CN115367790B - Method and device for preparing titanium tetrachloride - Google Patents
Method and device for preparing titanium tetrachloride Download PDFInfo
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- CN115367790B CN115367790B CN202211031253.6A CN202211031253A CN115367790B CN 115367790 B CN115367790 B CN 115367790B CN 202211031253 A CN202211031253 A CN 202211031253A CN 115367790 B CN115367790 B CN 115367790B
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- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
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Abstract
The invention discloses a method and a device for preparing titanium tetrachloride. The method comprises the following steps: preheating slag powder to a predetermined temperature, wherein the slag powder comprises one or more of: titanium carbide, titanium nitride, titanium carbonitride; feeding the preheated slag powder into a tubular reactor with an externally-applied magnetic field by utilizing a mixed gas flow containing chlorine and nitrogen, so that the mixed gas flow and the slag powder react in the tubular reactor to generate titanium tetrachloride; wherein the tubular reactor is arranged horizontally or the tubular reactor is inclined at a predetermined angle with respect to the horizontal and the feed inlet end of the tubular reactor is higher than the product outlet end. The invention can improve the reaction efficiency and the chlorination rate and reduce the production cost of titanium tetrachloride.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method and a device for preparing titanium tetrachloride.
Background
The current method for producing titanium tetrachloride is mainly a boiling chlorination method, namely, the titanium tetrachloride is rich in TiO 2 After mixing titanium raw material and petroleum coke according to a certain proportion, adding chlorine gas to carry out closed chemical reaction in a chlorination furnace, wherein the reaction temperature is generally higher than 900 ℃, and the titanium tetrachloride is obtained after the reaction is finished. However, due to the natural endowment of the titanium ore in China, the natural raw ore is mainly vanadium titano-magnetite, the content of calcium and magnesium in the ore is high, and TiO required by the traditional boiling chlorination process is prepared 2 More than or equal to 90 weight percent, and the treatment cost, the flow length and the difficulty of the titanium raw material with CaO and MgO less than or equal to 1.5 weight percent are high.
In the prior art, a process route for synchronously preparing titanium tetrachloride by treating titanium-containing blast furnace slag mainly by a high-temperature carbonization-low-temperature chlorination process exists, wherein titanium-containing blast furnace slag is carbonized to obtain slag containing titanium carbide, and the titanium carbide-containing slag is subjected to chlorination to obtain titanium tetrachloride.
The patent document with the application number of CN201610191369.4 discloses a preparation method of titanium tetrachloride, aiming at different grades of carbonized slag, the carbonized slag is classified in advance, different boiling chlorination processes are adopted to carry out boiling chlorination in different boiling chlorination reactors, and the boiling chlorination efficiency of the carbonized slag is improved. Patent application CN202010862320.3 discloses a method for chlorinating carbonized residues in a boiling chlorination reactor using a plurality of chlorination units.
The boiling chlorination reactor has the problems of complex structure, relatively independent operation parameters of each unit, relatively high operation difficulty, relatively long residence time of the carbonized slag in the reactor, low reaction efficiency, incomplete reaction of the titanium carbide in the carbonized slag, low chlorination rate, high production cost and the like.
Disclosure of Invention
The main object of the present invention is to provide a method and apparatus for preparing titanium tetrachloride, which solve at least one aspect of the above technical problems.
According to one aspect of the present invention, there is provided a process for producing titanium tetrachloride comprising: preheating slag powder to a predetermined temperature, wherein the slag powder comprises one or more of: titanium carbide, titanium nitride, titanium carbonitride; feeding the preheated slag powder into a tubular reactor with an externally-applied magnetic field by utilizing a mixed gas flow containing chlorine and nitrogen, so that the mixed gas flow and the slag powder react in the tubular reactor to generate titanium tetrachloride; wherein the tubular reactor is arranged horizontally or the tubular reactor is inclined at a predetermined angle with respect to the horizontal and the feed inlet end of the tubular reactor is higher than the product outlet end.
