CN112266013A - System and process for producing titanium tetrachloride from high-calcium magnesium titanium dioxide - Google Patents
System and process for producing titanium tetrachloride from high-calcium magnesium titanium dioxide Download PDFInfo
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Abstract
The invention relates to the technical field of metal smelting, in particular to a system and a process for producing titanium tetrachloride. The invention provides a system and a process for producing titanium tetrachloride from high-calcium magnesium titanium dioxide, which are characterized in that high-titanium slag, petroleum coke and chlorine gas which are used as raw materials are sent into a chlorination furnace, discharged gas enters a cyclone dust collector through a condensation flue for dust removal, discharged gas recovers dust in a wet-method condensation absorption tower, the temperature of the wet-method dust collection condensation tower is reduced to separate titanium tetrachloride solids, clean titanium tetrachloride liquid recovered by a condensation leaching tower enters a condenser again, waste gas enters a tail gas washing system after passing through the condenser and is discharged into the atmosphere after reaching the standard, the liquid enters a crude titanium tetrachloride storage tank, high-boiling-point impurities enriched in the chlorination furnace are discharged out of the chlorination furnace through a slag discharge device, slag enters a separation device to separate titanium dioxide, petroleum coke and chloride, and. The invention can improve the production efficiency and quality of titanium tetrachloride, and is energy-saving and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of metal smelting, and particularly relates to a system and a process for producing titanium tetrachloride from high-calcium magnesium titanium dioxide.
Background
Titanium tetrachloride is a widely used chemical raw material, and can be used for preparing organic titanium compounds, titanium-containing electronic ceramics, titanium sapphire and the like, and also has special application in the aspects of glass, hard alloy, leather, printing and dyeing industry and the like. At present, China is mainly using ilmenite (TiFe 0)3) Smelting the mixture into high titanium slag (Ti 0) by an electric furnace2) Petroleum coke is added into a chlorination furnace, and chlorine is introduced to generate crude titanium tetrachloride (TIC14), the existing large-scale boiling chlorination devices in China all use low-calcium magnesium materials (calcium oxide is less than or equal to 0.14 and magnesium oxide is less than or equal to 0.35) or use natural rutile and artificial rutile to produce crude titanium tetrachloride products with high recovery rate, but the boiling chlorination devices in the prior art are limited by imported titanium ore and rutile raw materials and can not meet the requirements of the existing titanium tetrachloride in China, and the boiling chlorination devices in the prior art have the following defects:
1. the small furnace type is used, the productivity is low, the productivity is backward, and the environment-friendly facility can not meet the environment-friendly requirement;
2. the production field has severe environment and large labor intensity, and is frequently stopped for maintenance,
3. the energy can not be fully utilized to achieve the purposes of saving energy, reducing emission and improving the production quality and efficiency of titanium tetrachloride.
Disclosure of Invention
In order to solve the technical problems, the invention provides a system and a process for producing titanium tetrachloride from high-calcium magnesium titanium dioxide, raw materials of high-titanium slag and petroleum coke are respectively fed into a chlorination furnace, discharged gas enters a cyclone dust collector through a condensation flue for dust removal, discharged gas recovers dust in a wet condensation absorption tower, titanium tetrachloride solid is cooled and separated in the wet condensation tower, clean titanium tetrachloride liquid recovered in a condensation leaching tower enters a condenser again, waste gas after passing through the condenser enters a tail gas washing system and is discharged into the atmosphere after reaching the standard, liquid enters a crude titanium tetrachloride storage tank, high-boiling-point impurities enriched in the chlorination furnace are discharged out of the chlorination furnace through a slag discharge device, slag enters a separation device for separating titanium dioxide, petroleum coke and chloride, and the titanium dioxide and the petroleum coke are dried and then returned to the raw materials; and the purposes of improving the reduction reaction efficiency of the titanium tetrachloride and improving the quality of the titanium tetrachloride are realized by arranging a gas explosion tube structure of inert gas and a process for detonating an explosive body on a system for producing the titanium tetrachloride by using the high-calcium magnesium titanium dioxide.
