Device and method for producing titanium tetrachloride by utilizing low-grade titanium ore and boiling chlorination furnace

Abstract

The invention relates to the field of production of titanium tetrachloride, in particular to a device and a method for producing titanium tetrachloride by utilizing low-grade titanium ore and a boiling chlorination furnace. The chlorination furnace (1) is connected with a quench tower (2), the cyclone dust collector is connected with a direct condenser (13), and the direct condenser (13) is connected with an indirect condenser; the low-grade titanium ore is creatively utilized to produce titanium tetrachloride, a proper amount of chlorine is introduced into the furnace top to prevent a quench tower from being blocked, and meanwhile, part of the chlorine on the furnace top and the fine-fraction titanium ore and the fine-fraction petroleum coke which are brought into the furnace top react again to improve the Ti yield. The crusher is additionally arranged below the cyclone dust collector to crush occasionally appearing ash discharging blocks, an ash discharging pipe is prevented from being blocked, 20% liquid caustic soda is creatively used for removing aluminum chloride, the two-stage cyclone series connection technology is used for achieving the purpose of reducing the solid content of crude titanium and the like, and after the temperature is reduced through spraying, equipment loss can be avoided; and the boiling point difference of ferrous chloride and ferric chloride is ingeniously utilized to realize safe production of the whole equipment, and blockage is avoided.

Description

Technical Field

[0001] The invention relates to the field of titanium tetrachloride production, and in particular to a device and method for producing titanium tetrachloride by using low-grade titanium ore and a boiling chlorination furnace. Background Art

[0002] At present, the titanium raw material TiO is used in domestic boiling chlorination 2 The content is about 85%. Due to the high price of high-titanium slag and rutile required for boiling chlorination furnaces in China, the cost of producing titanium tetrachloride raw materials is high, while the price of low-grade titanium concentrate is low. Using low-grade titanium concentrate as a raw material for boiling chlorination furnaces can greatly reduce the cost of producing titanium tetrachloride raw materials. However, there is no relevant technology at present.

[0003] On October 11, 2024, a search was conducted in the Chinese Patent Publication Database with "boiling chlorination furnace and Ti and petroleum coke" as the abstract keywords, and the option to allow synonym expansion was checked, but no relevant literature was found.

[0004] On October 11, 2024, an abstract search for "boiling chlorination furnace and Ti and petroleum coke" was conducted on China National Knowledge Infrastructure, and four documents were found, namely: 2017-04-26 Liu Jianliang; Ma Xiang; Li Jianjun; Wang Hongjiang; Jiang Shuan et al. published "Research and Development of Key Technologies for Industrialization of Large-scale Boiling Chlorination Titanium Dioxide"; 2015-01-31 Guo Zhibin; Li Yinan; Ma Gonglin published "New Process for Producing High-Purity Zirconium Oxychloride by Boiling Chlorination"; 2009-01-16 Lu Ping; Yang Yangjun; Huang Jiaxu; Chen Zhuchun; Liu Senlin published "Development of Boiling Chlorination Test Equipment and Related Process Research"; 1979-05-01 Pang Xianmin published "Research on Calcium and Magnesium Problems in the Boiling Chlorination Process of High-Titanium Slag". "Research and Development of Key Technologies for Industrialization of Titanium Dioxide by Large-Scale Boiling Chlorination Process" disclosed: The process of producing titanium tetrachloride by chlorination of high-titanium slag in a large-scale sieveless boiling chlorination furnace has made breakthroughs in the technology and equipment for producing titanium tetrachloride in a large-scale sieveless boiling chlorination furnace with a diameter of 7 meters, which still uses high-titanium slag; "New process for producing high-purity zirconium oxychloride by boiling chlorination" discloses that zircon sand and chlorine are used as the main raw materials, and silicon carbide, metallic silicon or a mixture of the two reacts with chlorine to release a large amount of heat to supplement the insufficient heat of the reaction of zircon sand, petroleum coke and chlorine, thereby ensuring the mass transfer of materials in the chlorination furnace; "Research on calcium and magnesium issues in the process of boiling chlorination of high-titanium slag" discloses the study of the chlorination characteristics of two titanium raw materials, and the successful realization of stable operation of high-titanium slag and artificial rutile on the platform device. The chlorination rate of high-titanium slag is >97%, and the chlorination rate of artificial rutile is >98%, proving that the platform has the function of systematically studying the boiling chlorination characteristics of a variety of titanium-rich materials.

[0005] None of the above technologies can solve the problem of low-grade titanium raw material TiO 2 A process for producing titanium tetrachloride.

[0006] On October 11, 2024, a search was conducted on the website of the United States Patent and Trademark Office for “fluidizing chlorination with titanium with petroleum coke”; the search URL was https: / / ppubs.uspto.gov / pubwebapp / .

[0007] Found: US17950491: Process for Selective Chlorination of AluminousOres for the Preparation of Aluminum; US18439211: Serviceable electrostaticstorage device; the two technologies are: a usable energy storage device, such as a capacitor, supercapacitor or ultracapacitor, comprising an electrode made of activated carbon produced from a low-cost source (such as thermal coal or another low-cost raw material); a carbon chlorination process for selectively producing AlCl from an alumina-containing raw material.

[0008] On October 11, 2024, a search was conducted on the Korean Patent Office for "fluidizing chlorination and titanium and petroleum coke", and no relevant literature was found; the search URL was http: / / eng.kipris.or.kr / enghome / main.jsp.

[0009] On October 11, 2024, a search was conducted on WIPO's https: / / patentscope2.wipo.int / for "fluidizingchlorinationandtitanium and petroleumcoke" and it was found that: GB727286-ZONINGDEVICE FOR HORIZONTAL FLUO-SOLID BEDS provides a fluidized bed, which is not related to this patent.

[0010] Completely different from the concept of this patent. Summary of the invention

[0011] Purpose of the invention: To provide a better device and method for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace. The specific purpose can be seen in the multiple substantial technical effects of the specific implementation part.