According to one embodiment of the invention, the predetermined angle is 5 ° to 15 °.
According to one embodiment of the invention, the predetermined temperature is 450 ℃ to 500 ℃.
According to one embodiment of the invention, before preheating the slag powder to the predetermined temperature, the method further comprises: crushing the slag raw material to obtain the slag powder with the granularity less than or equal to 10 mu m.
According to one embodiment of the invention, the chlorine is used in an amount of 105% of the chemical reaction equivalent required to react with the reactants in the slag powder.
According to one embodiment of the invention, the slag powder is allowed to stay in the tubular reactor for a time of 2s to 10s.
According to one embodiment of the invention, the temperature at which the mixed gas stream reacts with the slag powder is between 500 ℃ and 580 ℃.
According to one embodiment of the invention, the strength of the magnetic field is 0-2T.
According to another aspect of the present invention, there is provided an apparatus for producing titanium tetrachloride, comprising: a tubular reactor which is horizontally arranged or inclined at a predetermined angle with respect to the horizontal plane, and the raw material inlet end of which is higher than the product outlet end; the magnetic field generator is arranged outside the tubular reactor; the first pipe orifice of the three-way pipe is connected with the material inlet of the tubular reactor; a feed portion connected with the second nozzle of the tee, the feed portion for providing slag powder, wherein the slag powder comprises one or more of the following: titanium carbide, titanium nitride, titanium carbonitride; and the air supply part is connected with the third pipe orifice of the three-way pipe and is used for providing mixed air flow containing chlorine and nitrogen.
According to one embodiment of the invention, the magnetic field generator is arranged in the upper half of the tubular reactor.
According to the method for preparing titanium tetrachloride, disclosed by the embodiment of the invention, under the action of the mixed gas flow containing chlorine and nitrogen, slag powder is sprayed into the tubular reactor, substances such as titanium carbide, titanium nitride, titanium carbonitride and the like contained in the slag powder have weak magnetism, and the slag powder can be prevented from sinking and accumulating to the bottom of the tubular reactor by virtue of magnetic force through the tubular reactor adopting an externally-applied magnetic field, so that good dispersibility of the slag powder can be ensured, the contact area between the chlorine and the slag powder is further increased, the gas-solid reaction is promoted, and the reaction efficiency is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a flow chart of a method of preparing titanium tetrachloride according to an embodiment of the present invention;
FIG. 2 shows a schematic view of an apparatus for producing titanium tetrachloride according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
It should be noted that, in the embodiments of the present invention, all the expressions "first" and "second" are used to distinguish two entities with the same name but different entities or different parameters, and it is noted that the "first" and "second" are only used for convenience of expression, and should not be construed as limiting the embodiments of the present invention, and the following embodiments are not described one by one.
FIG. 1 shows a flow chart of a method of producing titanium tetrachloride according to an embodiment of the present invention. As shown in fig. 1, the method includes:
step S1, preheating slag powder to a predetermined temperature, wherein the slag powder comprises one or more of the following: titanium carbide, titanium nitride, titanium carbonitride;
s2, sending the preheated slag powder into a tubular reactor with an externally-applied magnetic field by utilizing a mixed gas flow containing chlorine and nitrogen, so that the mixed gas flow and the slag powder react in the tubular reactor to generate titanium tetrachloride; wherein the tubular reactor is arranged horizontally or the tubular reactor is inclined at a predetermined angle with respect to the horizontal and the feed inlet end of the tubular reactor is higher than the product outlet end.
In the method for preparing titanium tetrachloride according to the embodiment of the invention, the mixed gas flow containing chlorine and nitrogen is used as carrier gas, slag powder is sprayed into the tubular reactor after being accelerated by the mixed gas flow, substances such as titanium carbide, titanium nitride, titanium carbonitride and the like contained in the slag powder have weak magnetism, and the slag powder can be prevented from sinking and accumulating to the bottom of the tubular reactor by virtue of magnetic force through the tubular reactor adopting an externally-applied magnetic field, so that good dispersibility of the slag powder can be ensured, the contact area between the chlorine and the slag powder can be further increased, gas-solid reaction can be promoted, and the reaction efficiency can be improved. Wherein the magnetic force exerted by the slag powder is balanced with gravity so that the slag powder can be suspended in the tubular reactor.