In order to achieve the purpose, the system for producing titanium tetrachloride by using high-calcium magnesium titanium dioxide comprises a chlorination furnace, the bottom of the chlorination furnace is provided with a slag discharging device and a sludge separating device, a feeder for providing high-calcium magnesium titanium dioxide and petroleum coke is arranged on the side surface of the chlorination furnace, the bottom of the side surface of the chlorination furnace is provided with a chlorine gas inlet, a buffer tank provides chlorine gas for the chlorination furnace through the chlorine gas inlet, high-temperature chloride generated in the chlorination furnace enters a cyclone dust collector through a condensation flue at the top, a cooling device for instantly condensing the high-temperature chloride to reduce the temperature from 950 ℃ to 400 ℃ is arranged on the condensation flue, and titanium dioxide and petroleum coke which are deposited in an ash collecting chamber at the lower side of the cyclone dust collector and the separating device and have useful values are dried and then returned to a feeding bin for continuous use;
the top of the cyclone dust collector is connected with the top of the gravity dust collector through a pipeline, the top of the gravity dust collector is provided with an atomizer and a spray head for atomization, when the outlet temperature of the gravity dust collector is controlled at 250 ℃ for cooling, the gravity dust collector deposits collected chlorides and dust into a sludge treatment tank at the lower part, the sludge treatment tank pumps neutral chlorides into a filter press to filter and press separated solids into brick-shaped building materials, and then the pressed and filtered water is circulated back into the sludge treatment tank to carry out secondary recycling and dust collection;
the upper side of the gravity dust collector is communicated with the bottom of a wet condensation absorption tower, the wet condensation absorption tower collects incompletely collected dust and chloride particles into a slurry circulation tank, and a slurry pump is used for pumping the slurry into a condensation flue and the gravity dust collector to recover titanium tetrachloride again, so that solids in the titanium tetrachloride slurry are separated again;
the wet-process condensation absorption tower separates titanium tetrachloride liquid through cooling, the wet-process condensation absorption tower recovers clean crude titanium tetrachloride liquid through the condensation elution tower, the condensation elution tower feeds the crude titanium tetrachloride liquid into the condenser, the titanium chloride storage tank at the lower part of the condensation elution tower respectively feeds waste gas generated after the cooling of the condenser to the hydrochloric acid absorption tower and the sodium hydroxide absorption tower to carry out acid-base recovery treatment on the tail gas, the waste gas is discharged into the atmosphere through the discharge port after the acid-base recovery treatment is carried out on the tail gas, and solid waste at the bottom is fed into the circulation tank to be recycled.
According to the preferable technical scheme, a charging height display device is arranged on the side surface of the chlorination furnace and is used for helping to control the height of titanium dioxide and petroleum coke in the charging in the chlorination furnace to be 2.5-3.5 meters.
In a preferred technical scheme, the height of the titanium dioxide and the petroleum coke in the chlorination furnace is 2.5, 3.0 or 3.5 meters.
According to the preferable technical scheme, the bottom of the chlorination furnace is provided with a first gas explosion device, the first gas explosion device comprises a gas outlet pipe arranged at the bottom of the chlorination furnace, the gas outlet pipe is provided with a plurality of gas holes, and a first check valve, a first gas pump and a first gas supply device for supplying inert gas are sequentially arranged at the upstream position of the gas outlet pipe.
The preferred technical scheme, the bottom of chlorination furnace is equipped with the second and explodes gas device, the second explodes gas device include with the pipeline of mud sediment treatment tank intercommunication, pipeline is last to be equipped with pressure valve, third check valve, second air pump in proper order and to provide inert gas's second air feeder, be equipped with the branch road between pressure valve and the third check valve, be equipped with on the branch road and utilize inert gas to deliver the inside second check valve and the box of chlorination furnace with explosive pressure, pneumatic tube and branch road pipeline intercommunication on the second air pump, be equipped with the solenoid valve on the pneumatic tube, the explosive is ball type structure, the explosive outside is the casing of ball type, the core ball that the inside of explosive was made by explosive material.
According to the preferable technical scheme, the shell is made of graphite materials, and the explosive material of the core material ball is ammonium nitrate.
According to the preferable technical scheme, the shell is made of a mixture of graphite and calcium chloride, and the mass ratio of the mixture of graphite and calcium chloride is (1-2): 1.
according to the preferable technical scheme, the mass ratio of the graphite to the calcium chloride mixture is 1: 1. 1.5: 1 or 2: 1.
