CN113501541B - System and process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag - Google Patents
System and process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag Download PDFInfo
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Abstract
The invention discloses a system and a process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag, which relate to the field of utilization of solid waste metallurgical slag resources. Compared with the prior art, the invention has the beneficial effects that: greatly reduces the power consumption, solves the key problems of precipitation and adhesion of liquid phase after chlorination of calcium and magnesium, utilization of a large amount of heat released in the chlorination process of titanium carbide and control of heat balance in the furnace, and gives consideration to the comprehensive utilization of titanium extraction and a large amount of secondary waste residues and waste heat.
Description
Technical Field
The invention relates to the field of utilization of solid waste metallurgical slag resources, in particular to a system and a process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag.
Background
TiO in titanium-containing blast furnace slag 2 The content is 22-26% because of TiO 2 The titanium dioxide is dispersed and distributed in various minerals, and is difficult to separate and concentrate by a mineral separation method, and if the titanium is separated and extracted by an acid and alkali treatment technology, tiO is used 2 The grade of the titanium is low, so that the process has the disadvantages of high acid and alkali consumption, complex process, high production cost, undesirable titanium enrichment effect and great environmental pollution. And used as cement admixture, i.e. TIO 2 Too high content of (A) and essentially no activity, and can only be used as a sandstone material, and thus, no suitable way for large-scale utilization has been found so far.
The high temperature carbonization-low temperature selective chlorination process of the titanium-containing blast furnace slag is the process route with the most industrial prospect at present. The liquid molten titanium-containing blast furnace slag directly flows into a closed electric furnace to be heated to 1600-1800 ℃ and mixed with carbon for carbonization, the carbonized liquid blast furnace slag is naturally cooled in the air, then the liquid blast furnace slag is crushed and finely ground, the granular carbonized blast furnace slag is chlorinated by chlorine in a fluidized bed at 400-550 ℃ to generate titanium tetrachloride steam, and a crude titanium tetrachloride product and chlorinated slag are obtained through dust removal, condensation and separation.
The high temperature carbonization-low temperature selective chlorination process of the titanium-containing blast furnace slag has the problems that firstly, the titanium-containing blast furnace slag needs to be carbonized at high temperature, although the physical heat of the slag is fully utilized, the problem of overhigh power consumption in the carbonization process is still obvious, the power consumption cost for carbonization can account for 80 percent of the total cost, and the problems of large carbon powder loss, electrode fracture, long carbonization time and the like caused by furnace bottom expansion and serious foam slag of an electric furnace exist. 2. The carbonized liquid blast furnace slag needs to be cooled, then crushed and finely ground, and the liquid slag at 1650-1770 ℃ is directly cooled, so that a large amount of cooling water consumption and a large amount of heat loss are caused, and the existence of titanium carbide causes large power consumption and equipment loss of grinding. 3. The problems of slow reaction speed and low productivity exist in the low-temperature chlorination at the temperature of below 700 ℃; when chlorination is carried out at the temperature of above 700 ℃, calcium chloride and magnesium chloride can be formed in the chlorination process, and liquid phases of calcium and magnesium after chlorination are separated out, so that the fusion and bonding of a bed layer are easily caused, and the chlorination process cannot be carried out; and a large amount of heat released in the titanium carbide chlorination process is recycled and controlled in heat balance, and the key problem which needs to be solved in the low-temperature chlorination process is also solved. 4. In the chlorination residues of low-temperature chlorination, the chlorination rates of calcium and magnesium are still about 7 percent, and the content of chloride ions is far higher than the allowable standard of cement; the water washing is used for removing chlorine, and the washing residue belongs to an inactive mixed material, and the mixing amount of the inactive mixed material is not more than 15% of the mass of the cement according to the national regulation, so the application problem of the chlorination residue is still not solved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the system and the process for preparing titanium tetrachloride by titanium-containing blast furnace slag liquid chlorination, which can greatly reduce the power consumption, solve the key problems of precipitation and bonding of liquid phase after chlorination of calcium and magnesium, recycling of a large amount of heat released in the chlorination process of titanium carbide and control of heat balance in a furnace, and also give consideration to comprehensive utilization of titanium extraction and a large amount of secondary waste residues and waste heat.
In order to achieve the purpose, the invention is realized by the following technical scheme: the system for preparing titanium tetrachloride from titanium-containing blast furnace slag through liquid chlorination comprises a double-layer tundish, wherein the lower end of the double-layer tundish is connected with a liquid chlorination furnace, the bottom end of the liquid chlorination furnace is communicated with a carbothermic reduction furnace, the side edge of the carbothermic reduction furnace is communicated with a dry granulation and waste heat recovery device, and the liquid chlorination furnace is connected with a chlorine gas supply device through a pipeline.
The double-deck pouring basket is including the upper tundish and the lower floor pouring basket of dislocation set, through the mouth of a river intercommunication between upper tundish and the lower floor pouring basket, the lower floor pouring basket is through setting up the mouth of a river and the liquid chlorination furnace intercommunication of spouting in the middle of the lower floor pouring basket bottom, set up upper cavity stopper in the mouth of a river, set up lower floor cavity stopper in the mouth of a river.