[0012] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0013] The device for producing titanium tetrachloride by using low-grade titanium ore and a boiling chlorination furnace is characterized in that the device comprises a chlorination furnace 1, a quenching tower 2 is connected to the chlorination furnace 1, the quenching tower 2 is connected to a cyclone dust collector, the cyclone dust collector is connected to a direct condenser 13, the direct condenser 13 is connected to an indirect condenser, a pipeline below the indirect condenser is connected to a crude titanium tank 19, a direct cooling collection tank 14 is connected below the direct condenser 13, the direct cooling collection tank 14 is connected to the crude titanium tank 19 through a pipeline, and a direct cooling pump outlet of the direct cooling collection tank 14 also branches out a pipeline leading to a feeding tank 7 of the quenching tower 2;

[0014] The quenching tower 2 is arranged above the chlorination furnace 1;

[0015] Chlorination furnace 1 is a boiling chlorination furnace, which includes a double shell design. Circulating water enters from the bottom of the furnace and flows out from the top of the furnace through the shell from bottom to top, thereby cooling the furnace wall. Due to the use of the shell design, the shell is filled with water to isolate the oxygen in the air, which can greatly reduce the rust rate of the furnace wall. Since the shell is fully sealed, there is no situation where the furnace wall cooling water is heated to generate water vapor that fills the factory building, which protects the equipment in the factory building.

[0016] A further technical solution of the present invention is that a crusher 53 and a crusher 58 are arranged above the lower ash pipe of the cyclone dust collector. The crusher 53 and the crusher 58 can crush the lumps in the collected dust to prevent the lumps from clogging the lower ash pipe.

[0017] A further technical solution of the present invention is that upper half ball valve 1 54 , upper half ball valve 2 59 , lower half ball valve 1 55 , lower half ball valve 2 60 , star-shaped ash discharge valve 1 56 , star-shaped ash discharge valve 2 61 are arranged below crusher 1 53 and crusher 2 58 .

[0018] A further technical solution of the present invention is that indirect cooling adopts two-stage indirect cooling, the first stage is circulating water cooling, and the second stage is chilled brine cooling; the indirect condenser includes two groups, the first group is used for circulating water cooling, and the second group is used for chilled brine cooling.

[0019] A further technical solution of the present invention is that the air inlet mechanism of the chlorination furnace comprises an air inlet hole at the bottom and 36 air inlet holes at the side, for a total of 37 air inlet holes. The 36 air inlet holes at the side are distributed in three layers, with 12 air inlet holes in each layer. A flow meter and an air inlet valve are installed at each air inlet hole, and the flow rate can be adjusted by the air inlet valve to ensure that the bed layer boils fully and evenly.

[0020] A further technical solution of the present invention is that 8 DN15 Inconel tubes are installed on the top of the chlorination furnace 1, which are chlorine distribution pipes on the top of the furnace, and are inserted 1 meter deep. Chlorine is introduced through the top of the furnace to react with furnace gas and ferrous chloride attached to the quenching tower to generate ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attached objects in the quenching tower fall into the furnace, and the quenching tower is kept unobstructed. At the same time, an appropriate amount of chlorine is introduced into the top of the furnace, and part of the chlorine reacts with petroleum coke and titanium concentrate fine particles, further improving the Ti yield.

[0021] A further technical solution of the present invention is that a venturi tube 94 is arranged before the inlet of the cyclone dust collector; the liquid alkali is transported to the venturi tube by a metering pump and atomized into small liquid alkali droplets, which are mixed with AlCl in the crude titanium tetrachloride gas. 3 The aluminum hydroxide solid generated by the reaction is separated in a cyclone dust collector; the cyclone dust collector comprises two stages, and the two-stage cyclone separators are connected in series, so that the crude titanium tetrachloride gas and solid produced by the chlorination furnace are fully separated under the action of centrifugal force, so as to achieve the purpose of reducing the crude titanium solid content.

[0022] A further technical solution of the present invention is that a gas-liquid separator is arranged after the indirect condenser, the gas part of the gas-liquid separator is connected to a six-stage turbulent spray absorption tower, and the chlorinated tail gas adopts a six-stage turbulent spray absorption tower in series design. Each tower can be independently removed from the system for regular cleaning and maintenance. The first, second, third and sixth stages are water washing towers, and the fourth and fifth stages are alkali washing towers.

[0023] The method for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace is characterized by comprising the following steps:

[0024] Use TiO 2 Titanium concentrate with a content of 54% to 55% is used to produce titanium tetrachloride in a boiling chlorination furnace;

[0025] Titanium concentrate and petroleum coke are mixed several times to meet the production requirements. They are then metered into the chlorination furnace and react with chlorine at a high temperature of 850-1100°C.

[0026] Petroleum coke plays a catalytic role and participates in the reaction, allowing titanium concentrate and chlorine to react at a lower temperature. The reaction formula is:

[0027] (2-φ / 2)TiO 2 +C+(2-φ)Cl 2 =(1-φ / 2)TiCl 4 +(1-φ)CO 2 +φCO Where: TiO 2 Titanium dioxide is the main component of titanium concentrate, C is the main component of petroleum coke, and Cl 2 It is chlorine, TiCl 4It is the product of the chlorination process, titanium tetrachloride, CO is carbon monoxide, CO 2 is carbon dioxide, φ is the phi value, i.e. the ratio of carbon monoxide to the sum of carbon monoxide and carbon dioxide (φ=CO / (CO+CO2));

[0028] During the production process of the chlorination furnace, 20% of liquid alkali is sprayed in the titanium tetrachloride gas through the venturi tube alkali adding device at the cyclone inlet quench pipe to remove aluminum trichloride;

[0029] Reaction equation: AlCl 3 (g)+3NaOH(q)→Al(OH) 3 (s)+2NaCl(s)

[0030] During the reaction, crude TiCl 4 Liquid gas-liquid heat exchange is carried out to keep the temperature of the cyclone dust collector outlet gas at 165-180℃, which can protect the equipment and pipelines from high temperature damage and avoid TiCl 4 Gas condenses into liquid and blocks the cyclone dust collector. TiCl 4 The boiling point is 136℃. At the same time, the solid content in the crude titanium is also reduced by controlling the outlet temperature of the cyclone dust collector. 4 The spray volume is used to adjust the cyclone outlet temperature to ensure smooth production;

[0031] Crude TiCl from cyclone dust collector 4 After the gas enters the condensation system, in the direct condenser, the TiCl4 is first condensed by direct contact with the crude TiCl4 liquid. 4 and high boiling point chlorides, where the high boiling point chlorides include FeCl 3 、AlCl 3 、TiOCl 2 , and then TiCl is indirectly condensed in an indirect condenser with a coolant 4 And low boiling point chloride, low boiling point chloride is SiCl 4 , CCl 4； The coolant is circulating water and chilled brine, and most of the crude TiCl 4 The gas is condensed into liquid in the direct cooling and stored in the direct cooling collection tank. The remaining crude TiCl 4 The gas is condensed in the indirect cooling and flows into the crude titanium tank; the crude TiCl in the direct cooling collection tank 4 The liquid part enters the crude titanium tank through the overflow pipe and is transported to the refined titanium tetrachloride tank area by the crude titanium pump for standing; the remaining crude TiCl 4 After the liquid passes through the spiral plate heat exchanger, it enters the direct cooling system to circulate and spray to cool the gaseous TiCl 4A small part of the crude TiCl is transported to the quench tower feed tank through the condensate pump outlet. 4 Liquid, used for spraying in quench tower of chlorination furnace.