the invention also provides a process of a system for producing titanium tetrachloride from high-calcium magnesium titanium dioxide, which is characterized by comprising the following steps:
step 1: opening a switch, adding furnace materials into a chlorination furnace through a feeder by using a control device, wherein the furnace materials are high-calcium magnesium titanium dioxide and petroleum coke, adding the furnace materials into the chlorination furnace which is baked to 650 ℃ according to the dosage proportion, observing a furnace material height display device, and controlling the height of the high-calcium magnesium titanium dioxide and the height of the petroleum coke in the chlorination furnace to be 2.5-3.5 m;
step 2: injecting chlorine into a control device through a buffer tank and a chlorine inlet on a chlorination furnace, controlling the amount of the chlorine to be 5.5t/h, carrying out the reaction of titanium tetrachloride, controlling the temperature of the discharged titanium tetrachloride gas of the chlorination furnace to be 950 ℃, allowing high-temperature chloride generated in the chlorination furnace to enter a cyclone dust collector through a condensation flue at the top, and reducing the instantaneous condensation temperature of the high-temperature chloride to 400 ℃ from 950 ℃ on the condensation flue by using a cooling device;
and step 3: drying titanium dioxide and petroleum coke which are deposited in an ash collecting chamber and a separating device at the lower side of the cyclone dust collector and have useful values, and returning the dried titanium dioxide and petroleum coke to the feeding bin for continuous use;
step 4) turning on switches of the atomizer and the spray head, cooling the gas entering the gravity dust collector to 250 ℃ by the atomizer at the top, and collecting the collected dust to a dust treatment system below the dust collector;
and 5: depositing the collected chloride and dust into a sludge treatment tank at the lower part by using a gravity dust collector, controlling the outlet temperature of the gravity dust collector at 250 ℃ for cooling, pumping neutral chloride slurry in the sludge treatment tank into a filter press to filter and press separated solid into brick-shaped building materials, and then circulating the pressed and filtered water back into the sludge treatment tank for secondary recycling of dust collection materials;
step 6: gas at the upper part of the gravity dust collector enters a wet condensation absorption tower, incompletely collected dust and chloride particles are collected into a slurry circulation tank by using the wet condensation absorption tower, and then a slurry pump is used for pumping the slurry into a condensation flue and the gravity dust collector to recover titanium tetrachloride again, so that the solids in the titanium tetrachloride slurry are separated again;
and 7: separating titanium tetrachloride liquid from a wet condensation absorption tower by cooling, recovering clean crude titanium tetrachloride liquid from the wet condensation absorption tower through a condensation leaching tower, sending the crude titanium tetrachloride liquid into a condenser by the condensation leaching tower, sending waste gas generated by cooling the condenser to a hydrochloric acid absorption tower and a sodium hydroxide absorption tower respectively to carry out acid-base recovery treatment on tail gas, discharging the treated waste gas to the atmosphere through a discharge port after reaching the standard, and sending the solid waste at the bottom into a circulation tank to carry out recovery treatment;
and 8: opening a switch on the first gas explosion device, enabling an air outlet pipe arranged at the bottom of the chlorination furnace to spray inert gas from an air hole, boiling and rolling residues at the bottom of the chlorination furnace by the inert gas, and enabling titanium tetrachloride to fully react;
and step 9: and opening a switch of the second gas explosion device, sending the explosive body into the chlorination furnace by using inert gas, heating and exploding the explosive body at high temperature, and blasting and overturning sludge in the chlorination furnace to fully react titanium tetrachloride.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention improves the actual yield of the high-calcium magnesium titanium dioxide metallic titanium, reduces the discharge of chloride, realizes the continuous production of titanium tetrachloride in the production of the high-calcium magnesium titanium dioxide, avoids the defect of low utilization rate of the titanium dioxide caused by the accumulation of calcium and magnesium in the raw materials in a fluidized bed furnace after the reaction,
2. the invention improves the quality of the titanium tetrachloride and obtains economic and social benefits of energy conservation and environmental protection.
Drawings
FIG. 1 is a front view of the structure of example 1 of a system for producing titanium tetrachloride from high calcium magnesium titanium dioxide according to the present invention;
FIG. 2 is a front view of the structure of example 2 of the system for producing titanium tetrachloride from high calcium magnesium titanium dioxide according to the present invention;
FIG. 3 is a cross-sectional view of the first explosion apparatus of FIG. 2;
FIG. 4 is a structural view of a second aerator of FIG. 2;
fig. 5 is a structural view of the explosive body in fig. 4.
Reference numerals
