CN116588970A - System and method for refining crude titanium tetrachloride by removing vanadium - Google Patents
System and method for refining crude titanium tetrachloride by removing vanadium Download PDFInfo
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- CN116588970A CN116588970A CN202310486111.7A CN202310486111A CN116588970A CN 116588970 A CN116588970 A CN 116588970A CN 202310486111 A CN202310486111 A CN 202310486111A CN 116588970 A CN116588970 A CN 116588970A
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- titanium tetrachloride
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 156
- 238000007670 refining Methods 0.000 title claims abstract description 38
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 28
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- 238000010438 heat treatment Methods 0.000 claims abstract description 70
- 239000007788 liquid Substances 0.000 claims abstract description 66
- VZVLQKOGWNLVAC-UHFFFAOYSA-J tetrachlorotitanium vanadium Chemical compound [V].Cl[Ti](Cl)(Cl)Cl VZVLQKOGWNLVAC-UHFFFAOYSA-J 0.000 claims abstract description 21
- 238000007599 discharging Methods 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 35
- 229910052719 titanium Inorganic materials 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 35
- 238000010992 reflux Methods 0.000 claims description 31
- 230000001105 regulatory effect Effects 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
- C01G23/024—Purification of tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a system and a method for refining crude titanium tetrachloride by removing vanadium, wherein the system comprises the following steps: a crude titanium tetrachloride heating unit for heating a crude titanium tetrachloride liquid of a first predetermined pressure to a predetermined temperature; the crude titanium tetrachloride reaction unit comprises a reaction tank, the reaction tank is connected with the crude titanium tetrachloride heating unit through a first pipeline, the first pipeline is used for conveying crude titanium tetrachloride liquid heated to a second preset pressure with a preset temperature into the reaction tank, the second preset pressure is smaller than the first preset pressure, and the reaction tank is connected with a second pipeline which is used for conveying organic matters; and the mud discharging unit is connected with the bottom of the reaction tank through a pipeline. According to the crude titanium tetrachloride vanadium removal refining system and method provided by the invention, the heating section and the reaction section of the crude titanium tetrachloride are separated, so that the scaling rate of the heating section is reduced, and the system operation efficiency is greatly improved.
Description
Technical Field
The invention relates to the field of titanium tetrachloride refining, in particular to a system and a method for refining crude titanium tetrachloride by removing vanadium.
Background
Titanium tetrachloride (TiCl) 4 ) Is used for producing pigment titanium white and titanium spongeThe most important intermediate products of the titanium series, which are produced mainly by reacting titanium dioxide-containing raw materials with chlorine at high temperature, are titanium tetrachloride, the industrial crude titanium tetrachloride generally containing various impurities, mainly VOCl 3 、FeCl 3 And the like, the raw materials need to enter a refining system for impurity removal and purification.
The removal of vanadium from crude titanium tetrachloride is an important process for refining titanium tetrachloride. Not only for the purpose of decoloring but also for the purpose of deoxidizing vanadium as an impurity. In crude titanium tetrachloride, vanadium is mainly present as VOCl 3 In the form, its boiling point is 127.2 ℃ and is close to the boiling point of 136.4 ℃ of titanium tetrachloride, tiCl 4 —VOCl 3 The difference in boiling point was 9.2℃and their relative volatility was α=1.22. Therefore, the separation by adopting a common physical rectification method is difficult, and at present, vanadium is generally removed by adopting a chemical method, for example, an organic vanadium removal process is widely adopted at home and abroad, and the main technical thought of the process is as follows: adding organic matters into crude titanium tetrachloride liquid, stirring uniformly, heating the mixed liquid to 120-138 ℃, gradually cracking the organic matters into highly dispersed and highly active micro carbon particles, and selectively reducing VOCl by the newly generated carbon particles 3 Precipitating, and removing vanadium slag by adopting a solid-liquid separation method.
However, the vanadium can be removed from the existing organic matters, so that VOCl can be effectively removed 3 The content of vanadium in the crude titanium tetrachloride is about 2000ppm, but when the content of vanadium in the crude titanium tetrachloride is further increased, for example, more than 10000ppm, the solid phase matters generated by the vanadium removal reaction are greatly increased, and the heating section and the reaction section of the crude titanium tetrachloride are both together, so that the heating equipment of the refining system is seriously scaled, and further the thermal efficiency is greatly reduced, and the problem of time-consuming cleaning of scaling is caused.
