;

[0093] Settling tank two 35 is connected with centrifuge two 37, centrifuge two 37 is connected with pyrolysis furnace two 38.

[0094] It should be noted that all chemical components are not irreplaceable, and can be replaced by similar components and devices that can achieve similar functions.

[0095] Pioneeringly, the above various effects exist independently, and the combination of the above results can also be completed by a set of structures.

[0096] It should be noted that the multiple schemes provided by the patent contain the basic scheme itself, are independent of each other and do not restrict each other, but they can also be combined with each other without conflict to achieve multiple effects together.

[0097] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of protection.

Claims

1. A method for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride, characterized in that, The method comprises the following steps: The crude titanium tetrachloride is added with naphthenic oil in the refining process, and VOCI3 in the crude titanium is reduced to VOCI2 and enters the refining slurry; TiCl4 is recovered from the refining slurry, and then VOCI2 is converted into VOCI3 gas by heating and passing in chlorine; The VOCI3 gas is condensed to obtain VOCI3 liquid; Finally, the VOCI3 gas is evaporated, condensed and recovered to obtain pure VOCI3 liquid.

2. The method according to claim 1, wherein the crude titanium tetrachloride is prepared by mixing a titanium-rich material with petroleum coke, and then chlorinating the mixture in a chlorination furnace under fluidized state to obtain the crude titanium tetrachloride; V2O5 in the titanium-rich material reacts with chlorine and petroleum coke at high temperature in the chlorination furnace to generate VOCI3, which enters the crude titanium tetrachloride through a condensing system; Chemical equation: V2O5+2C+3Cl2=2VOCI3+CO+CO2; In the refining process, the crude titanium tetrachloride enters a vanadium removal distillation kettle (1), is uniformly mixed with a vanadium removal agent, is heated by a vanadium removal heater, and is carbonized and cracked into nascent carbon at high temperature, so that the nascent carbon reacts with vanadyl trichloride to reduce the vanadyl trichloride into vanadyl dichloride and then into a slurry which is discharged from the vanadium removal distillation kettle (1) and is removed from the vanadyl trichloride; Chemical equation: 2VOCI3+C=2VOCI2+COCl2; The slurry enters a settling tank (6), is thickened by a thickener (7), and then the bottom slurry enters a centrifuge (9) below the thickener, the supernatant returns to a crude titanium storage tank (17), the centrifuge (9) separates the slurry again under the action of centrifugal force, the separated supernatant returns to the settling tank (6), and the separated slurry enters a pyrolysis furnace (10) for continuous drying, titanium tetrachloride gas is evaporated and sequentially passes through a direct condenser (11) and a first-stage indirect condenser, the condensed titanium tetrachloride enters a direct cooling collection tank (12), the high liquid level overflows to the settling tank (6), and the condensed titanium tetrachloride from the first-stage indirect condenser flows to the crude titanium storage tank (17); The high-temperature vanadium slag is introduced into a small chlorination furnace (20), heated chlorine is introduced into the chlorination furnace (20), and the vanadium slag reacts with the heated chlorine to generate vanadyl trichloride: chemical equation: 2VOCI2+Cl2=2VOCI3.

3. The method according to claim 2, wherein the vanadyl trichloride gas from the chlorination furnace (20) is condensed into vanadyl trichloride liquid by a direct condenser (22) and an indirect condenser, the condensed vanadyl trichloride enters a direct cooling collection tank (23), and the condensed vanadyl trichloride from the indirect condenser flows to a vanadyl trichloride storage tank (29). ​ ​ The vanadium oxytrichloride in the storage tank is delivered to the vanadium oxytrichloride distillation kettle (30) by the magnetic pump (10) for heating and distillation, and the vanadium oxytrichloride gas is condensed into the vanadium oxytrichloride reflux tank (33) through the vanadium oxytrichloride condenser (32) after entering the vanadium oxytrichloride distillation column (31) from the top, part of the vanadium oxytrichloride in the vanadium oxytrichloride reflux tank (33) is refluxed into the vanadium oxytrichloride distillation column (31), and part of the vanadium oxytrichloride is delivered to the tank area vanadium oxytrichloride storage tank for storage and sale by the vanadium oxytrichloride reflux pump (34).

4. The method of extracting vanadium oxytrichloride from crude titanium tetrachloride according to claim 3, wherein The direct condenser one (11) of the titanium tetrachloride recovery, through the direct cooling pump one (13), delivers the titanium tetrachloride in the direct cooling collection tank one (12) to the spiral plate heat exchanger one (14) for cooling and then enters the direct condenser one (11), the titanium tetrachloride liquid from top to bottom is in direct contact with the titanium tetrachloride gas from bottom to top through the tower plate to transfer mass and heat, so that the titanium tetrachloride gas is condensed into titanium tetrachloride liquid; The titanium tetrachloride gas that is not cooled into liquid enters the indirect condenser for further condensation; the cooling medium in the spiral plate heat exchanger one (14) is circulating water; the indirect condensation is two-stage condensation in series, that is, the first-stage indirect condenser one (15) and the second-stage indirect condenser one (16), and the cooling medium of the two stages is refrigerated brine.