In the figure, 1-chlorination furnace; 2-condensation flue; 3-cyclone dust collector; 4-gravity dust collector; 5-spray head, 6-atomizer; 7-wet condensation absorption tower; 8-condensation leaching tower; 9-a heat exchanger; 10-a condenser; 11-hydrochloric acid absorption column; 12-sodium hydroxide absorption tower; 13-a discharge port; 14-a circulation tank; 15-a coarse titanium chloride storage tank; 16-a titanium chloride storage tank; 17-a slurry circulation tank; 18-a sludge treatment tank; 19-a filter press; 20-sludge separation device; 21-a feeding bin; 22-a slag discharge device; 23-a separation device; 24-chlorine buffer tank; 25-a feeder; 26-an ash collecting chamber; 27-a first gas explosion device, 271-a first gas supply device, 272-a first air pump, 273-a first one-way valve, 274-an air hole, 275-an air outlet pipe; 28-a second air blasting device, 281-a second one-way valve, 282-an explosive body, 2821-a shell, 2822-a core ball, 283-a box body, 284-an air pressure pipe, 285-an electromagnetic valve, 286-a second air supply device, 287-a second air pump, 288-a third one-way valve, 289-a pressure valve and 2810-a conveying pipeline. In the figure, the arrows indicate the direction of conveyance of the raw material or gas.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1
As shown in fig. 1, the system for producing titanium tetrachloride from high-calcium magnesium titanium dioxide provided by the invention comprises a feeder 25 and a buffer tank 24 which respectively convey high-titanium slag, petroleum coke and chlorine into a chlorination furnace 1, discharged gas enters a cyclone dust collector 3 for dust removal through a condensation flue 2, discharged gas recovers dust in a wet condensation absorption tower 7, the wet condensation absorption tower 7 is cooled to separate titanium tetrachloride solid, the condensed and eluted titanium tetrachloride liquid recovered from a tower 8 enters a condenser 10, the waste gas enters a tail gas washing system after passing through the condenser 10, and the waste gas is discharged into the atmosphere after reaching the standard; the liquid enters a crude titanium tetrachloride storage tank 15, high boiling point impurities enriched in the chlorination furnace 1 are discharged out of the chlorination furnace 1 through a slag discharge device 22, furnace slag enters a separation device to separate titanium dioxide, petroleum coke and chloride, and the titanium dioxide and the petroleum coke are dried and then return to the original materialsThe feeding bin 21 for feeding continues to be used. In the embodiment, the chlorination furnace 1 with the slag discharging device 22 and the sludge-slag separating device 20 at the bottom is adopted, and the chlorination furnace 1 is selected from
The chlorination furnace of (1), the side of the chlorination furnace 1 is provided with a feeder 25 for providing titanium dioxide and petroleum coke, the chlorination furnace 1 is provided with a chlorine gas inlet at the bottom of the side, a buffer tank 24 provides chlorine gas for the chlorination furnace 1 through the chlorine gas inlet, high-temperature chloride generated in the chlorination furnace 1 enters a cyclone dust collector 3 through a condensation flue 2 at the top, a cooling device for instantly condensing the high-temperature chloride to reduce the temperature from 950 ℃ to 400 ℃ is arranged on the condensation flue 2, and titanium dioxide and petroleum coke with useful values deposited in an ash collecting chamber 26 at the lower side of the cyclone dust collector 3 and a separating device 23 are dried and then returned to a feeding bin 21 for continuous use; the top of the cyclone dust collector 3 is connected with the top of the gravity dust collector 4 through a pipeline, the top of the gravity dust collector 4 is provided with an atomizer 6 and a spray head 5 for atomization, when the outlet temperature of the gravity dust collector 4 is controlled at 250 ℃ for cooling, the gravity dust collector 4 deposits the collected chloride and dust into a sludge treatment tank 18 at the lower part, the sludge treatment tank 18 pumps the neutral chloride slurry into a filter press 19, filters and presses the filtered solid into brick-shaped building materials, and then circulates the pressed water back into the sludge treatment tank 18 for secondary recycling of dust collection materials;
the upper side of the gravity dust collector 4 is communicated with the bottom of the wet condensation absorption tower 7, the wet condensation absorption tower 7 collects incompletely collected dust and chloride particles into a slurry circulation tank 17, and a slurry pump is used for pumping the slurry into the condensation flue 2 and the gravity dust collector 4 for recycling titanium tetrachloride again, so that the solids in the titanium tetrachloride slurry are separated again;
the wet condensation absorption tower 7 separates titanium tetrachloride liquid through temperature reduction, the wet condensation absorption tower 7 recovers clean crude titanium tetrachloride liquid through the condensation leaching tower 8, the condensation leaching tower 8 feeds the crude titanium tetrachloride liquid into the condenser 10, waste gas generated after the titanium chloride storage tank 16 at the lower part is cooled by the condenser 10 is respectively fed into the hydrochloric acid absorption tower 11 and the sodium hydroxide absorption tower 12 to carry out acid-base recovery treatment on the tail gas, and the treated tail gas is discharged into the atmosphere through the discharge port 13 after reaching the standard; the solid waste at the bottom is sent to a circulation tank 14 for recycling. Wherein, in order to control the height of the charging materials of the high calcium magnesium titanium dioxide and the petroleum coke in the chlorination furnace 1 to be 2.5-3.5 meters, the chlorination furnace 1 is provided with a charging material height display device on the side surface, and the charging material height display device is used for helping to control the height of the charging materials of the high calcium magnesium titanium dioxide and the petroleum coke in the chlorination furnace 1 to be 2.5-3.5 meters. The preferred technical proposal is that the height of the high calcium magnesium titanium dioxide and the petroleum coke in the chlorination furnace 1 is 2.5, 3.0 or 3.5 meters. In this example, the height of the high calcium magnesium titanium dioxide and the petroleum coke in the chlorination furnace 1 is 3.0 meters.