One end of the tubular reactor is provided with a raw material inlet, the other end of the tubular reactor is provided with a product outlet, the end provided with the raw material inlet is taken as a raw material inlet end, and the end provided with the product outlet is taken as a product outlet end. The product outlet end of the tubular reactor is inclined downwards relative to the raw material inlet end, so that the raw material inlet end is higher than the product outlet end, and slag powder is fed in and discharged out. The slag powder can move in the tubular reactor under the action of gravity, so that the pushing load of the mixed gas flow can be reduced, the consumption or pressure of the mixed gas flow is reduced, and the cost is saved.
In an embodiment of the present invention, the predetermined angle is 5 ° to 15 °. The setting of the angle range can play a role in promoting the movement of the slag powder, and can prevent the slag powder from leaving the tubular reactor too quickly due to insufficient reaction caused by too large angle.
In the embodiment of the invention, the residence time of the slag powder in the tubular reactor is 2-10 s, and the time range can ensure that the slag powder and chlorine fully react.
In an embodiment of the invention, the chlorine is used in an amount of 105% of the chemical reaction equivalent required to react with the reactants in the slag powder. The chlorine amount is proper and excessive, so that the reaction is ensured to be fully carried out. If only chlorine is used to blow the slag powder, the amount of gas may be insufficient, so that the present invention uses a mixed gas stream comprising chlorine and nitrogen to feed the slag powder into the tubular reactor.
Before the slag powder is sent into the tubular reactor, the slag powder and chlorine can be ensured to quickly reach the reaction temperature in the tubular reactor by preheating the slag powder. In an embodiment of the present invention, the predetermined temperature is 450 ℃ to 500 ℃. The predetermined temperature is suitable for the slag powder and chlorine to reach the desired reaction temperature in the tubular reactor.
In the embodiment of the invention, the temperature of the mixed gas flow for reacting with the slag powder is 500-580 ℃, and the temperature range can ensure that the slag powder and chlorine react efficiently and sufficiently. In some embodiments, the reaction temperature may be too high, in which case the reaction temperature may be kept within the above-described range by taking cooling measures.
In an embodiment of the invention, the magnetic field has a strength of 0 to 2T, which is in a range that ensures suspension of slag powder in the tubular reactor.
The method further comprises, prior to preheating the slag powder to the predetermined temperature: crushing the slag raw material to obtain the slag powder with the granularity less than or equal to 10 mu m, thereby ensuring that the slag powder is fully contacted with chlorine. The slag raw material may be slag obtained after carbonizing blast furnace slag containing titanium oxide.
In the embodiment of the invention, the content of titanium carbide, titanium nitride and titanium carbonitride in the slag powder is 10-100 percent by weight.
The titanium tetrachloride produced in the tubular reactor is crude titanium tetrachloride. The method of the present invention may further comprise: and (3) carrying out cyclone dust collection treatment, spray condensation treatment and refining on the generated crude titanium tetrachloride to obtain refined titanium tetrachloride.
According to the method for preparing titanium tetrachloride, disclosed by the embodiment of the invention, the slag containing titanium carbide, titanium nitride or titanium carbonitride is used as a raw material, so that the chlorination reaction temperature can be reduced; the materials are further dispersed by utilizing the weak magnetic characteristics of substances such as titanium carbide, titanium nitride or titanium carbonitride, so that the contact area between chlorine and slag can be increased, and the gas-solid reaction is promoted; the tubular reactor has simple structure and convenient control; the slag powder reacts with chlorine instantaneously, so that the reaction efficiency is high, the chlorination rate is high, and the production cost is low.