Based on this, the prior art still remains to be improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a crude titanium tetrachloride vanadium removal refining system and method, which can solve the problems that heating equipment is seriously scaled and further heat efficiency is greatly reduced and time-consuming cleaning of scaling is required due to the fact that a heating section and a reaction section of the crude titanium tetrachloride are both together in the conventional organic matter vanadium removal process.
In one aspect, the embodiment of the invention discloses a crude titanium tetrachloride vanadium removal refining system, which comprises:
a crude titanium tetrachloride heating unit for heating a crude titanium tetrachloride liquid of a first predetermined pressure to a predetermined temperature;
the crude titanium tetrachloride reaction unit comprises a reaction tank, the reaction tank is connected with the crude titanium tetrachloride heating unit through a first pipeline, the first pipeline is used for conveying crude titanium tetrachloride liquid heated to a second preset pressure of the preset temperature into the reaction tank, the second preset pressure is smaller than the first preset pressure, and the reaction tank is connected with a second pipeline which is used for conveying organic matters;
and the mud discharging unit is connected with the bottom of the reaction tank through a pipeline.
According to one embodiment of the invention, the crude titanium tetrachloride heating unit comprises a steam heat exchanger connected to a third pipe for transporting the crude titanium tetrachloride liquid at the first predetermined pressure and a fourth pipe for transporting superheated steam, respectively.
According to one embodiment of the invention, a crude titanium flowmeter and a crude titanium regulating valve are arranged on the third pipeline to regulate the flow rate of crude titanium tetrachloride liquid entering the steam heat exchanger; and a steam flowmeter and a steam regulating valve are arranged on the fourth pipeline to regulate the flow of the superheated steam entering the steam heat exchanger.
According to one embodiment of the invention, the preset temperature is 150-160 ℃, the first preset pressure is 400-500 kPa, the second preset pressure is 200-300 kPa, an orifice plate is arranged on a pipeline which is close to a feed inlet of the reaction tank in the first pipeline, and a thermometer and a pressure gauge are arranged on the first pipeline.
According to one embodiment of the invention, a stirrer is arranged in the reaction tank, an insulation layer is arranged outside the reaction tank, and a liquid level meter is arranged in the reaction tank.
According to one embodiment of the invention, an organic flow meter and an organic matter regulating valve are arranged on the second pipeline to regulate the flow rate of organic matters entering the reaction tank, and the ratio of the total mass of the organic matters flowing into the reaction tank to the total mass of vanadium elements in the total refined crude titanium tetrachloride is 1:1.5-1:3.
According to one embodiment of the present invention, further comprising: the rectifying tower is connected with the reaction tank through a fifth pipeline, a sixth pipeline connected with the reaction tank is further arranged at the bottom of the rectifying tower, the rectifying tower is connected with the rectifying titanium tank through a seventh pipeline, a condenser is arranged on the seventh pipeline between the rectifying tower and the rectifying titanium tank, a pipeline-connected rectifying titanium pump and a reflux pipeline are further arranged between the upper portion of the rectifying tower and the rectifying titanium tank so as to feed part of titanium tetrachloride in the rectifying titanium tank into the rectifying tower to control the temperature of the upper portion of the rectifying tower to be 120-130 ℃, and a reflux flowmeter and a reflux regulating valve are arranged on the reflux pipeline, and one end of the reflux pipeline extends to the upper portion of the rectifying tower and is provided with a spray head.
According to one embodiment of the invention, the reflux ratio in the reflux line is 1:10 to 1:15, the reflux ratio being the mass ratio of the total of the refluxed titanium tetrachloride to the total of the refined crude titanium tetrachloride.
According to one embodiment of the invention, the mud discharging unit comprises a circulating pump, an eighth pipeline, a ninth pipeline and a tenth pipeline, wherein the circulating pump is connected with the bottom of the reaction tank through the eighth pipeline, the tenth pipeline is connected with the circulating pump, a first regulating valve is arranged on the tenth pipeline to discharge mud through opening the regulating valve, one end of the ninth pipeline is connected with the tenth pipeline, and the other end of the ninth pipeline is connected with the upper part of the reaction tank.