The invention also provides a process of a system for producing titanium tetrachloride from high-calcium magnesium titanium dioxide, which comprises the following steps:
step 1: turning on a switch, adding furnace materials into the chlorination furnace 1 through a feeder 25 by using a control device, wherein the furnace materials are high-calcium magnesium titanium dioxide and petroleum coke, adding the furnace materials into the chlorination furnace 1 which is baked to reach 650 ℃ according to the dosage ratio, observing a furnace material height display device, and controlling the height of the high-calcium magnesium titanium dioxide and the height of the petroleum coke in the chlorination furnace 1 to be 2.5-3.5 meters;
step 2: injecting chlorine into a control device through a buffer tank 24 and a chlorine inlet on a chlorination furnace 1, controlling the amount of the chlorine to be 5.5t/h, carrying out the reaction of titanium tetrachloride, controlling the temperature of the discharged titanium tetrachloride gas of the chlorination furnace 1 to be 950 ℃, enabling high-temperature chloride generated in the chlorination furnace 1 to enter a cyclone dust collector 3 through a condensation flue 2 at the top, and reducing the instantaneous condensation temperature of the high-temperature chloride to 400 ℃ from 950 ℃ on the condensation flue 2 by using a cooling device;
and step 3: titanium dioxide and petroleum coke which are deposited in an ash collecting chamber 26 at the lower side of the cyclone dust collector 3 and a separating device 23 and have useful values are dried and then returned to the feeding bin 21 for continuous use;
step 4) turning on switches of the atomizer 6 and the spray head 5, cooling the gas entering the gravity dust collector 4 to 250 ℃ by the atomizer 6 at the top, and collecting the collected dust to a dust treatment system below the dust collector;
and 5: depositing the collected chloride and dust into a sludge treatment tank 18 at the lower part by using a gravity dust collector 4, controlling the outlet temperature of the gravity dust collector 4 at 250 ℃ for cooling, pumping the neutral chloride slurry in the sludge treatment tank 18 into a filter press 19, filtering and pressing the separated solid into brick-shaped building materials, and then circulating the pressed and filtered water back into the sludge treatment tank 18 for secondary recycling of dust collection;
step 6: gas at the upper part of the gravity dust collector 4 enters a wet condensation absorption tower 7, incompletely collected dust and chloride particles are collected into a slurry circulation tank 17 by using the wet condensation absorption tower 7, and then a slurry pump is used for pumping the slurry into a condensation flue 2 and the gravity dust collector 4 for recycling titanium tetrachloride again, so that the solid in the titanium tetrachloride slurry is separated again;
and 7: the wet condensation absorption tower 7 is cooled to separate titanium tetrachloride liquid, the wet condensation absorption tower 7 is used for recycling clean crude titanium tetrachloride liquid through the condensation leaching tower 8, the condensation leaching tower 8 sends the crude titanium tetrachloride liquid into the condenser 10, the titanium chloride storage tank 16 at the lower part of the condensation leaching tower 8 is used for respectively sending waste gas generated after the cooling of the condenser 10 to the hydrochloric acid absorption tower 11 and the sodium hydroxide absorption tower 12 for carrying out acid-base recycling treatment on the tail gas, the treated waste gas is discharged into the atmosphere through the discharge port 13 after reaching the standard, and then the solid waste at the bottom is sent to the circulation tank 14 for recycling treatment.
In the embodiment, high calcium magnesium, titanium dioxide and petroleum coke are added into a boiling chlorination furnace 1 which is baked to reach 650 ℃ according to the dosage ratio, so that the high calcium magnesium titanium dioxide and the petroleum coke are kept in the boiling chlorination furnace 1 for 2.5 to 3.5 meters, chlorine is introduced, the chlorine amount is controlled to be 5.5t/h, the temperature of the discharged titanium tetrachloride gas is 950 ℃, the contained dust enters a cyclone dust collector for dust removal through a condensation flue 2, and the dust is collected, treated and separated to obtain valuable materials and returns to a feeder for recycling; after the temperature of the high-temperature gas is reduced to 400 ℃ after the high-temperature gas is discharged from the cyclone dust collector, the high-temperature gas enters the gravity dust collector 4, the temperature of the gas is reduced to 250 ℃ by using the atomizer 11 at the top of the dust collector, the collected dust is collected in a dust treatment system below the dust collector and is pumped to a neutral slurry pump to be sent to a dust collectorNeutral water is pressed and filtered by a filter press for recycling production, dry slag obtained by filter pressing is sent to a brick making factory for manufacturing building materials, furnace gas containing titanium tetrachloride and part of high-temperature chlorination dust enters a wet condensation dust remover, the temperature is continuously reduced to obtain titanium tetrachloride mud with slightly high solid content, the titanium tetrachloride mud is collected in a mud circulation groove, the mud in the mud groove is pumped to a condensation flue of a boiling chlorination furnace, a condensation atomization device of a gravity dust collector 4 removes solid dust and solid chloride, the titanium tetrachloride mud is evaporated and recovered by utilizing the temperature of the furnace gas, and the recovered titanium tetrachloride is purer. Furnace gas after wet condensation and dust collection enters a condensation leaching tower 8 to recover titanium tetrachloride liquid, and waste gas enters a tail gas treatment system to treat HCL and Cl after titanium tetrachloride is separated by a condenser2Then the titanium tetrachloride liquid which is condensed and recycled is collected into a crude titanium tetrachloride storage tank for storage. The chlorination furnace 1 detects the change condition of material components in the furnace, when calcium chloride and magnesium chloride contained in the fluidized bed furnace 1 are enriched to 5%, a furnace bottom deslagging system is opened to carry out deslagging operation, discharged furnace slag enters a separation system to separate titanium dioxide, petroleum coke, chloride and the like, and the obtained titanium dioxide and petroleum coke are respectively dried and then enter a raw material feeder 25 to be recycled. The process is suitable for producing titanium tetrachloride by using high-calcium-magnesium titanium dioxide in China, the obtained titanium tetrachloride is clean and low in solid content, and is beneficial to refining the titanium tetrachloride, the process improves the actual yield of the high-calcium-magnesium titanium dioxide metallic titanium, reduces the emission of chloride, realizes continuous production of the titanium tetrachloride by using the high-calcium-magnesium titanium dioxide, and avoids the defect of low utilization rate of the titanium dioxide caused by accumulation in a fluidized bed furnace after the reaction of calcium and magnesium in the raw materials.