FIG. 2 shows a schematic view of an apparatus for producing titanium tetrachloride according to an embodiment of the present invention. As shown in fig. 2, the apparatus 100 includes: a tubular reactor 10, the tubular reactor 10 being disposed horizontally, or the tubular reactor 10 being inclined at a predetermined angle with respect to the horizontal plane, and the raw material inlet end 12 of the tubular reactor 10 being higher than the product outlet end 14; a magnetic field generator 20 disposed outside the tubular reactor 10; the three-way pipe 30, a first pipe orifice 32 of the three-way pipe 30 is connected with the material inlet 16 of the tubular reactor 10; a feed portion 40 connected to the second nozzle 34 of the tee 30, the feed portion 40 being adapted to provide a slag powder, wherein the slag powder comprises one or more of: titanium carbide, titanium nitride, titanium carbonitride; and a gas supply part 50 connected to the third nozzle 36 of the tee 30, the gas supply part 50 being for supplying a mixed gas flow containing chlorine and nitrogen.
The tubular reactor 10 has a raw material inlet 16 at one end and a product outlet at the other end, the end provided with the raw material inlet 16 being the raw material inlet end 12 and the end provided with the product outlet being the product outlet end 14. The product outlet end 14 of the tubular reactor 10 is inclined downwardly relative to the feed inlet end 12 such that the feed inlet end 12 is higher than the product outlet end 14. The predetermined angle by which the tubular reactor 10 is inclined with respect to the horizontal plane may be 5 ° to 15 °.
In an embodiment of the present invention, a magnetic field generator 20 is provided at the upper half of the tubular reactor 10 for providing an upward attractive force to the slag powder to counteract the gravity of the slag powder. The upper half may include a region occupying 1/4 to 3/4 of the sidewall of the tubular reactor 10 in the circumferential direction. For example, if the tubular reactor 10 is cylindrical, the upper half comprises: in the cross section of the tubular reactor 10, the area is 1/4 to 3/4 of the circumference. The magnetic field generator 20 may be disposed in the middle of the tubular reactor 10.
The following description is made with reference to specific examples.
Example 1
The method comprises the steps of taking 13.0wt% of slag containing titanium carbide as a raw material, crushing the slag through a stirring mill in a preparation stage to obtain slag powder, wherein the proportion of particles with the granularity smaller than 10 mu m in the slag powder is larger than 98%, and placing the slag powder into a raw material bin for standby;
the test begins and the chlorine flow is regulated to 102m 3 /h, nitrogen flow of 36m 3 And/h, setting the slag feeding rate to be 1t/h, preheating powder to 450 ℃, mixing the powder into the mixed gas flow of chlorine and nitrogen, accelerating, spraying the powder into a tubular reactor, and controlling the inlet gas speed to be 0.2m/s and the reaction section temperature to be 500-550 ℃; the generated crude titanium tetrachloride is subjected to cyclone dust collection, spray condensation to obtain refined titanium tetrachloride, and the refined titanium tetrachloride is collected into a storage tank.
Example 2
60.0wt% of slag powder containing titanium carbide is used as a raw material, the particle ratio of the particles with the granularity smaller than 10 mu m in the slag powder is larger than 98%, and the slag powder is put into a raw material bin for standby;
the test begins and the chlorine flow is regulated to 142m 3 /h, nitrogen flow 40m 3 Setting the slag feeding rate to 300kg/h, preheating powder to 450 ℃, mixing the powder with a mixed gas flow of chlorine and nitrogen, accelerating, spraying the powder into a tubular reactor, and controlling the inlet gas speed to 2.5m/s and the reaction section temperature to 500-550 ℃; the generated crude titanium tetrachloride is subjected to cyclone dust collection, spray condensation to obtain refined titanium tetrachloride, and the refined titanium tetrachloride is collected into a storage tank.