On the other hand, the embodiment of the invention also discloses a method for refining the crude titanium tetrachloride by using the crude titanium tetrachloride vanadium removal refining system according to any one of the embodiments, which comprises the following steps:
firstly adding unheated crude titanium tetrachloride liquid into a reaction tank, wherein the volume of the crude titanium tetrachloride liquid accounts for 30-50% of the volume of the reaction tank;
introducing the crude titanium tetrachloride liquid with the first preset pressure into a crude titanium tetrachloride heating unit, and introducing the heated crude titanium tetrachloride liquid with the second preset pressure at 150-160 ℃ into the reaction tank through the crude titanium tetrachloride heating unit;
the organic matters are led into the reaction tank in proportion;
when the temperature of the top of the rectifying tower reaches more than 130 ℃, opening reflux spraying of a reflux pipeline, and establishing heat balance of the system;
when the total volume of the mixed liquid in the reaction tank exceeds 80% of the volume of the reaction tank, discharging slurry through a slurry discharging unit;
detecting the impurity content in the titanium tetrachloride in the refined titanium tank, and outputting the refined titanium tetrachloride after the impurity content meets the requirement.
By adopting the technical scheme, the invention has at least the following beneficial effects:
according to the crude titanium tetrachloride vanadium removal refining system and method provided by the invention, the crude titanium tetrachloride heating section and the reaction section are separated through the independently arranged crude titanium tetrachloride heating unit and the reaction tank which are connected through the first pipeline, so that the problem of serious scaling of heating equipment caused by the increase of solid matters generated by the vanadium removal reaction is avoided, and the problems of reduced heat efficiency and time-consuming scaling cleaning of the heating section are solved. In addition, when the crude titanium tetrachloride is heated by the crude titanium tetrachloride heating unit, tiCl is contained in the crude titanium tetrachloride 4 、VOCl 3 The solid residues are remained in the heating equipment after other substances which are easy to evaporate into gas are evaporated, so that the heating equipment is also scaled, and the crude titanium tetrachloride is still in a liquid state after being heated by the crude titanium tetrachloride heating unit in the refining system, so that the scaling problem of the heating equipment when the crude titanium tetrachloride is heated by the crude titanium tetrachloride heating unit is avoided, and the heat exchange efficiency of the heating equipment is further avoidedReduced rate and time consuming cleaning. According to the crude titanium tetrachloride vanadium removal refining system and method provided by the invention, the heating section and the reaction section of the crude titanium tetrachloride are separated, so that the scaling rate of the heating section is reduced, and the system operation efficiency is greatly 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 is a schematic diagram of a crude titanium tetrachloride vanadium removal refining system according to one 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.
According to a first aspect of the present invention, as shown in FIG. 1, an embodiment of the present invention discloses a crude titanium tetrachloride vanadium removal refining system comprising:
a crude titanium tetrachloride heating unit 100, the crude titanium tetrachloride heating unit 100 being for heating a crude titanium tetrachloride liquid of a first predetermined pressure to a predetermined temperature;
a crude titanium tetrachloride reaction unit 200, the crude titanium tetrachloride reaction unit 200 comprising a reaction tank 210, the reaction tank 210 being connected to the crude titanium tetrachloride heating unit 100 by a first pipe 110, the first pipe 110 feeding a crude titanium tetrachloride liquid heated to a second predetermined pressure of a predetermined temperature, the second predetermined pressure being smaller than the first predetermined pressure, the reaction tank 210 being provided with a second pipe 220 connected thereto, the second pipe 220 being for conveying organic matter;
and a mud discharging unit 300, wherein the mud discharging unit 300 is connected with the bottom of the reaction tank 210 through a pipe.
According to the embodiment of the invention, the crude titanium tetrachloride heating unit 100 and the reaction tank 210 which are connected through the first pipeline 110 are independently arranged, so that the problem of serious scaling of heating equipment caused by the increase of solid matters generated by the vanadium removal reaction is avoided, the state of the crude titanium tetrachloride after the crude titanium tetrachloride is heated by the crude titanium tetrachloride heating unit 100 in the refining system provided by the invention is still in a liquid state, the scaling problem of the heating equipment when the crude titanium tetrachloride is heated by the crude titanium tetrachloride heating unit 100 is avoided, and the problems of reduced heat exchange efficiency of the heating equipment and time-consuming scaling cleaning are further avoided.
In some embodiments, the crude titanium tetrachloride heating unit 100 includes a steam heat exchanger 120, the steam heat exchanger 120 being connected to a third conduit 130 and a fourth conduit 140, respectively, the third conduit 130 being for delivering a crude titanium tetrachloride liquid at a first predetermined pressure and the fourth conduit 140 being for delivering superheated steam. The adoption of the steam heat exchanger 120 can lead the crude titanium tetrachloride liquid to be heated uniformly, and the temperature of the steam and the flow rate of the steam are strong in controllability. It will be appreciated that the heating of the crude titanium tetrachloride in the embodiments of the present invention is not limited to a steam heat exchanger, but may be other heating means for the crude titanium tetrachloride. For example, in other embodiments, the crude titanium tetrachloride may be heated, and a hot blast stove may be used.