The liquid chlorination furnace comprises a furnace top, a furnace body and a furnace bottom, wherein the inner furnace wall of the liquid chlorination furnace is divided into an upper section and a lower section, the upper section is an air flow section, the lower section is a molten pool section, the air flow section comprises a jacket structure, the top end of the furnace top is communicated with a water injection port, and one side of the water injection port is provided with a chlorine gas nozzle which forms an angle of 30-60 degrees with the central line of the water injection port.
The other side of the water injection port is provided with an uptake flue, the uptake flue is of a water-cooled wall structure, the top of the uptake flue is provided with a gas guiding pipeline, and the water-cooled wall of the uptake flue is coated with a fire-resistant acid-resistant coating.
The uptake top sets up the export, sets up the condenser through the export intercommunication, the condenser top links to each other with vapour and liquid separator, the condenser passes through the pipeline with the liquid outlet of vapour and liquid separator bottom and links to each other, and communicates titanium tetrachloride separation recovery unit in the lump, and the gas outlet at vapour and liquid separator top passes through pipeline intercommunication tee bend distributing valve, tee bend distributing valve passes through pipeline distribution part gas and passes through fan pressurization and communicate lower floor cavity stopper rod, and pressure is 0.8 ~ 1.0Mpa, inserts petroleum coke storehouse on the pipeline, and the petroleum coke powder fineness is 200-300 meshes, tee bend distributing valve passes through pipeline distribution part gas and gets into tail gas treatment discharging equipment.
The furnace bottom is of a conical bottom structure, and a sliding water gap is formed in the furnace bottom and communicated with the carbothermic reduction furnace.
The bottom of the carbothermic reduction furnace is provided with a bottom blowing spray pipe, the upper part of the carbothermic reduction furnace is provided with a carbon material inlet and a furnace gas outlet pipeline, the carbon material inlet is connected with a carbon material storage bin, the furnace gas outlet pipeline is communicated with an upper layer hollow stopper rod through a communicating pipe, the communicating pipe is connected with oxygen-enriched air and an additive storage tank, the side edge of the carbothermic reduction furnace is provided with a slag liquid outlet, and the slag liquid outlet is communicated with a dry-process granulator waste heat recovery device.
And a vent hole is formed in the jacket structure, and nitrogen is introduced into the jacket through the vent hole.
The process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag comprises the following steps:
s1, enabling titanium-containing blast furnace slag liquid at 1350-1450 ℃ discharged by a blast furnace to flow into an upper-layer tundish, adding an additive through pneumatic transmission, adding the additive into the slag liquid through an upper-layer hollow stopper rod, lifting the upper-layer hollow stopper rod, and enabling the slag liquid to flow into a lower-layer tundish;
s2, introducing oxygen-enriched air into the lower-layer hollow stopper rod, metering petroleum coke, adding carbon into the titanium-containing blast furnace slag liquid, lifting the lower-layer hollow stopper rod, mixing the slag liquid and the carbon in a contraction section and a straight pipe section of a water gap, and flowing into a liquid chlorination furnace;
s3, spraying the slag liquid from a water gap, impacting the slag liquid by high-speed high-concentration chlorine gas to form dispersed liquid drops, fully contacting the gas liquid, and carrying out Fe 2 O 3 、TiO 2 Chlorinated, chlorinated Fe 2 O 3 、TiO 2 Gasifying, wherein the flue gas enters an ascending flue along with the reacted flue gas, and the un-chlorinated or gasified slag liquid falls into the bottom of the furnace;
s4, enabling the slag liquid to flow into a carbothermic reduction furnace arranged at the lower part through a furnace bottom water gap, adding a carbonaceous material into the carbothermic reduction furnace, introducing smoke into the bottom of the carbothermic reduction furnace for stirring, gasifying and separating the additive from the slag liquid by carbothermic reduction, enabling the slag liquid to enter a dry granulation and waste heat recovery device from one side of the carbothermic reduction furnace, and granulating and cooling the slag liquid into blast furnace slag with latent hydraulicity;
s5, the furnace gas of the liquid chlorination furnace rises through an ascending flue, is cooled and cooled, meanwhile, the low-boiling-point gas is solidified, and is settled together with liquid drops carried by the gas and falls into a liquid level, the primarily cooled furnace gas enters a titanium tetrachloride separation and recovery device, titanium tetrachloride is condensed into liquid state and is separated from the furnace gas, the liquid is further purified and filtered to form a titanium tetrachloride solution, part of the furnace gas after being separated from the titanium tetrachloride is pressurized and conveyed to a lower-layer hollow stopper rod through a three-way shunt valve to be used as pneumatic conveying gas, unreacted chlorine in the furnace gas is recycled, and the redundant furnace gas passes through an absorber and a separator, and HCl is separated out and emptied through a chimney;
s6, pressurizing furnace gas of the carbothermic reduction furnace, feeding the furnace gas into an upper-layer hollow stopper rod, feeding slag liquid for recycling, introducing nitrogen into a jacket, wherein the air pressure in the jacket is slightly larger than that in the liquid chlorination furnace chamber, and the nitrogen penetrates through vent holes in the inner wall of the jacket to form a nitrogen gas film on the inner wall of the liquid chlorination furnace chamber so as to prevent the corrosion of high-temperature chlorine.