[0032] A further technical solution of the present invention is that a dust beating tank is provided at the bottom of the cyclone dust collector to make slurry from the cyclone dust collection ash and transport it to the wastewater and waste residue system for treatment;

[0033] After titanium tetrachloride is collected by direct condenser and indirect condenser, the remaining gas components are mainly CO, CO 2 、N 2 、SO 2 , HCl non-condensable gas, a small amount of uncooled titanium tetrachloride gas, containing trace amounts of Cl 2 The exhaust gas is treated by exhaust gas washing and then discharged after reaching the standard.

[0034] 20% liquid alkali sodium hydroxide is used to remove aluminum chloride. A Venturi tube is installed in the quenching pipe 4 meters before the cyclone inlet. The liquid alkali is transported to the Venturi tube through a metering pump and atomized into small liquid alkali droplets to react with AlCl in the crude titanium tetrachloride gas. 3 The aluminum hydroxide solid generated by the reaction is separated in a cyclone dust collector; 20% liquid alkali sodium hydroxide and TiCl 4 No reaction;

[0035] Chemical formula: AlCl 3 (g)+3NaOH(q)→Al(OH) 3 (s)+2NaCl(s);

[0036] The refined vanadium removal slurry is treated by the slurry vanadium extraction process. The refined vanadium removal slurry does not return to the chlorination feed tank, which further reduces the frequency of blockage of the quench tower and reduces the crude titanium solid content.

[0037] The high iron content of titanium concentrate reacts with chlorine to form ferrous chloride. The quench tower mud spraying easily causes the quench tower to be blocked. Eight DN15 Incon tubes are installed from the top of the furnace, inserted 1 meter deep, and an appropriate amount of chlorine is introduced through the top of the furnace to react with the furnace gas and the ferrous chloride attached to the quench tower to form ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attached materials in the quench tower fall into the furnace, keeping the quench tower unobstructed. The boiling point of ferrous chloride is 700℃, and the boiling point of ferric chloride is 316℃.

[0038] Chemical formula: 2FeCl 2 (s)+Cl 2 (g) = 2FeCl 3 (g)

[0039] An appropriate amount of chlorine is introduced into the furnace top, and part of the chlorine reacts with petroleum coke and titanium concentrate fine particles, further improving the Ti yield.

[0040] The present invention adopting the above technical scheme has the following beneficial effects compared with the prior art: there is no situation where the furnace wall cooling water is heated to generate water vapor that fills the factory building, which plays a protective role on the equipment in the factory building; it is innovative to use low-grade titanium ore to produce titanium tetrachloride, and to use appropriate chlorine gas to pass through the furnace top to prevent the quenching tower from being blocked. At the same time, part of the furnace top chlorine gas reacts with the fine-grained titanium ore and fine-grained petroleum coke brought into the furnace top by the gas to increase the Ti yield. A crusher is installed under the cyclone dust collector to crush the occasional ash blocks to prevent the ash pipe from being blocked. It is innovative to use 20% liquid alkali to remove aluminum chloride, and use two-stage cyclone series technology to achieve the purpose of reducing the solid content of crude titanium, etc. After spraying to reduce the temperature, equipment loss can be avoided, and the difference in boiling points between ferrous chloride and ferric chloride is cleverly used to achieve overall equipment safety production without blockage. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to further illustrate the present invention, the following is further described in conjunction with the accompanying drawings:

[0042] Figure 1 is a flow chart of the chlorination process of the invention;

[0043] Figure 2 To invent the layout of the boiling chlorination furnace;

[0044] Figure 3 This is a diagram of the double cyclone tandem technology device;

[0045] Figure 4 This is a schematic diagram of the tail gas system of the chlorination furnace;

[0046] Figure 5 This is a diagram of the technical device for removing aluminum chloride with liquid caustic soda;

[0047] Among them: 1. Chlorination furnace, 2. Rapid cooling tower, 3. First-stage cyclone dust collector, 4. Second-stage cyclone dust collector, 5. 1# crusher, 6. 2# crusher, 7. 1# star-shaped ash discharge valve, 8. 2# star-shaped ash discharge valve, 9. 1# dust pulping tank, 10. 2# dust pulping tank, 11. Dust pulping scrubber, 12. Dust pulping scrubber fan, 13. Direct condenser, 14. Direct cooling collection tank, 15. 1# spiral plate heat exchanger, 16. 2# spiral plate heat exchanger, 17. 1# condensation pump, 18. 2# condensation pump, 19. Crude titanium tank, 20. Crude titanium pump, 21. Indirect condenser #1 of primary intercooler, 22. Indirect condenser #2 of primary intercooler, 23. Indirect condenser #3 of secondary intercooler, 24. Indirect condenser #4 of secondary intercooler, 25. Gas-liquid separator #1, 26. Gas-liquid separator #2, 27. Tail gas tower #1, 28. Tail gas tower #2, 29. Tail gas tower #3, 30. Tail gas tower #4, 31. Tail gas tower #5, 32. Tail gas tower #6, 33. Tail gas tower #1 titanium fan, 34. Tail gas tower #2 titanium fan, 35. To chimney, 36. From recycled wastewater, 37. To wastewater system; 38. Chlorination furnace 、39. Chlorination furnace feed port、40. Chlorination furnace air inlet coil with 36 air inlets、41. Furnace top chlorine device、42. Bottom air inlet、43. Furnace wall cooling water inlet pipe、44. Furnace wall cooling water outlet pipe、45. Furnace wall cooling water drain valve、46. Chlorination furnace quenching tower、47. Spray gun under quenching tower、48. Spray gun in quenching tower、49. Spray gun on quenching tower、50. Furnace shell double shell、51 Bed sampling device;52. First-stage cyclone dust collector、53. Crusher 1、54. Upper half wall ball valve 1、55. Lower half wall ball valve 1、56. Star-shaped ash unloading Valve 1, 57. Second-stage cyclone dust collector, 58. Second crusher, 59. Second upper wall ball valve, 60. Second lower wall ball valve, 61. Second star-shaped ash discharge valve; 62. First-stage tail gas tower, 63. Second-stage tail gas tower, 64. Third-stage tail gas tower, 65. Fourth-stage tail gas tower, 66. Fifth-stage tail gas tower, 67. Sixth-stage tail gas tower, 68. 1# tail gas titanium fan, 69. 2# tail gas titanium fan, 70. Chimney, 71. Inlet valve of the total tail gas system, 72. Branch inlet valve; 73. Isolation valve; 91. Rapid cooling pipe, 92. Regulating valve, 93. Flow meter, 94. Venturi tube. DETAILED DESCRIPTION