In some embodiments, a crude titanium flow meter 131 and a crude titanium regulating valve 132 are provided on the third conduit 130 to regulate the flow of crude titanium tetrachloride liquid into the steam heat exchanger 120; a steam flow meter 141 and a steam adjusting valve 142 are provided on the fourth pipe 140 to adjust the flow rate of the superheated steam entering the steam heat exchanger 120. In this embodiment, the coarse titanium damper 132 is disposed on the third conduit 130 proximate the steam heat exchanger 120 and the steam damper 142 is disposed on the fourth conduit 140 proximate the steam heat exchanger 120. The flow rate of the crude titanium in the third pipe 130 and the flow rate of the steam in the fourth pipe 140 can be monitored in real time by providing the crude titanium flow meter 131 and the steam flow meter 141, respectively, and the flow rate of the crude titanium tetrachloride liquid entering the steam heat exchanger 120 and the flow rate of the superheated steam entering the steam heat exchanger 120 can be adjusted in real time by providing the crude titanium adjusting valve 132 and the steam adjusting valve 142, respectively.
In some embodiments, the predetermined temperature is 150-160 ℃, the first predetermined pressure is 400-500 kPa, the second predetermined pressure is 200-300 kPa, an orifice plate 111 is provided on a pipe in the first pipe 110 near the feed inlet of the reaction tank 210, and a thermometer 112 and a pressure gauge 113 are provided on the first pipe 110. In this embodiment, by increasing the pressure of the crude titanium tetrachloride liquid entering the crude titanium tetrachloride heating unit 100, vaporization of the crude titanium tetrachloride liquid during heating can be prevented, and TiCl in the crude titanium tetrachloride can be prevented 4 、VOCl 3 And other substances which are easy to evaporate into gas can be evaporated to leave solid residues in the heating equipment. Since there is a loss in the pressure of the crude titanium tetrachloride liquid during the piping and during the heating of the crude titanium tetrachloride heating unit, the first predetermined pressure of the crude titanium tetrachloride liquid fed to the crude titanium tetrachloride heating unit is greater than the second predetermined pressure of the heated crude titanium tetrachloride liquid.
In the above-described embodiment, in the actual operation of the refining system, before the heated crude titanium tetrachloride liquid is introduced into the reaction tank 210, a part of the unheated crude titanium tetrachloride liquid is introduced into the reaction tank 210, and then the crude titanium tetrachloride is introduced into the crude titanium tetrachloride heating unit 100 to heat it, and the high-pressure crude titanium tetrachloride liquid heated to a temperature of 150 to 160 ℃ is introduced into the reaction tank 210 to be mixed with the unheated crude titanium tetrachloride liquid previously introduced into the reaction tank 210, and the temperature of the mixed liquid of the reaction tank 210 is maintained in a temperature range for vaporizing titanium tetrachloride, for example, 136 to 140 ℃.
Further, in the above-described embodiment, in order to prevent the crude titanium tetrachloride from gasifying due to the pressure decrease before entering the reaction tank 210, the orifice plate 111 is provided in the first pipe 110 near the feed inlet of the reaction tank 210, and the orifice plate 111 can restrict the flow rate of the crude titanium tetrachloride liquid, thereby increasing the pressure of the crude titanium tetrachloride liquid before the orifice plate, preventing the pressure of the crude titanium tetrachloride liquid from decreasing before entering the reaction tank 210. By providing the thermometer 112 and the pressure gauge 113 on the first pipe 110, the temperature and pressure of the crude titanium tetrachloride liquid in the first pipe 110 can be monitored in real time, so that the system can be adjusted in real time according to the monitored data.
In some embodiments, a stirrer 211 is disposed in the reaction tank 210, an insulation layer 213 is disposed outside the reaction tank 210, and a liquid level gauge 212 is disposed in the reaction tank 210. By providing the stirrer 211, the crude titanium tetrachloride liquid and the organic matter can be sufficiently mixed, which is advantageous in promoting the progress of the vanadium removal reaction and in improving the rate of the vanadium removal reaction. By providing the heat insulating layer 213, the heat loss of the reaction tank 210 can be prevented, and the temperature of the reaction tank 210 can be always controlled within the temperature range for vaporizing titanium tetrachloride. By providing the level gauge 212, the volume of the mixed liquid in the reaction tank 210 can be monitored in real time, and then when the liquid level condition of the reaction tank exceeds the set range, the mud is discharged in time by controlling the mud discharging unit 300.