In S2, the fixed carbon content of petroleum coke is more than 95%, the volatile component is 2-4%, the granularity is less than or equal to 0.075mm, the carbon blending ratio is 140-160% of the theoretical amount of complete reaction, and the oxygen-enriched air pressure is 0.8-1.0 Mpa.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the process for preparing titanium tetrachloride by high-temperature carbonization-low-temperature chlorination, the process omits a high-temperature carbonization stage, saves energy consumption of high-temperature carbonization and power consumption of crushing and grinding before entering a low-temperature chlorination furnace, simplifies process flow and equipment, and is relatively simple in production implementation and control operation.
2. Compared with the boiling chlorination process, the liquid chlorination method for the titanium-containing blast furnace slag solves the problem of CaCl generation by chlorination 2 And MgCl 2 Two kinds of chlorides with low melting point and high boiling point are melted into liquid phase adhesion furnace burden in a boiling chlorination furnace (800-1000 ℃), so that the furnace burden is agglomerated, and a boiling layer is damaged, thereby solving the problems that the titaniferous blast furnace slag of the high-calcium magnesium salt cannot be directly subjected to fluidized chlorination, but must be carbonized at high temperature, and carbonized slag is chlorinated at low temperature.
3. The liquid chlorination method of the titanium-containing blast furnace slag solves the problems that a large amount of reaction heat energy in the chlorination process needs to be led out in boiling chlorination and low-temperature chlorination, and the temperature and the heat balance in the furnace are difficult to control.
4. The liquid chlorination method of the titanium-containing blast furnace slag ensures that CaO in the slag liquid is not chlorinated or is rarely chlorinated, the cooled chlorinated slag can be free from washing, the activity of the blast furnace slag is achieved, and the problem of resource utilization of the titanium-containing blast furnace slag is solved.
5. The titanium-containing blast furnace slag liquid chlorination device prevents chlorine from strongly corroding the furnace wall at high temperature by using the inert gas film, and prolongs the service life and the safety of equipment.
Drawings
FIG. 1 is a system diagram for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag.
Reference numerals shown in the drawings: 1. a chlorine gas supply device; 2. a double-layer tundish; 3. an upper layer hollow stopper rod; 4. a hollow stopper rod at the lower layer; 5. an additive storage tank; 6. a petroleum coke storage bin; 7. spraying a water gap; 8. a chlorine gas nozzle; 9. a liquid chlorination furnace; 10. a rising flue; 11. a carbothermic reduction furnace; 12. a bottom blowing nozzle; 13. a carbon material storage bin; 14. a condenser; 15. a gas-liquid separator; 16. a titanium tetrachloride separation and recovery device; 17. a tail gas treatment and discharge device; 18. a dry granulation and waste heat recovery device.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the present application.
The first embodiment is as follows:
the system for preparing titanium tetrachloride through liquid chlorination of titanium-containing blast furnace slag shown in fig. 1 comprises a double-layer tundish 2, wherein the lower end of the double-layer tundish 2 is connected with a liquid chlorination furnace 9, the bottom end of the liquid chlorination furnace 9 is communicated with a carbothermic reduction furnace 11, the side edge of the carbothermic reduction furnace 11 is communicated with a dry granulation and waste heat recovery device, the liquid chlorination furnace 9 is connected with a chlorine gas supply device 1 through a pipeline, the chlorine gas supply device 1 comprises a liquid chlorine tank, a vaporizer and a buffer tank, and the pressure of the buffer tank is controlled to be 0.4Mpa.
Further, package 2 is including the upper tundish and the lower floor's tundish of dislocation set, through the mouth of a river intercommunication between upper tundish and the lower floor's tundish, the lower floor's tundish is through setting up the injection water mouth 7 and the liquid chlorination furnace 9 intercommunication in the middle package bottom of lower floor, set up upper cavity stopper rod 3 in the mouth of a river, set up lower floor's cavity stopper rod 4 in the injection mouth of a river 7.
Further, the liquid chlorination furnace 9 comprises a furnace top, a furnace body and a furnace bottom, the inner layer furnace wall of the liquid chlorination furnace 9 is divided into an upper section and a lower section, the upper section is an air flow section, the lower section is a molten pool section, the furnace wall is built by water-cooling pipes and a plurality of layers of refractory and heat-insulating materials, the inner wall of the furnace chamber can be hung with slag to form a refractory material protective layer, the air flow section comprises a jacket structure, the inner wall of the jacket is made of stainless steel materials and silicon nitride ceramics, vent holes are uniformly and densely distributed on the stainless steel materials and the silicon nitride ceramics to form an inner wall anticorrosion inert gas air film, the top end of the furnace top is communicated with a water injection port 7, one side of the water injection port 7 is provided with a chlorine gas nozzle 8 which forms an angle of 45 degrees with the central line of the water injection port 7, and the outer layer of the liquid chlorination furnace 9 is a furnace shell welded by steel materials.