5. The process for extracting vanadium oxytrichloride from crude titanium tetrachloride as claimed in claim 4, wherein, The vanadium oxytrichloride direct condenser is the direct condenser two (22), the vanadium oxytrichloride in the direct cooling collection tank two (23) is delivered to the spiral plate heat exchanger two (25) for cooling and then enters the direct condenser two (22) by the direct cooling pump two (24), the vanadium oxytrichloride liquid from top to bottom is in direct contact with the vanadium oxytrichloride gas from bottom to top through the tower plate to transfer mass and heat, so that the vanadium oxytrichloride gas is condensed into vanadium oxytrichloride liquid; the vanadium oxytrichloride gas that is not cooled into liquid enters the indirect condenser for further condensation; the cooling medium in the spiral plate heat exchanger two (25) is circulating water; the indirect condensation is two-stage condensation in series, that is, the first-stage indirect condenser two (26) and the second-stage indirect condenser two (27), and the cooling medium of the two stages is refrigerated brine.

6. The process for extracting vanadium oxytrichloride from crude titanium tetrachloride as claimed in claim 5 wherein, The vanadium oxytrichloride system: when the solid content in the vanadium oxytrichloride distillation kettle (30) reaches the control standard, the sludge is discharged to the sedimentation tank two (35), the sludge in the sedimentation tank two (35) is thickened by the thickener two (36), the bottom sludge enters the centrifuge two (37) below the thickener two (36), and the supernatant flows to the vanadium oxytrichloride secondary storage tank (39) by itself, and then is delivered to the vanadium oxytrichloride distillation kettle (30) by the magnetic pump; the centrifuge two (37) separates the solid and liquid under the action of centrifugal force by rotation to further thicken the sludge, the separated clear liquid returns to the sedimentation tank two (35), and the separated sludge of the centrifuge two (37) enters the pyrolysis furnace two (38) for continuous drying, and the evaporated vanadium oxytrichloride gas is recovered in sequence through the direct condenser two (22) and the indirect condenser.

7. The process for extracting vanadium oxytrichloride from crude titanium tetrachloride as claimed in claim 5 wherein, The pyrolysis furnace is designed as a horizontal roller and uses electric heating; the vanadium oxytrichloride distillation kettle is designed for electromagnetic induction heating. Main process control parameters 。 8. A device for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride, characterized in that, The vanadium removal distillation kettle (1) is connected with a vanadium removal distillation tower (2), the vanadium removal distillation tower (2) is connected with a vanadium removal condenser (3), the vanadium removal condenser (3) is connected with a vanadium removal reflux tank (4), and the vanadium removal reflux tank (4) is connected with the vanadium removal distillation tower (2) through a vanadium removal reflux pump (5); The vanadium removal distillation kettle (1) is connected with a thickener (7), and the thickener (7) and a settling tank (6) are arranged integrally; the settling tank (6) is connected with a titanium tetrachloride storage tank (8); The thickener (7) is connected with a centrifugal machine (9), and the centrifugal machine (9) is connected with a pyrolysis furnace (10); The thickener (7) is connected with a direct cooling collection tank (12), and the direct cooling collection tank (12) is connected with a spiral plate heat exchanger (14) through a direct cooling pump (13); the spiral plate heat exchanger (14) is connected with a direct condenser (11); The direct condenser (11) is connected with a first-stage indirect condenser (15) and a second-stage indirect condenser (16); The first-stage indirect condenser (15) and the second-stage indirect condenser (16) are connected with a crude titanium storage tank (17), and the crude titanium storage tank (17) is connected with a crude titanium pump (18) and a gas-liquid separator (19); The pyrolysis furnace (10) is connected with a chlorination furnace (20).

9. The device for extracting vanadyl chloride from crude titanium tetrachloride according to claim 8, characterized in that, The chlorination furnace (20) is connected with a cyclone dust collector (21), the cyclone dust collector (21) is connected with a direct condenser (22), the direct condenser (22) is connected with a direct cooling collection tank (23), and the direct cooling collection tank (23) is connected with a spiral plate heat exchanger (25) through a direct cooling pump (24); The direct cooling collection tank (23) is connected with a vanadyl chloride storage tank (29); The vanadyl chloride storage tank (29) is connected with a first-stage indirect condenser (26), a second-stage indirect condenser (27), and a gas-liquid separator (28).

10. The apparatus for extracting and converting vanadium oxytrichloride from crude titanium tetrachloride according to claim 9, wherein The vanadyl chloride storage tank (29) is connected with a vanadyl chloride distillation kettle (30), the vanadyl chloride distillation kettle (30) is connected with a vanadyl chloride distillation tower (31), the vanadyl chloride distillation tower (31) is connected with a vanadyl chloride condenser (32), the vanadyl chloride condenser (32) is connected with a vanadyl chloride reflux tank (33), the vanadyl chloride reflux tank (33) is connected with a reflux pump (34), and the reflux pump (34) is connected with the vanadyl chloride distillation tower (31); The vanadyl chloride distillation kettle (30) is connected with a settling tank (35), and the settling tank (35) is arranged with a thickener (36), the thickener (36) is connected with a vanadyl chloride second-stage storage tank (39) and a magnetic pump (40), and the magnetic pump (40) is connected with the vanadyl chloride distillation kettle (30); The settling tank (35) is connected with a centrifugal machine (37), and the centrifugal machine (37) is connected with a pyrolysis furnace (38).

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