[0048] The present invention is further explained below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. In the description of the present invention, it should be noted that the orientation or position relationship indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "top", "bottom", etc. is based on the orientation or position relationship shown in the accompanying drawings, which is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention. In addition, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected, or indirectly connected through an intermediate medium, or it can be the internal connection of two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood in specific circumstances.

[0049] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0050] This patent provides a variety of parallel solutions. The different expressions are improved solutions or parallel solutions based on the basic solution. Each solution has its own unique characteristics. In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other. The fixing method not described in the text can be any fixing method such as thread fixing, bolt fixing or glue bonding.

[0051] Embodiment 1: In conjunction with all the accompanying drawings; A device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace, characterized in that the device comprises a chlorination furnace 1, a quenching tower 2 is connected to the chlorination furnace 1, the quenching tower 2 is connected to a cyclone dust collector, the cyclone dust collector is connected to a direct condenser 13, the direct condenser 13 is connected to an indirect condenser, a pipeline below the indirect condenser is connected to a crude titanium tank 19, a direct cooling collection tank 14 is connected below the direct condenser 13, the direct cooling collection tank 14 is connected to the crude titanium tank 19 through a pipeline, and a direct cooling pump outlet of the direct cooling collection tank 14 also branches out a pipeline leading to a feeding trough of the quenching tower 2;

[0052] The quenching tower 2 is arranged above the chlorination furnace 1;

[0053] Chlorination furnace 1 is a boiling chlorination furnace, which includes a double shell design. Circulating water enters from the bottom of the furnace and flows out from the top of the furnace through the shell from bottom to top, thereby cooling the furnace wall. Due to the use of the shell design, the shell is filled with water to isolate the oxygen in the air, which can greatly reduce the rust rate of the furnace wall. Since the shell is fully sealed, there is no situation where the furnace wall cooling water is heated to generate water vapor that fills the factory building, which protects the equipment in the factory building.

[0054] The substantial technical effect and implementation process of the technical solution herein, i.e., the basic function thereof, are as follows: A method for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace, characterized in that it comprises the following steps:

[0055] Use TiO 2 Titanium concentrate with a content of 54% to 55% is used to produce titanium tetrachloride in a boiling chlorination furnace;

[0056] Titanium concentrate and petroleum coke are mixed several times to meet the production requirements. They are then metered into the chlorination furnace and react with chlorine at a high temperature of 850-1100°C.

[0057] Petroleum coke plays a catalytic role and participates in the reaction, allowing titanium concentrate and chlorine to react at a lower temperature. The reaction formula is:

[0058] (3-φ / 2)TiO 2 +C+(2-φ)Cl 2 =(1-φ / 2)TiCl 4 +(1-φ)CO 2 +φCO Where: TiO 2 Titanium dioxide is the main component of titanium concentrate, C is the main component of petroleum coke, and Cl 2 It is chlorine, TiCl 4 It is the product of the chlorination process, titanium tetrachloride, CO is carbon monoxide, CO 2 is carbon dioxide, φ is the phi value, that is, the ratio of carbon monoxide to the sum of carbon monoxide and carbon dioxide (φ=CO / (CO+CO 2 ));

[0059] During the production process of the chlorination furnace, 20% of liquid alkali is sprayed in the titanium tetrachloride gas through a venturi tube alkali adding device at the quench pipe 4 meters away from the cyclone inlet to remove aluminum trichloride;

[0060] Reaction equation: AlCl 3 (g)+3NaOH(q)→Al(OH) 3 (s)+2NaCl(s)

[0061] During the reaction, crude TiCl4 liquid is sprayed into the quench tower for gas-liquid heat exchange, so that the temperature of the cyclone dust collector outlet gas is maintained at 165-180°C, which can protect the equipment and pipelines from high temperature damage and avoid the TiCl 4 Gas condenses into liquid and blocks the cyclone dust collector. TiCl 4 The boiling point is 136℃. At the same time, the solid content in the crude titanium is also reduced by controlling the outlet temperature of the cyclone dust collector. 4 The spray volume is used to adjust the cyclone outlet temperature to ensure smooth production;

[0062] Crude TiCl from cyclone dust collector 4 After the gas enters the condensation system, in the direct condenser, the TiCl4 is first condensed by direct contact with the crude TiCl4 liquid. 4 and high boiling point chlorides, where the high boiling point chlorides include FeCl 3 、AlCl 3 、TiOCl 2 , and then TiCl is indirectly condensed in an indirect condenser with a coolant 4 And low boiling point chloride, low boiling point chloride is SiCl 4 , CCl 4； The coolant is circulating water and chilled brine, and most of the crude TiCl 4 The gas is condensed into liquid in the direct cooling and stored in the direct cooling collection tank. The remaining crude TiCl 4 The gas is condensed in the indirect cooling and flows into the crude titanium tank; the crude TiCl in the direct cooling collection tank 4 The liquid part enters the crude titanium tank through the overflow pipe and is transported to the refined titanium tetrachloride tank area by the crude titanium pump for standing; the remaining crude TiCl 4 After the liquid passes through the spiral plate heat exchanger, it enters the direct cooling system to circulate and spray to cool the gaseous TiCl 4 A small part of the crude TiCl is transported to the quench tower feed tank through the condensate pump outlet. 4 Liquid, used for spraying in quench tower of chlorination furnace.