Furthermore, an ascending flue 10 is arranged on the other side of the injection water gap 7, the ascending flue 10 is of a water-cooled wall structure, a gas outlet pipeline is arranged at the top of the ascending flue 10, and a water-cooled wall of the ascending flue 10 is coated with a refractory and acid-resistant coating.
Further, the top of uptake 10 sets up the export, sets up condenser 14 through the export intercommunication, condenser 14 top links to each other with vapour and liquid separator 15, condenser 14 passes through the pipeline with the liquid outlet of vapour and liquid separator 15 bottom and links to each other, and communicates titanium tetrachloride separation recovery unit 16 in the lump, and titanium tetrachloride separation recovery unit 16 includes condenser, vapour and liquid separator, filter, foam tower and titanium tetrachloride storage tank, and the gas outlet at vapour and liquid separator 15 top passes through pipeline intercommunication tee bend distribution valve, tee bend distribution valve passes through pipeline distribution part gas and passes through fan pressurization and communicate hollow stopper rod 4 in lower floor, and pressure is 0.9Mpa, inserts petroleum coke storage bin 6 on the pipeline, and the petroleum coke powder fineness is 260 meshes, tee bend distribution valve passes through pipeline distribution part gas and gets into tail gas treatment discharging equipment 17, and tail gas treatment discharging equipment 17 includes receiver, vapour and liquid separator, dilute hydrochloric acid storage tank and chimney.
Further, the furnace bottom is of a conical bottom structure, a sliding water gap is arranged on the furnace bottom and is communicated with the carbothermic reduction furnace 11, the water gap is made of high-temperature-resistant ceramics and is provided with a heat insulation layer, the water gap is designed to be a sliding water gap, the liquid level of the liquid chlorination furnace 9 is adjusted, the carbothermic reduction furnace 11 is in a cylindrical shape, a square barrel shape or a rectangular barrel shape, and a horizontal cylindrical shape is selected in the embodiment.
Further, a bottom blowing spray pipe 12 is arranged at the bottom of the carbothermic reduction furnace 11, a carbon material inlet and a furnace gas outlet pipeline are arranged at the upper part of the carbothermic reduction furnace 11, the carbon material inlet is connected with a carbon material storage bin 13, the furnace gas outlet pipeline is communicated with an upper layer hollow stopper rod 3 through a communicating pipe, the communicating pipe is connected with oxygen-enriched air and an additive storage tank 5, a slag liquid outlet is arranged at the side edge of the carbothermic reduction furnace 11, the slag liquid outlet is communicated with a dry-method granulator waste heat recovery device 18, and the dry-method granulator waste heat recovery device 18 comprises a bubble atomization nozzle or a pneumatic atomization nozzle, a waste heat boiler and a granulated slag collection system.
Furthermore, the inside of the jacket structure is provided with a vent hole, and nitrogen is introduced into the jacket through the vent hole.
The process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag comprises the following steps:
s1, enabling 1400-DEG C titanium-containing blast furnace slag liquid discharged by a blast furnace to flow into an upper-layer tundish, simultaneously adding an additive through pneumatic conveying, adding the additive into the slag liquid through an upper-layer hollow stopper rod 3, lifting the upper-layer hollow stopper rod 3, and enabling the slag liquid to flow into a lower-layer tundish;
s2, introducing oxygen-enriched air into the lower-layer hollow stopper rod 4, metering and adding petroleum coke, adding carbon into the titanium-containing blast furnace slag liquid, lifting the lower-layer hollow stopper rod 4, mixing the slag liquid and the carbon in a contraction section and a straight pipe section of a water gap, and flowing into a carbothermic reduction furnace 11;
s3, spraying the slag liquid from a water gap, impacting the slag liquid by high-speed high-concentration chlorine gas to form dispersed liquid drops, fully contacting the gas liquid, and carrying out Fe 2 O 3 、TiO 2 Chlorinated, chlorinated Fe 2 O 3 、TiO 2 Gasifying, wherein the flue gas enters the uptake flue 10 along with the reacted flue gas, and the un-chlorinated or gasified slag liquid falls into the bottom of the furnace;
s4, enabling the slag liquid to flow into a carbothermic reduction furnace 11 arranged at the lower part through a furnace bottom water gap, adding a carbonaceous material into the carbothermic reduction furnace 11, introducing smoke at the bottom for stirring, gasifying and separating the additive from the slag liquid by carbothermic reduction, enabling the slag liquid to enter a dry granulation and waste heat recovery device 18 from one side of the carbothermic reduction furnace, and granulating and cooling the slag liquid into blast furnace slag with latent hydraulicity;
s5, the furnace gas of the liquid chlorination furnace 9 rises through an ascending flue, is cooled and solidified, meanwhile, low-boiling-point gas is solidified, and is settled together with liquid drops carried by the gas and falls into the liquid level, the cooled furnace gas enters a titanium tetrachloride separation and recovery device 16, the titanium tetrachloride is condensed into liquid to be separated from the furnace gas, the liquid is further purified and filtered to form a titanium tetrachloride solution, part of the furnace gas after being separated from the titanium tetrachloride is pressurized and conveyed to a lower-layer hollow stopper rod 4 through a three-way shunt valve to be used as pneumatic conveying gas, unreacted chlorine in the furnace gas is recycled, and the redundant furnace gas passes through an absorber and a separator to be separated out HCl and is emptied through a chimney;
s6, pressurizing furnace gas of the carbothermic reduction furnace 11, allowing the furnace gas to enter the upper-layer hollow stopper rod 3, allowing the furnace gas to enter slag liquid for recycling, introducing nitrogen into the jacket, wherein the pressure in the jacket is slightly greater than that in the furnace chamber of the liquid chlorination furnace 9, and allowing the nitrogen to penetrate through vent holes in the inner wall of the jacket to form a nitrogen gas film on the inner wall of the furnace chamber of the liquid chlorination furnace 9, so that the corrosion of high-temperature chlorine is prevented.