Example 3
Taking 90.0wt% of slag powder containing titanium carbide as a raw material, wherein the particle ratio of particles with the granularity smaller than 10 mu m in the slag powder is larger than 98%, and placing the slag powder into a raw material bin for standby;
the test begins and the chlorine flow is regulated to 142m 3 /h, nitrogen flow 40m 3 The slag feeding is set to be 200kg/h, powder is preheated to 450 ℃ and then mixed into the mixed gas flow of chlorine and nitrogen, the mixed gas flow is sprayed into a tubular reactor after acceleration, the inlet gas speed is 2.5m/s, and the temperature of a reaction section is 500-550 ℃; the generated crude titanium tetrachloride is subjected to cyclone dust collection, spray condensation to obtain refined titanium tetrachloride, and the refined titanium tetrachloride is collected into a storage tank.
Those of ordinary skill in the art will appreciate that: the above discussion of any embodiment is merely exemplary and is not intended to imply that the scope of the disclosure of embodiments of the invention, including the claims, is limited to such examples; combinations of features of the above embodiments or in different embodiments are also possible within the idea of an embodiment of the invention, and there are many other variations of the different aspects of the embodiments of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, and the like, which are made within the spirit and principles of the embodiments of the invention, are included within the scope of the embodiments of the invention.
Claims (7)
1. A process for preparing titanium tetrachloride comprising:
preheating slag powder to a predetermined temperature, wherein the slag powder comprises one or more of: titanium carbide, titanium nitride, titanium carbonitride;
feeding the preheated slag powder into a tubular reactor with an externally-applied magnetic field by utilizing a mixed gas flow containing chlorine and nitrogen, so that the mixed gas flow and the slag powder react in the tubular reactor to generate titanium tetrachloride; wherein the tubular reactor is arranged horizontally, or the tubular reactor is inclined at a predetermined angle relative to the horizontal plane and the raw material inlet end of the tubular reactor is higher than the product outlet end;
wherein the predetermined angle is 5-15 degrees; the strength of the magnetic field is 0-2T; so that the residence time of the slag powder in the tubular reactor is 2-10 s.
2. The method of claim 1, wherein the predetermined temperature is 450 ℃ to 500 ℃.
3. The method of claim 1, wherein prior to preheating the slag powder to the predetermined temperature, the method further comprises:
crushing the slag raw material to obtain the slag powder with the granularity less than or equal to 10 mu m.
4. The method of claim 1 wherein the chlorine is present in an amount of 105% of the chemical reaction equivalent required to react with the reactants in the slag powder.
5. The method according to claim 1, characterized in that the temperature at which the mixed gas stream reacts with the slag powder is 500-580 ℃.
6. An apparatus for producing titanium tetrachloride, comprising:
a tubular reactor which is horizontally arranged or inclined at a predetermined angle with respect to the horizontal plane, and the raw material inlet end of which is higher than the product outlet end;
the magnetic field generator is arranged outside the tubular reactor;
the first pipe orifice of the three-way pipe is connected with the material inlet of the tubular reactor;
a feed portion connected with the second nozzle of the tee, the feed portion for providing slag powder, wherein the slag powder comprises one or more of the following: titanium carbide, titanium nitride, titanium carbonitride;
the air supply part is connected with the third pipe orifice of the three-way pipe and is used for providing mixed air flow containing chlorine and nitrogen;
wherein the predetermined angle is 5-15 degrees.
7. The apparatus of claim 6, wherein the magnetic field generator is disposed in an upper half of the tubular reactor.
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| CN202211031253.6A CN115367790B (en) | 2022-08-26 | 2022-08-26 | Method and device for preparing titanium tetrachloride |
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| CN202211031253.6A CN115367790B (en) | 2022-08-26 | 2022-08-26 | Method and device for preparing titanium tetrachloride |
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| CN115367790B true CN115367790B (en) | 2023-09-05 |
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| CN111961771A (en) * | 2020-08-25 | 2020-11-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Titanium-containing blast furnace slag chlorination device |
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| US9816192B2 (en) * | 2011-12-22 | 2017-11-14 | Universal Technical Resource Services, Inc. | System and method for extraction and refining of titanium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111961771A (en) * | 2020-08-25 | 2020-11-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Titanium-containing blast furnace slag chlorination device |
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