[0063] Embodiment 2: As a further improved solution or parallel solution or optional independent solution, a crusher 1 53 and a crusher 2 58 are arranged above the lower ash pipe of the cyclone dust collector. The crusher 1 53 and the crusher 2 58 can crush the lumps in the dust to prevent the lumps from blocking the lower ash pipe. The substantial technical effect of the technical solution here and its implementation process are as follows: avoid blockage.

[0064] Embodiment 3: As a further improved solution or parallel solution or optional independent solution, upper half ball valve 1 54, upper half ball valve 2 59, lower half ball valve 1 55, lower half ball valve 2 60, star-shaped ash discharge valve 1 56, star-shaped ash discharge valve 2 61 are arranged below crusher 1 53 and crusher 2 58. The substantial technical effect and implementation process of the technical solution here are as follows: The figures of this embodiment and the figures of embodiment 2 refer to Figure 3 .

[0065] Embodiment 4: As a further improved scheme or parallel scheme or optional independent scheme, the indirect cooling adopts two-stage indirect cooling, the first stage is circulating water cooling, and the second stage is chilled brine cooling; the indirect condenser comprises two groups, the first group is used for circulating water cooling, and the second group is used for chilled brine cooling. The substantial technical effect and the implementation process of the technical scheme here are as follows: the indirect cooling adopts two-stage indirect cooling, the first stage is circulating water cooling, and the second stage is chilled brine cooling, which improves the yield of titanium tetrachloride.

[0066] Embodiment 5: As a further improved scheme or parallel scheme or optional independent scheme, the air intake mechanism of the chlorination furnace includes an air intake hole at the bottom plus 36 air intake holes on the side, totaling 37 air intake holes. The 36 air intake holes on the side are distributed in three layers, with 12 air intake holes on each layer; each air intake hole is equipped with a flow meter and an air intake hole valve, and the flow rate can be adjusted through the air intake hole valve to ensure that the bed layer is fully and evenly boiling. The substantial technical effect and implementation process of the technical scheme here are as follows: The air intake of the chlorination furnace adopts a combined air intake method of one air intake hole at the bottom and 36 air intake holes on the side, which are distributed in three layers, with 12 air intake holes on each layer. Each air intake hole is equipped with a flow meter, and the flow rate is adjusted through the air intake hole valve to ensure that the bed layer is fully and evenly boiling.

[0067] Embodiment 6: As a further improved scheme or parallel scheme or optional independent scheme, 8 DN15 Inconel tubes are installed on the top of the chlorination furnace 1, which are the top chlorine gas distribution pipes, inserted 1 meter deep, and chlorine is introduced through the top of the furnace to react with the furnace gas and the ferrous chloride attached to the quenching tower to generate ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attachments in the quenching tower fall into the furnace, keeping the quenching tower unobstructed. The substantial technical effect and implementation process of the technical scheme here are as follows: Because the high iron content of titanium concentrate reacts with chlorine to generate ferrous chloride, the quenching tower mud spraying is easy to cause the quenching tower to be blocked, and this embodiment solves this problem.

[0068] An appropriate amount of chlorine is introduced into the furnace top to react with petroleum coke and titanium concentrate fine particles, further improving the Ti yield.

[0069] Embodiment 7: As a further improved solution or parallel solution or optional independent solution, a venturi tube 94 is arranged before the inlet of the cyclone dust collector; the liquid alkali is transported to the venturi tube by a metering pump and atomized into small liquid alkali droplets, which react with AlCl in the crude titanium tetrachloride gas. 3 The aluminum hydroxide solid generated by the reaction is separated in a cyclone dust collector; the cyclone dust collector comprises two stages, and the two-stage cyclone separators are connected in series, so that the crude titanium tetrachloride gas and solid produced by the chlorination furnace are fully separated under the action of centrifugal force, so as to achieve the purpose of lowering the crude titanium solid content.

[0070] Embodiment 8: As a further improved scheme or a parallel scheme or an optional independent scheme, a gas-liquid separator is arranged after the indirect condenser, and the gas part of the gas-liquid separator is connected to a six-stage turbulent spray absorption tower. The chlorinated tail gas adopts a six-stage turbulent spray absorption tower in series design. Each tower can be independently removed from the system for regular cleaning and maintenance. The first, second, third and sixth stages are water washing towers, and the fourth and fifth stages are alkali washing towers.

[0071] Embodiment 9: As a further improved solution or parallel solution or optional independent solution, a dust slurry tank is provided at the bottom of the cyclone dust collector to make slurry from the cyclone dust collection ash and transport it to the wastewater and waste residue system for treatment;

[0072] After titanium tetrachloride is collected by direct condenser and indirect condenser, the remaining gas components are mainly CO, CO 2 、N 2 、SO 2 , HCl and other non-condensable gases, a small amount of uncooled titanium tetrachloride gas, containing trace amounts of Cl 2 The exhaust gas is treated by exhaust gas washing and then discharged after reaching the standard.

[0073] 20% liquid alkali sodium hydroxide is used to remove aluminum chloride. A Venturi tube is installed in the quenching pipe before the cyclone inlet. The liquid alkali is transported to the Venturi tube through a metering pump and atomized into small liquid alkali droplets to react with AlCl in the crude titanium tetrachloride gas. 3 The aluminum hydroxide solid generated by the reaction is separated in a cyclone dust collector; 20% liquid alkali sodium hydroxide and TiCl 4 No reaction;

[0074] Chemical formula: AlCl 3 (g)+3NaOH(q)→Al(OH) 3 (s)+2NaCl(s);

[0075] The refined vanadium removal slurry is treated by the slurry vanadium extraction process. The refined vanadium removal slurry does not return to the chlorination feed tank, which further reduces the frequency of blockage of the quench tower and reduces the crude titanium solid content.

[0076] The high iron content of titanium concentrate reacts with chlorine to form ferrous chloride. The quench tower mud spraying easily causes the quench tower to be blocked. Eight DN15 Incon tubes are installed from the top of the furnace, inserted 1 meter deep, and an appropriate amount of chlorine is introduced through the top of the furnace to react with the furnace gas and the ferrous chloride attached to the quench tower to form ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attached materials in the quench tower fall into the furnace, keeping the quench tower unobstructed. The boiling point of ferrous chloride is 700℃, and the boiling point of ferric chloride is 316℃.