Example 2
This example is further improved on the basis of example 1, with the difference that: as shown in fig. 2-4, in order to improve the yield of high-calcium magnesium titanium dioxide metallic titanium and reduce the emission of chlorides, and to make the efficiency of producing titanium tetrachloride from high-calcium magnesium titanium dioxide higher, and to improve the efficiency of continuous production, a first aeration device 27 is arranged at the bottom of the chlorination furnace 1, the first aeration device 27 comprises an air outlet pipe 275 arranged at the bottom of the chlorination furnace 1, a plurality of air holes 274 are arranged on the air outlet pipe 275, a first check valve 273, a first air pump 272 and a first air supply device 271 for supplying inert gas are sequentially arranged at the upstream position of the air outlet pipe 275, the inert gas can carry out boiling rolling on the residue at the bottom of the chlorination furnace 1, and the air flow blows the residue at the bottom upwards to form a circulating convection flow with regular up and down flow, so that the titanium tetrachloride can carry out sufficient.
Wherein, the bottom of the chlorination furnace 1 is further provided with a second aeration device 28, the second aeration device 28 comprises a conveying pipeline 2810 communicated with the sludge treatment tank 18, the conveying pipeline 2810 is sequentially provided with a pressure valve 289, a third one-way valve 288, a second air pump 287 and a second air supply device 286 for providing inert gas, a branch is arranged between the pressure valve 289 and the third one-way valve 288, the branch is provided with a second one-way valve 281 and a box body 283 which utilize the inert gas to pump the explosive 282 into the chlorination furnace 1, an air pressure pipe 284 on the second air pump 287 is communicated with the branch pipeline, the air pressure pipe 284 is provided with an electromagnetic valve 285, the explosive 282 is of a spherical structure, the exterior of the explosive 282 is a spherical shell 2821, the interior of the explosive 282 is a core ball 2822 made of explosive materials, the core material balls 2822 are made of ammonium nitrate, the mass of the core material balls 2822 made of ammonium nitrate is selected to be 5-20 g, the mass is selected according to the amount or depth of precipitated solids, the larger or deeper the amount or depth of the precipitated solids is, the larger the mass of the selected core material balls 2822 is, and the core material balls 2822 are preferably of different specifications such as 5 g, 10 g, 15 g or 20 g. In a preferred technical scheme, in order to prevent chlorine from being consumed, the shell 2821 is made of graphite material, the explosive material of the core material ball 2822 is ammonium nitrate, and when the core material ball 2822 is heated and exploded, irregular convection is formed, so that the substance at the bottom is more fully reacted with chlorine. Wherein, in order to prevent the amount of chlorine that consumes and can guarantee that titanium dioxide, petroleum coke normally take place complete reaction with chlorine, casing 2821 is preferably made for the mixture of graphite and calcium chloride, and the mass ratio scope of graphite and calcium chloride mixture is 1 ~ 2: 1, according to the preferable technical scheme, the mass ratio of the mixture of graphite and calcium chloride is 1: 1. 1.5: 1 or 2: 1. in this example, the mass ratio of the selected graphite to calcium carbonate mixture was 1.5: 1.
in order to improve the production efficiency of titanium tetrachloride, on the basis of embodiment 1, the invention also provides a process of a system for producing titanium tetrachloride from high-calcium magnesium titanium dioxide, which further comprises the following steps after step 7:
and 8: opening a switch on the first gas explosion device 27, and enabling the gas outlet pipe 275 arranged at the bottom of the chlorination furnace 1 to spray inert gas from the gas hole 274, wherein the inert gas is argon or helium, and the inert gas can boil and roll the residues at the bottom of the chlorination furnace 1 to enable titanium tetrachloride to fully react;
and step 9: the switch of the second gas explosion device 28 is turned on, the explosive 282 is sent into the chlorination furnace 1 by using inert gas, the explosive 282 is heated and exploded at high temperature, mud residue in the chlorination furnace 1 is fried and overturned to form an irregular overturning state, the reaction of titanium tetrachloride is fully performed, the reaction efficiency is improved, and the quality of the titanium tetrachloride is improved.