In S2, the fixed carbon content of the petroleum coke is 96%, the volatile matter content is 3%, the granularity is 0.075mm, the carbon blending ratio is 150% of the theoretical amount of complete reaction, and the oxygen-enriched air pressure is 0.9Mpa.
Example two:
the process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag comprises the following steps:
s1, enabling titanium-containing blast furnace slag liquid discharged by a blast furnace at 1380 ℃ to flow into an upper-layer tundish, adding an additive through pneumatic conveying, adding the additive into the slag liquid through an upper-layer hollow stopper rod 3, lifting the upper-layer hollow stopper rod 3, and enabling the slag liquid to flow into a lower-layer tundish;
s2, introducing oxygen-enriched air into the lower-layer hollow stopper rod 4, metering and adding petroleum coke, adding carbon into the titanium-containing blast furnace slag liquid, lifting the lower-layer hollow stopper rod 4, mixing the slag liquid and the carbon in a contraction section and a straight pipe section of a water gap, and flowing into a carbothermic reduction furnace 11;
s3, spraying the slag liquid from a water gap, impacting the slag liquid by high-speed high-concentration chlorine gas to form dispersed liquid drops, fully contacting the gas liquid, and carrying out Fe 2 O 3 、TiO 2 Chlorinated, chlorinated Fe 2 O 3 、TiO 2 Gasifying, wherein the flue gas enters the uptake flue 10 along with the reacted flue gas, and the un-chlorinated or gasified slag liquid falls into the bottom of the furnace;
s4, enabling the slag liquid to flow into a carbothermic reduction furnace 11 arranged at the lower part through a furnace bottom water gap, adding carbonaceous materials into the carbothermic reduction furnace 11, introducing smoke at the bottom for stirring, gasifying and removing additives from the slag liquid by carbothermic reduction, enabling the slag liquid to enter a dry granulation and waste heat recovery device 18 from one side of the carbothermic reduction furnace, and granulating and cooling the slag liquid into blast furnace slag with latent hydraulicity;
s5, the furnace gas of the liquid chlorination furnace 9 rises through an ascending flue, is cooled and solidified, meanwhile, low-boiling-point gas is solidified, and is settled together with liquid drops carried by the gas and falls into the liquid level, the cooled furnace gas enters a titanium tetrachloride separation and recovery device 16, the titanium tetrachloride is condensed into liquid to be separated from the furnace gas, the liquid is further purified and filtered to form a titanium tetrachloride solution, part of the furnace gas after being separated from the titanium tetrachloride is pressurized and conveyed to a lower-layer hollow stopper rod 4 through a three-way shunt valve to be used as pneumatic conveying gas, unreacted chlorine in the furnace gas is recycled, and the redundant furnace gas passes through an absorber and a separator to be separated out HCl and is emptied through a chimney;
s6, pressurizing furnace gas of the carbothermic reduction furnace 11, feeding the furnace gas into the upper-layer hollow stopper rod 3, feeding slag liquid for recycling, introducing nitrogen into the jacket, wherein the pressure in the jacket is slightly greater than that in the furnace chamber of the liquid chlorination furnace 9, and the nitrogen penetrates through vent holes in the inner wall of the jacket to form a nitrogen gas film on the inner wall of the furnace chamber of the liquid chlorination furnace 9, so that the corrosion of high-temperature chlorine is prevented.
In S2, the fixed carbon content of the petroleum coke is 97%, the volatile matter content is 3.8%, the granularity is 0.07mm, the carbon blending ratio is 155% of the theoretical amount of complete reaction, and the oxygen-enriched air pressure is 0.95Mpa.