[0077] Chemical formula: 2FeCl 2 (s)+Cl 2 (g) = 2FeCl 3 (g)

[0078] An appropriate amount of chlorine is introduced into the furnace top to react with petroleum coke and titanium concentrate fine particles, further improving the Ti yield.

[0079] At present, domestic boiling chlorination uses titanium-rich materials (rutile, high-titanium slag) TiO 2 The content is about 85%. The present invention uses TiO 2 Titanium concentrate with a content of 54% to 55% is used The invention discloses a process for producing titanium tetrachloride by using a large-scale boiling chlorination furnace with a diameter of 14.6 meters.

[0080] Raw material index:

[0081] Table 1 Titanium concentrate control indicators

[0082]

[0083] Table 2 Composition and content of titanium concentrate

[0084]

[0085] Table 3 Petroleum coke control indicators

[0086]

[0087] Table 4 Composition and content of petroleum coke

[0088]

[0089]

[0090] Process principle:

[0091] Low-grade titanium concentrate and petroleum coke are mixed multiple times and finally made into specifications that meet production requirements. They are then metered into the chlorination furnace and react with chlorine under high temperature.

[0092] Petroleum coke plays a catalytic role and participates in the reaction, allowing titanium concentrate and chlorine to react at a lower temperature. The reaction formula is:

[0093] (4-φ / 2)TiO 2 +C+(2-φ)Cl 2 =(1-φ / 2)TiCl 4 +(1-φ)CO 2 +φCO Where: TiO 2 Titanium dioxide is the main component of titanium concentrate, C is the main component of petroleum coke, and Cl 2 It is chlorine, TiCl 4 It is the product of the chlorination process, titanium tetrachloride, CO is carbon monoxide, CO 2 is carbon dioxide, φ is the phi value, that is, the ratio of carbon monoxide to the sum of carbon monoxide and carbon dioxide (φ=CO / (CO+CO 2 )).

[0094] During the production process of the chlorination furnace, 20% liquid alkali is sprayed into the titanium tetrachloride gas through a Venturi tube alkali adding device at the cyclone inlet quench pipe to remove aluminum trichloride.

[0095] Reaction equation: AlCl 3 (g)+3NaOH(q)→Al(OH) 3 (s)+2NaCl(s)

[0096] During the reaction, crude TiCl4 liquid is sprayed into the quench tower for gas-liquid heat exchange, so that the temperature of the gas at the outlet of the cyclone dust collector is maintained at 165-180°C. This can protect the equipment and pipelines from high temperature damage and prevent the TiCl4 gas from condensing into liquid to block the cyclone dust collector (TiCl 4 The boiling point is 136℃), and the solid content in the crude titanium is also reduced by controlling the outlet temperature of the cyclone dust collector. 4 The spray volume is used to adjust the cyclone outlet temperature to ensure smooth production.

[0097] Crude TiCl from cyclone dust collector 4 After the gas enters the condensation system, in the direct condenser, the TiCl4 is first condensed by direct contact with the crude TiCl4 liquid. 4 and high boiling point chlorides (FeCl 3 、AlCl 3 、TiOCl 2 Then TiCl is indirectly condensed in an indirect condenser with a coolant (circulating water and chilled brine). 4 and low boiling point chlorides (SiCl 4 , CCl 4 ), most of the crude TiCl 4The gas is condensed into liquid in the direct cooling and stored in the direct cooling collection tank. The remaining crude TiCl 4 The gas is condensed in the indirect cooling and flows into the crude titanium tank. 4 The liquid part enters the crude titanium tank through the overflow pipe and is transported to the refined titanium tetrachloride tank area by the crude titanium pump for standing; the remaining crude TiCl 4 After the liquid passes through the spiral plate heat exchanger, it enters the direct cooling system to circulate and spray to cool the gaseous TiCl 4 A small part of the crude TiCl is transported to the quench tower feed tank through the condensate pump outlet. 4 Liquid, used for spraying in quench tower of chlorination furnace.

[0098] After titanium tetrachloride is collected by direct condenser and indirect condenser, the remaining gas components are mainly CO, CO 2 、N 2 , HCl and other non-condensable gases, a small amount of uncooled titanium tetrachloride gas, containing trace amounts of Cl 2 The exhaust gas is treated through exhaust gas leaching and discharged after meeting the treatment standards.

[0099] Process route:

[0100] The present invention uses The large-scale boiling chlorination furnace without sieve plate has a combined air intake mode of side air intake and bottom air intake. The side air intake is divided into three layers with a total of 36 air intake holes, 12 air intake holes in each layer, and 1 air intake hole in the bottom air intake. The PD pump pneumatic conveying pump is used for feeding. An automatic slag discharge system is set at the bottom of the chlorination furnace. The mixture and chlorine are introduced into the chlorination furnace to react at high temperature to generate titanium tetrachloride gas, which passes through the quenching tower, quenching pipe, cyclone dust collector, direct condenser, indirect condenser, gas-liquid separator, and chlorinated tail gas in turn. A dust slurry tank is set at the bottom of the cyclone dust collector to make slurry from the cyclone dust collection ash and transport it to the wastewater and waste residue system for treatment.

[0101] Main process parameters:

[0102]

[0103] (1) The furnace type used in this process is The 14.6-meter large boiling chlorination furnace has an innovative double-shell design. The circulating water enters from the bottom of the furnace and flows out from the top of the furnace through the shell layer, thereby cooling the furnace wall. Due to the use of the shell design, the shell layer is filled with water to isolate the oxygen in the air, so this innovation greatly reduces the corrosion rate of the furnace wall and extends the service life of the furnace wall. At the same time, the furnace wall produces less rust and has high heat exchange efficiency. In addition, because the shell layer is fully sealed, there is no situation where the furnace wall cooling water is heated to generate water vapor that fills the factory building, which plays a certain protective role for the equipment in the factory building.

[0104] (2) A crusher is innovatively installed on the ball valve on the upper wall of the cyclone ash pipe to crush the lumps in the dust collection and prevent the lumps from clogging the ash pipe.