The preferred embodiments and examples have been described in detail with reference to the accompanying drawings, but the invention is not limited to the embodiments and examples described above, and various changes can be made within the knowledge of those skilled in the art without departing from the present concept.
Claims (9)
1. The system for producing titanium tetrachloride from high-calcium magnesium titanium dioxide comprises a chlorination furnace (1) with a slag discharging device (22) and a sludge separating device (20) arranged at the bottom, wherein a feeder (25) for providing high-calcium magnesium titanium dioxide and petroleum coke is arranged on the side surface of the chlorination furnace (1), a chlorine gas inlet is arranged at the bottom of the side surface of the chlorination furnace (1), and a buffer tank (24) provides chlorine gas for the chlorination furnace (1) through the chlorine gas inlet, and is characterized in that high-temperature chloride generated in the chlorination furnace (1) enters a cyclone dust collector (3) through a condensation flue (2) at the top, a cooling device for instantly condensing the high-temperature chloride to reduce the temperature from 950 ℃ to 400 ℃ is arranged on the condensation flue (2), and titanium dioxide, titanium dioxide and petroleum coke which have useful values and are settled in an ash collecting chamber (26) and a separating device (23) at the lower side of the cyclone dust collector (3), The petroleum coke is dried and then returns to the feeding bin (21) for continuous use;
the top of the cyclone dust collector (3) is connected with the top of a gravity dust collector (4) through a pipeline, an atomizer (6) and a spray head (5) for atomization are arranged at the top of the gravity dust collector (4), the outlet temperature of the gravity dust collector (4) is controlled to be 250 ℃ for cooling, the gravity dust collector (4) deposits collected chloride and dust into a sludge treatment tank (18) at the lower part, the sludge treatment tank (18) sends a neutral chloride slurry pump to a pressure filter (19), solids separated by pressure filtration are filtered and pressed into brick-shaped building materials, and then the pressed and filtered water is circulated back into the sludge treatment tank (18) for secondary recycling of dust collection materials;
the upper side of the gravity dust collector (4) is communicated with the bottom of a wet condensation absorption tower (7), the wet condensation absorption tower (7) collects incompletely collected dust and chloride particles into a slurry circulation tank (17), and a slurry pump is used for pumping the slurry into a condensation flue (2) and the gravity dust collector (4) to recover titanium tetrachloride again, so that solids in the titanium tetrachloride slurry are separated again;
wet process condensation absorption tower (7) separate out titanium tetrachloride liquid through the cooling, clean thick titanium tetrachloride liquid is retrieved through condensation drip washing tower (8) in wet process condensation absorption tower (7), condensation drip washing tower (8) are through sending into condenser (10) with thick titanium tetrachloride liquid in, titanium chloride storage tank (16) of lower part, and the waste gas that produces after condenser (10) cooling is sent to hydrochloric acid absorption tower (11) and sodium hydroxide absorption tower (12) respectively and is carried out acid-base recovery processing to tail gas, discharges after handling and discharges after up to standard and discharge into the atmosphere through discharge port (13), sends the solid waste of bottom to and carries out recovery processing in circulation groove (14).
2. The system for producing titanium tetrachloride through high calcium magnesium titanium dioxide according to the claim 1, characterized in that the chlorination furnace (1) is laterally provided with a charge height display device, and the charge height display device is used for helping to control the height of the high calcium magnesium titanium dioxide and the petroleum coke in the charge in the chlorination furnace (1) to be between 2.5 and 3.5 meters.
3. The system for producing titanium tetrachloride according to claim 2, wherein the height of the high calcium magnesium titanium dioxide and the petroleum coke in the chlorination furnace (1) is 2.5, 3.0 or 3.5 meters.
4. The system for producing titanium tetrachloride through high-calcium magnesium titanium dioxide according to claim 1, wherein a first gas explosion device (27) is arranged at the bottom of the chlorination furnace (1), the first gas explosion device (27) comprises a gas outlet pipe (275) arranged at the bottom of the chlorination furnace (1), a plurality of gas holes (274) are formed in the gas outlet pipe (275), and a first check valve (273), a first gas pump (272) and a first gas supply device (271) for supplying inert gas are sequentially arranged at the upstream position of the gas outlet pipe (275).
5. The system for producing titanium tetrachloride through high calcium magnesium titanium dioxide according to claim 4, wherein a second gas explosion device (28) is arranged at the bottom of the chlorination furnace (1), the second gas explosion device (28) comprises a conveying pipeline (2810) communicated with the sludge treatment tank (18), a pressure valve (289), a third one-way valve (288), a second gas pump (287) and a second gas supply device (286) for providing inert gas are sequentially arranged on the conveying pipeline (2810), a branch is arranged between the pressure valve (289) and the third one-way valve (288), a second one-way valve (281) and a box body (283) for pumping explosive (282) to the inner bottom of the chlorination furnace (1) through inert gas are arranged on the branch, a gas pressure pipe (284) on the second gas pump (287) is communicated with the branch pipeline, a solenoid valve (285) is arranged on the gas pressure pipe (284), the explosive body (282) is of a spherical structure, the outer part of the explosive body (282) is a spherical shell (2821), and the inner part of the explosive body (282) is a core material ball (2822) made of explosive materials.