The working principle of the system of the invention is as follows:
baking the system to raise the temperature, when the baking temperatures of the double-layer tundish 2, the liquid chlorination furnace 9 and the carbothermic reduction furnace 11 reach 1000 ℃, enabling 1400 ℃ liquid blast furnace slag discharged by the blast furnace to flow into the upper-layer tundish, and adding an additive of the additive storage tank 5 into the upper-layer hollow stopper rod 3 when the liquid level of the upper-layer tundish reaches an operation position; simultaneously, oxygen-enriched air is introduced, the additive is sprayed out of the upper layer hollow stopper rod 3 through air force and enters the titanium-containing blast furnace slag liquid, the additive and calcium oxide and magnesium oxide in the slag liquid are preferentially combined into inorganic salt, the upper layer hollow stopper rod 3 is lifted, the titanium-containing blast furnace slag liquid flows into the lower layer tundish through the middle water gap, and the additive is uniformly mixed in the slag liquid in the process. The addition amount of the additive is adjusted according to the content of calcium and magnesium in the slag liquid and is 1.1 times of the theoretical addition amount; the oxygen-enriched air pressure was 2000Pa.
The slag liquid of the blast furnace slag containing titanium is combined with an additive to enter a lower-layer tundish, petroleum coke powder and oxygen-enriched air are added into the lower-layer hollow stopper rod 4 in a metering mode, a rod head of the lower-layer hollow stopper rod 4 is lifted to the middle position of a cylinder of a water gap, the petroleum coke powder is sprayed out from an air guide through hole in the rod head of the lower-layer hollow stopper rod 4 at a high speed under the action of the oxygen-enriched air, is accelerated to be mixed violently in a straight pipe section together with slag liquid through a water gap necking, and is sprayed into a liquid chlorination furnace 9, the fixed carbon content of the petroleum coke powder used here is 96%, the volatile content is 3%, the granularity is 0.075mm, the carbon distribution ratio is 150% of the theoretical amount of complete reaction, and the oxygen-enriched air pressure is 0.9MPa.
The slag liquid entering the liquid chlorination furnace 9 forms liquid drops under the accelerated impact of the pressure gas of the mixed petroleum coke powder, the chlorine nozzle 8 on the liquid chlorination furnace 9 sprays high-speed airflow which meets the sprayed slag liquid and is crushed into finer liquid drops, the reaction surface area is rapidly enlarged to cause good element chlorination kinetic conditions, and TiO in the slag liquid 2 And other elements which are easy to chlorinate are chlorinated immediately, the chloride with the boiling point lower than the furnace temperature is gasified and enters the furnace gas, and the chloride with the boiling point higher than the furnace temperature falls into the furnace bottom along with the chlorination residue liquid.
Inert gas nitrogen is introduced into a jacket at the upper part of the furnace body of the liquid chlorination furnace 9, the pressure of the jacket is slightly higher than the pressure in the furnace, and the nitrogen forms a gas film on the inner wall of the hearth through the vent holes to prevent high-temperature chloride from being corroded; the water-cooled copper sleeve at the lower part of the furnace body is introduced with cooling water, so that the inner wall of the hearth is bonded, cooled and formed into a slag layer, and the furnace wall is protected to prevent the slag liquid from being corroded at high temperature.
The furnace gas mixed with nitrogen rises to the uptake flue 10, cooling water is introduced into the cooling wall and the cooling hanger of the uptake flue 10, the furnace gas is cooled to 220 ℃, chlorides with the boiling point lower than 240 ℃ are condensed again, and the chlorides are settled and fall into furnace bottom slag liquid; the uncondensed furnace gas enters a condenser 14, and the condensed liquid in the cooler 14 adopts cooled crude TiCl 4 The liquid is sprayed from the top of the device and contacts with the furnace gas rising from the bottom in the reverse direction, and TiCl in the furnace gas 4 And other impurities are coagulated into liquid, the gas-liquid mixture is separated by a gas-liquid separator 15, and the liquid flows into a titanium tetrachloride separation and recovery device 16 to be primarily purified, namelyIs industrial (crude) titanium tetrachloride liquid; while the other gases escape from the separator 15 and the escaping gases contain more CO and CO 2 、Cl 2 HCl and other gases, wherein the gases pass through a three-way distribution valve to ensure that most of the gases are pressurized and introduced into the lower hollow stopper rod 4 and then enter the liquid chlorination furnace 9 for cyclic utilization, the rest residual gases pass through the three-way distribution valve to enter a tail gas treatment and discharge device 17, and Cl is contained in the tail gas treatment and discharge device 17 2 HCl is absorbed and then evacuated.
Because CO and CO are added into the liquid chlorination furnace 9 2 、Cl 2 And HCl gas, the addition of petroleum coke powder is properly reduced in operation, and the oxygen-enriched air quantity is reduced at the same time.
And the slag liquid at the bottom of the liquid chlorination furnace 9 flows into the carbothermic reduction furnace 11 through a water gap, a sliding inserting plate arranged in the middle of the water gap is adjusted, the liquid level in the liquid chlorination furnace 9 is adjusted, the liquid level plays a role in liquid sealing, and the liquid level further carries out chlorination reaction.