[0105] Process technical indicators:

[0106] 1. TiO in titanium concentrate 2 Mass fraction: 54%~55%;

[0107] 2. Bed height 6.5 to 8.5 meters;

[0108] 3. Coke ratio = 6:1~7.5:1;

[0109] 4. Chlorine flow rate: 18-22t / h;

[0110] 5. Furnace operation rate: ≥95%;

[0111] 6. Chlorination furnace service life: 18 to 24 months;

[0112] 7. Ti yield: 95%~97%;

[0113] 1. Install 8 DN15 Inconel pipes (chlorine gas distribution pipes on the furnace top) from the furnace top, insert them 1 meter deep, and introduce a proper amount of chlorine through the furnace top to react with the furnace gas and the ferrous chloride attached to the quenching tower to generate ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attachments in the quenching tower fall into the furnace, keeping the quenching tower unobstructed (the boiling point of ferrous chloride is 700℃, and the boiling point of ferric chloride is 316℃).

[0114] Chemical formula: 2FeCl 2 (s)+Cl 2 (g) = 2FeCl 3 (g)

[0115] 2. In the process of the present invention, 20% liquid alkali (sodium hydroxide) is used to remove aluminum chloride. A venturi tube is installed in the quenching pipe 4 meters before the cyclone inlet. The liquid alkali is transported to the venturi tube through a metering pump and atomized into small liquid alkali droplets to react with AlCl in the crude titanium tetrachloride gas. 3 The aluminum hydroxide solid generated by the reaction is separated in a cyclone dust collector.

[0116] Chemical formula: AlCl 3 (g)+3NaOH(q)→Al(OH) 3 (s)+2NaCl(s)

[0117] 5. The innovative two-stage cyclone separator series technology is adopted to fully separate the crude titanium tetrachloride gas and solid produced by the chlorination furnace under the action of centrifugal force, so as to achieve the purpose of lower solid content of crude titanium.

[0118] 6. The refined vanadium removal slurry of this process is treated by the vanadium extraction process of the slurry. The refined vanadium removal slurry does not return to the chlorination feed tank, which further reduces the frequency of blockage of the quench tower.

[0119] 7. The chlorinated tail gas adopts a six-stage turbulent spray absorption tower in series design. Each tower can be independently removed from the system for regular cleaning and maintenance. The first, second, third and sixth stages are water washing towers, and the fourth and fifth stages are alkali washing towers. The concentration of liquid alkali is 5% to 10%.

[0120] In general, this patent relates to the field of titanium tetrachloride production, and in particular to a device and method for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace. A quenching tower 2 is connected to the chlorination furnace 1, the quenching tower 2 is connected to a cyclone dust collector, the cyclone dust collector is connected to a direct condenser 13, the direct condenser 13 is connected to an indirect condenser, the pipeline below the indirect condenser is connected to a crude titanium tank 19, and a direct cooling collection tank 14 is connected below the direct condenser 13; there is no situation where the furnace wall cooling water is heated to generate water vapor that fills the factory building, which plays a protective role for the equipment in the factory building; it is a pioneering use of low-grade titanium ore to produce titanium tetrachloride, and appropriate chlorine is introduced into the furnace top to prevent the quenching tower from being blocked. At the same time, part of the furnace top chlorine reacts again with the fine-grained titanium ore and fine-grained petroleum coke brought into the furnace top by the gas to increase the Ti yield. A crusher is installed under the cyclone dust collector to break up occasional ash lumps and prevent blockage of the ash pipe. 20% liquid alkali is used to remove aluminum chloride in a pioneering way, and two-stage cyclone series technology is used to reduce the solid content of crude titanium. Equipment losses can be avoided by lowering the temperature through spraying. The difference in boiling points between ferrous chloride and ferric chloride is cleverly used to achieve overall equipment safety production without blockage.

[0121] The basic principle, main features and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the protection required.

Claims

1. A device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace, characterized in that: The device comprises a chlorination furnace (1), a quenching tower (2) connected to the chlorination furnace (1), the quenching tower (2) connected to a cyclone dust collector, the cyclone dust collector connected to a direct condenser (13), the direct condenser (13) connected to an indirect condenser, a pipeline below the indirect condenser connected to a crude titanium tank (19), a direct cooling collection tank (14) connected below the direct condenser (13), the direct cooling collection tank (14) connected to the crude titanium tank (19) through a pipeline, and a direct cooling pump outlet of the direct cooling collection tank (14) also branches out a pipeline leading to a feed tank (7) of the quenching tower (2); The quenching tower (2) is arranged above the chlorination furnace (1); The chlorination furnace (1) is a boiling chlorination furnace, which includes a double shell design. Circulating water is introduced from the bottom of the furnace and flows out from the top of the furnace through the shell from bottom to top, so as to cool the furnace wall. Due to the use of the shell design, the shell is filled with water to isolate the oxygen in the air, which can greatly reduce the rust rate of the furnace wall. Since the shell is fully sealed, there is no situation where the furnace wall cooling water is heated to generate water vapor that fills the factory building, which plays a protective role on the equipment in the factory building.

2. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 1, characterized in that: A crusher 1 (53) and a crusher 2 (58) are arranged above the ash lower pipe of the cyclone dust collector. The crusher 1 (53) and the crusher 2 (58) can crush the lumps in the collected dust to prevent the lumps from clogging the ash lower pipe.

3. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 2, characterized in that: An upper half ball valve 1 (54), an upper half ball valve 2 (59), a lower half ball valve 1 (55), a lower half ball valve 2 (60), and a star-shaped ash discharge valve (56) are arranged below the first crusher (53) and the second crusher (58).

4. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 1, characterized in that: The indirect cooling adopts two-stage indirect cooling, the first stage is circulating water cooling, and the second stage is chilled brine cooling; the indirect condenser includes two groups, the first group is used for circulating water cooling, and the second group is used for chilled brine cooling.

5. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 1, characterized in that: The air inlet mechanism of the chlorination furnace includes an air inlet hole at the bottom and 36 air inlet holes on the side. The 36 air inlet holes are distributed in three layers, with 12 air inlet holes in each layer. Each air inlet hole is equipped with a flow meter and an air inlet valve. The gas flow rate can be adjusted through the air inlet valve to ensure that the bed layer boils fully and evenly.

6. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 1, characterized in that: Eight DN15 Inconel pipes are installed on the top of the chlorination furnace (1), which are the top chlorine gas distribution pipes. The pipes are inserted 1 meter deep. Chlorine gas is introduced through the top of the furnace to react with the furnace gas and the ferrous chloride attached to the quenching tower to generate ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attached materials in the quenching tower fall into the furnace, keeping the quenching tower unobstructed.

7. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 1, characterized in that: A venturi tube (94) is arranged before the inlet of the cyclone dust collector; liquid alkali is transported to the venturi tube by a metering pump to be atomized into small liquid alkali droplets, which react with AlCl3 in the crude titanium tetrachloride gas to generate aluminum hydroxide solids, which are separated in the cyclone dust collector; the cyclone dust collector comprises two stages, and the two stages of cyclone separators are connected in series, so that the crude titanium tetrachloride gas produced by the chlorination furnace and the solids are fully separated under the action of centrifugal force, so as to achieve the purpose of lowering the solid content of the crude titanium tetrachloride.

8. The device for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 1, characterized in that: A gas-liquid separator is arranged after the indirect condenser. The gas part of the gas-liquid separator is connected to a six-stage turbulent spray absorption tower. The chlorinated tail gas adopts a six-stage turbulent spray absorption tower in series design. Each tower can be independently removed from the system for regular cleaning and maintenance. The first, second, third and sixth stages are water washing towers, and the fourth and fifth stages are alkali washing towers.

9. A method for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace, characterized in that: The following steps are included: Using titanium concentrate with a TiO2 content of 54% to 55%, titanium tetrachloride is produced in a fluidized chlorination furnace; Titanium concentrate and petroleum coke are mixed several times to meet the production requirements. They are then metered into the chlorination furnace and react with chlorine at a high temperature of 850-1100°C. Petroleum coke plays a catalytic role and participates in the reaction, allowing titanium concentrate and chlorine to react at a lower temperature. The reaction formula is: (1-φ / 2)TiO2+C+(2-φ)Cl2=(1-φ / 2)TiCl4+(1-φ)CO2+φCO wherein: TiO2 is titanium dioxide, the main component of titanium concentrate, C is carbon, the main component of petroleum coke, Cl2 is chlorine, TiCl4 is titanium tetrachloride, the product of the chlorination stage, CO is carbon monoxide, CO2 is carbon dioxide, and φ is the phi value, i.e., the ratio of carbon monoxide to the sum of carbon monoxide and carbon dioxide (φ=CO / (CO+CO2)); During the production process of the chlorination furnace, 20% of liquid alkali is sprayed in the titanium tetrachloride gas through a venturi tube alkali adding device at the quench pipe 4 meters away from the cyclone inlet to remove aluminum trichloride; Reaction equation: AlCl3(g)+3NaOH(q)→Al(OH)3(s)+2NaCl(s) During the reaction, crude TiCl4 liquid is sprayed into the quench tower for gas-liquid heat exchange, so that the temperature of the gas at the outlet of the cyclone dust collector is maintained at 165-180°C. This can protect the equipment and pipelines from high temperature damage and prevent the TiCl4 gas from condensing into liquid to block the cyclone dust collector. The boiling point of TiCl4 is 136°C. At the same time, the solid content in the crude titanium is also reduced by controlling the outlet temperature of the cyclone dust collector. The cyclone outlet temperature is adjusted by adjusting the TiCl4 spraying amount of the quench tower spray gun to ensure smooth production. After the crude TiCl4 gas from the cyclone dust collector enters the condensation system, in the direct condenser, the crude TiCl4 liquid is first used to condense TiCl4 and high-boiling point chlorides by direct contact. The high-boiling point chlorides here include FeCl3, AlCl3, and TiOCl2. Then, in the indirect condenser, the coolant is used to indirectly condense TiCl4 and low-boiling point chlorides. The low-boiling point chlorides are SiCl4, CCl 4； The coolant is circulating water and chilled brine. Most of the crude TiCl4 gas is condensed into liquid in the direct cooling and stored in the direct cooling collection tank. The remaining crude TiCl4 gas is condensed in the indirect cooling and flows into the crude titanium tank. The crude TiCl4 liquid part in the direct cooling collection tank enters the crude titanium tank through the overflow pipe and is transported to the refined titanium tetrachloride tank area by the crude titanium pump for standing. The remaining crude TiCl4 liquid enters the direct cooling system after heat exchange in the spiral plate heat exchanger to circulate and spray to cool the gaseous TiCl4. A small part of the crude TiCl4 liquid is transported to the quenching tower feeding trough through the condensation pump outlet for spraying the chlorination furnace quenching tower.

10. The method for producing titanium tetrachloride using low-grade titanium ore and a boiling chlorination furnace as claimed in claim 9, characterized in that: A dust slurry tank is set at the bottom of the cyclone dust collector to make slurry from the cyclone dust collection ash and transport it to the wastewater and waste residue system for treatment; After titanium tetrachloride is collected by direct condenser and indirect condenser, the remaining gas components are mainly CO, CO2, N2, SO2, HCl non-condensable gases, a small amount of uncooled titanium tetrachloride gas, and a trace amount of Cl2 gas. These tail gases are treated by tail gas leaching and discharged after the treatment meets the standards; 20% sodium hydroxide is used to remove aluminum chloride. A venturi tube is installed in the quench pipe 4 meters before the cyclone inlet. Liquid alkali is transported to the venturi tube through a metering pump and atomized into small liquid alkali droplets, which react with AlCl3 in the crude titanium tetrachloride gas to form aluminum hydroxide solids, which are separated in the cyclone dust collector. Chemical equation: AlCl3(g)+3NaOH(q)→Al(OH)3(s)+2NaCl(s); The refined vanadium removal slurry is treated by the slurry vanadium extraction process. The refined vanadium removal slurry does not return to the chlorination feed tank, which further reduces the frequency of blockage of the quench tower and reduces the crude titanium solid content. Titanium concentrate has a high iron content and reacts with chlorine to form ferrous chloride. Mud spraying in the quench tower can easily cause the quench tower to be blocked. 8 DN15 Inconel pipes are installed from the top of the furnace, inserted 1 meter deep, and an appropriate amount of chlorine is introduced through the top of the furnace to react with the furnace gas and the ferrous chloride attached to the quench tower to form ferric chloride. The ferric chloride reaches the boiling point and becomes gaseous, so that the attached materials in the quench tower fall into the furnace, keeping the quench tower unobstructed. The boiling point of ferrous chloride is 700℃, and the boiling point of ferric chloride is 316℃; Chemical equation: 2FeCl2(s)+Cl2(g)=2FeCl3(g) An appropriate amount of chlorine is introduced into the furnace top to react with petroleum coke and titanium concentrate fine particles, further improving the Ti yield.

Images