6. The system for producing titanium tetrachloride according to claim 5, wherein the housing (2821) is made of a graphite material, and the explosive material of the core material ball (2822) is ammonium nitrate.
7. The system for producing titanium tetrachloride through high-calcium magnesium titanium dioxide according to claim 5, wherein the shell (2821) is made of a mixture of graphite and calcium chloride, and the mass ratio of the mixture of graphite and calcium chloride ranges from 1 to 2: 1.
8. the system for producing titanium tetrachloride according to claim 7, wherein the mass ratio of the mixture of graphite and calcium chloride is 1: 1. 1.5: 1 or 2: 1.
9. a process for using the high calcium magnesium titanium dioxide production titanium tetrachloride system of any one of claims 1 to 8, said process comprising the steps of:
step 1: opening a switch, adding furnace materials into the chlorination furnace (1) through a feeder (25) by using a control device, wherein the furnace materials are high-calcium magnesium titanium dioxide and petroleum coke, adding the furnace materials into the chlorination furnace (1) which is baked to reach 650 ℃ according to the dosage proportion, observing a furnace material height display device, and controlling the height of the high-calcium magnesium titanium dioxide and the height of the petroleum coke in the chlorination furnace (1) to be between 2.5 and 3.5 meters;
step 2: injecting chlorine into a control device through a buffer tank (24) and a chlorine inlet on a chlorination furnace (1), controlling the amount of the chlorine to be 5.5t/h, carrying out a reaction of titanium tetrachloride, controlling the temperature of the discharged titanium tetrachloride gas of the chlorination furnace (1) to be 950 ℃, allowing high-temperature chloride generated in the chlorination furnace (1) to enter a cyclone dust collector (3) through a condensation flue (2) at the top, and reducing the instantaneous condensation temperature of the high-temperature chloride from 950 ℃ to 400 ℃ on the condensation flue (2) by using a cooling device;
and step 3: titanium dioxide and petroleum coke which are deposited in an ash collecting chamber (26) at the lower side of the cyclone dust collector (3) and a separating device (23) and have useful values are dried and then returned to the feeding bin (21) for continuous use;
step 4), turning on switches of the atomizer (6) and the spray head (5), cooling the gas entering the gravity dust collector (4) to 250 ℃ by the atomizer (6) at the top, and collecting the collected dust to a dust treatment system below the dust collector;
and 5: depositing the collected chloride and dust into a sludge treatment tank (18) at the lower part by using a gravity dust collector (4), controlling the outlet temperature of the gravity dust collector (4) at 250 ℃ for cooling, pumping neutral chloride in the sludge treatment tank (18) to a filter press (19) to filter and press the separated solid into brick-shaped building materials, and then circulating the water obtained by pressure filtration back into the sludge treatment tank (18) for secondary recycling of dust collection;
step 6: gas at the upper part of the gravity dust collector (4) enters a wet condensation absorption tower (7), incompletely collected dust and chloride particles are collected in a slurry circulation tank (17) by using the wet condensation absorption tower (7), and then a slurry pump is used for conveying the slurry into a condensation flue (2) and the gravity dust collector (4) to recover titanium tetrachloride again, so that the solid in the titanium tetrachloride slurry is separated again;
and 7: separating titanium tetrachloride liquid from a wet condensation absorption tower (7) by cooling, recovering clean crude titanium tetrachloride liquid from the wet condensation absorption tower (7) through a condensation leaching tower (8), sending the crude titanium tetrachloride liquid into a condenser (10) through the condensation leaching tower (8), sending waste gas generated by cooling the condenser (10) into a hydrochloric acid absorption tower (11) and a sodium hydroxide absorption tower (12) respectively for acid-base recovery treatment of tail gas, discharging the treated tail gas to the atmosphere through a discharge port (13) after reaching the standard, and sending the solid waste at the bottom into a circulation tank (14) for recovery treatment;
and 8: opening a switch on the first gas explosion device (27), and enabling an air outlet pipe (275) arranged at the bottom of the chlorination furnace (1) to eject inert gas from an air hole (274), wherein the inert gas boils and rolls the residues at the bottom of the chlorination furnace (1) to enable titanium tetrachloride to fully react;
and step 9: and opening a switch of the second gas explosion device (28), conveying the explosive body (282) into the chlorination furnace (1) by using high-pressure inert gas, heating and exploding the explosive body (282) at high temperature, and exploding and stirring sludge in the chlorination furnace (1) to fully react titanium tetrachloride.
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