Adding carbonaceous material into the carbothermic reduction furnace 11, and spraying CO into the furnace bottom 2 The slag liquid is combined with CaO and MgO additives, and is reduced under the condition of carbothermic reduction and under the stirring of furnace bottom gas, caO and MgO are removed and enter furnace gas, a horizontal cylinder of the carbothermic reduction furnace 11 is arranged, the contact area of the slag liquid and carbonaceous materials is large, gas sprayed out of the furnace bottom causes the liquid level of the slag liquid to turn over, the contact of the slag liquid and the carbonaceous materials is strengthened, and the reduction reaction is rapid and thorough; furnace gas after carbothermic reduction enters the upper hollow stopper rod 3 through a pipeline, and is sprayed into newly added slag liquid for cyclic utilization; the slag liquid after carbothermic reduction flows into a dry granulation and waste heat recovery device 18, and the slag liquid is granulated pneumatically, cooled to 150 ℃ by a waste heat boiler and discharged to form granulated slag.
The recycled furnace gas is a reducing atmosphere, and after the recycled gas is added, the addition amount of additives is properly reduced in the operation process, so that the oxygen-enriched air amount is reduced. The reducing atmosphere reduces the high-valence titanium of the titanium-containing blast furnace slag into low-valence titanium on one hand, and heats the slag liquid on the other hand to increase the fluidity of the slag liquid.
The invention is different from the prior art in that the prior art is that the gas-solid chlorination, the titanium-rich slag or the titanium-containing blast furnace slag carbonized at high temperature are crushedGrinding into fine particles, suspending in chlorine gas or floating on chlorine salt solution, adding carbon for chlorination reaction, because CaO and MgO have preferential TiO 2 Tendency to chloridize, and CaCl 2 、MgOCl 2 The melting point is low, and the liquid phase after the calcium and magnesium chlorination is separated out to cause bed layer adhesion, so that the liquid phase formed by the calcium and magnesium chlorination is a barrier which cannot be used in the past; therefore, the titanium-rich slag is adopted, and CaO + MgO/% -is strictly controlled to be less than or equal to 1.5%, but the high-quality titanium-rich ore is few; or deeply reducing the titanium-containing blast furnace slag by using carbon at high temperature to ensure that TiO in the slag 2 The product is converted into TiC, and the low-temperature selective chlorination is carried out below 700 ℃, but the chlorination test has serious calcium and magnesium chlorination and weak selectivity. And the heat release of the chlorination of the carbide slag is large, the chlorination temperature is controlled to be below 700 ℃, redundant heat must be discharged, and how to lead out the huge reaction heat on large-scale chlorination equipment is a very difficult technical problem of adopting TiC low-temperature selective chlorination. The invention adopts the gas-liquid chlorination, adopts the liquid titanium-containing blast furnace slag, utilizes the chlorine gas to blow and chlorinate in the liquid state, solves the restriction factors of the technology, improves the chlorination reaction rate, simplifies the flow, reduces the equipment investment and greatly reduces the energy consumption.
Claims (7)
1. The system for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag is characterized in that: the device comprises a double-layer tundish (2), wherein the lower end of the double-layer tundish (2) is connected with a liquid chlorination furnace (9), the bottom end of the liquid chlorination furnace (9) is communicated with a carbothermic reduction furnace (11), the side edge of the carbothermic reduction furnace (11) is communicated with a dry granulation and waste heat recovery device, the liquid chlorination furnace (9) is connected with a chlorine gas supply device (1) through a pipeline, the double-layer tundish (2) comprises an upper-layer tundish and a lower-layer tundish which are arranged in a staggered manner, the upper-layer tundish and the lower-layer tundish are communicated through a water gap, the lower-layer tundish is communicated with the liquid chlorination furnace (9) through a water injection port (7) arranged at the bottom end of the lower-layer tundish, an upper-layer hollow stopper (3) is arranged in the water gap, a lower-layer hollow stopper (4) is arranged in the water injection port (7), the liquid chlorination furnace (9) comprises a water injection port, a furnace bottom, the inner layer of the liquid chlorination furnace (9) is divided into an upper section and a lower section, the upper section is an air flow section, the lower section is of the air flow section and comprises a jacket structure, the top end communicated with the water injection port (7), the carbon material injection port (7), a furnace wall inlet (11) and a carbon blowing nozzle (11) and a carbon material blowing nozzle (12) arranged at one side of the top of the furnace top of the furnace (11) and a carbon furnace wall (11) and a carbon blowing furnace wall of the carbon reduction furnace, a furnace gas outlet pipeline of the carbothermic reduction furnace (11) is communicated with the upper layer hollow stopper rod (3) through a communicating pipe, the communicating pipe is connected with oxygen-enriched air and an additive storage tank (5), a slag liquid outlet is formed in the side edge of the carbothermic reduction furnace (11), and the slag liquid outlet is communicated with a dry method granulator waste heat recovery device.
2. The system for preparing titanium tetrachloride by the liquid chlorination of the titanium-containing blast furnace slag according to claim 1, characterized in that: and an uptake (10) is arranged on the other side of the injection water gap (7), the uptake (10) is of a water-cooled wall structure, a gas guide pipeline is arranged at the top of the uptake, and the water-cooled wall of the uptake (10) is coated with a refractory acid-resistant coating.
3. The system for preparing titanium tetrachloride by the liquid chlorination of the titanium-containing blast furnace slag according to claim 2, characterized in that: the utility model discloses a titanium tetrachloride separating and recycling device, including uptake flue (10), condenser (14), gas-liquid separator (15), condenser (14), tee bend distribution valve, fan, pressure be 0.8 ~ 1.0Mpa, insert petroleum coke storage bin (6) on the pipeline, the petroleum coke powder fineness is 200-300 meshes, tee bend distribution valve passes through pipeline distribution part gas and gets into tail gas treatment discharging equipment (17).
4. The system for preparing titanium tetrachloride by the liquid chlorination of the titanium-containing blast furnace slag according to claim 1, characterized in that: the furnace bottom is of a conical bottom structure, and a sliding water gap is arranged at the furnace bottom and communicated with the carbothermic reduction furnace (11).
5. The system for preparing titanium tetrachloride through liquid chlorination of titanium-containing blast furnace slag according to claim 1, wherein: and a vent hole is formed in the jacket structure, and nitrogen is introduced into the jacket through the vent hole.
6. The process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag is characterized by comprising the following steps:
s1, allowing titanium-containing blast furnace slag liquid at 1350-1450 ℃ discharged by a blast furnace to flow into an upper-layer tundish, adding an additive through pneumatic transmission, adding the additive into the slag liquid through an upper-layer hollow stopper rod (3), lifting the upper-layer hollow stopper rod (3), and allowing the slag liquid to flow into a lower-layer tundish;
s2, introducing oxygen-enriched air into the lower-layer hollow stopper rod (4), metering petroleum coke, adding carbon into the titanium-containing blast furnace slag liquid, lifting the lower-layer hollow stopper rod (4), mixing the slag liquid and the carbon in a contraction section and a straight pipe section of a water gap, and flowing into a liquid chlorination furnace (9);
s3, spraying the slag liquid from a water gap, impacting the slag liquid by high-speed high-concentration chlorine gas to form dispersed liquid drops, fully contacting the gas liquid, and carrying out Fe 2 O 3 、TiO 2 Chlorinated, chlorinated Fe 2 O 3 、TiO 2 Gasifying, wherein the flue gas enters an ascending flue (10) along with the reacted flue gas, and the un-chlorinated or gasified slag liquid falls into the bottom of the furnace;
s4, the slag liquid flows into a carbothermic reduction furnace (11) arranged at the lower part through a furnace bottom water gap, carbonaceous materials are added into the carbothermic reduction furnace (11), flue gas is introduced into the bottom for stirring, the additive is gasified and separated from the slag liquid by carbothermic reduction, the slag liquid enters a dry granulation and waste heat recovery device (18) from one side of the carbothermic reduction furnace (11), and the slag liquid is granulated and cooled into blast furnace slag with latent hydraulicity;
s5, the furnace gas of the liquid chlorination furnace (9) rises through a rising flue, is cooled, is solidified, and is settled together with liquid drops carried by the gas and falls into the liquid level, the primarily cooled furnace gas enters a titanium tetrachloride separation and recovery device (16), titanium tetrachloride is condensed into liquid to be separated from the furnace gas, the liquid is further purified and filtered to form a titanium tetrachloride solution, part of the furnace gas after the titanium tetrachloride is separated is pressurized and conveyed to a lower-layer hollow stopper rod (4) through a three-way shunt valve to be used as pneumatic conveying gas, unreacted chlorine in the furnace gas is continuously recycled, and the redundant furnace gas passes through an absorber and a separator, and HCl is separated out and is emptied through a chimney;
s6, pressurizing furnace gas of the carbothermic reduction furnace (11), feeding the furnace gas into the upper-layer hollow stopper rod (3), feeding slag liquid for recycling, introducing nitrogen into the jacket, wherein the pressure in the jacket is slightly greater than that in the furnace chamber of the liquid chlorination furnace (9), and the nitrogen penetrates through vent holes in the inner wall of the jacket to form a nitrogen gas film on the inner wall of the furnace chamber of the liquid chlorination furnace (9) so as to prevent the corrosion of high-temperature chlorine.
7. The process for preparing titanium tetrachloride by the liquid chlorination of the titanium-containing blast furnace slag according to claim 6, wherein the chlorination comprises the following steps: in S2, the fixed carbon content of petroleum coke is more than 95%, the volatile component is 2-4%, the granularity is less than or equal to 0.075mm, the carbon blending ratio is 140-160% of the theoretical amount of complete reaction, and the oxygen-enriched air pressure is 0.8-1.0 Mpa.
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