In some embodiments, an organic flow meter 221 and an organic flow regulating valve 222 are provided on the second conduit 220 to regulate the flow of organic material into the reaction tank 210, the ratio of the total mass of organic material flowing into the reaction tank 210 to the total mass of vanadium elements in the total refined crude titanium tetrachloride being 1:1.5 to 1:3. In this example, the ratio of the organic matter to the vanadium element in the crude titanium tetrachloride was set according to the actual reaction efficiency of the organic matter.
In some embodiments, the crude titanium tetrachloride vanadium removal refining system further comprises: the rectifying tower 400 is connected with the reaction tank 210 through a fifth pipeline 410, a sixth pipeline 420 connected with the reaction tank 210 is further arranged at the bottom of the rectifying tower 400, the rectifying tower 400 is connected with the rectifying titanium tank 500 through a seventh pipeline 430, a condenser 510 is arranged on the seventh pipeline 430 between the rectifying tower 400 and the rectifying titanium tank 500, a pipeline-connected rectifying titanium pump 530 and a reflux pipeline 520 are further arranged between the upper part of the rectifying tower 400 and the rectifying titanium tank 500 so as to send titanium tetrachloride in the rectifying titanium tank 500 into the rectifying tower 400 to control the temperature of the upper part of the rectifying tower 400 to be 120-130 ℃, a reflux flowmeter 521 and a reflux regulating valve 522 are arranged on the reflux pipeline 520, and one end of the reflux pipeline 520 extends to the upper part of the rectifying tower 400 and is provided with a spray head 523.
In the above embodiment, a circulation loop of crude titanium tetrachloride is formed between the reaction tank 210 and the rectifying tower 400 through the fifth pipeline 410 and the sixth pipeline 420, the gaseous crude titanium tetrachloride enters the rectifying tower 400 along the fifth pipeline 410 to become liquid, and part of the liquid crude titanium tetrachloride returns to the reaction tank 210 along the sixth pipeline 420, so that the vanadium removal reaction of the crude titanium tetrachloride is more thoroughly performed, and the vanadium removal effect of the crude titanium tetrachloride is improved.
In addition, in the above embodiment, by the refined titanium pump 530 and the return line 520 provided between the rectifying tower 400 and the refined titanium tank 500, part of the titanium tetrachloride in the refined titanium tank 500 is returned to the rectifying tower 400 and sprayed out through the spray head 523, so that the temperature at the top of the rectifying tower 400 is controlled. The spray head 523 can spray the titanium tetrachloride liquid in different directions, which is advantageous for the titanium tetrachloride liquid to be fully contacted with the gas-liquid mixture at the top of the rectifying tower 400, thereby promoting the cooling of the top of the rectifying tower.
In some embodiments, the reflux ratio in the reflux line is from 1:10 to 1:15, the reflux ratio being the mass of titanium tetrachloride total refluxed to the mass of crude titanium tetrachloride total refined.
In some embodiments, the mud discharging unit 300 includes a circulation pump 310, an eighth pipe 320, a ninth pipe 330, and a tenth pipe 340, the circulation pump 310 is connected to the bottom of the reaction tank 210 through the eighth pipe 320, the tenth pipe 340 is connected to the circulation pump 310, a regulating valve 341 is provided on the tenth pipe 340 to discharge mud by opening the regulating valve 341, one end of the ninth pipe 330 is connected to the tenth pipe 340, and the other end of the ninth pipe 330 is connected to the upper portion of the reaction tank 210. In this embodiment, when the refining system is operated, the circulation pump 310 is turned on, the mixed liquid in the reaction tank 210 circulates among the eighth pipeline 320, the circulation pump 310 and the ninth pipeline 330, which is advantageous for fully mixing and fully reacting the mixed liquid in the reaction tank 210, promoting the complete progress of the vanadium removal reaction, and when the volume of the mixed liquid in the reaction tank 210 exceeds the set range, the first adjusting valve 341 on the tenth pipeline 340 may be turned on to discharge the slurry, and the discharged slurry is directed to the slurry treatment system. In other embodiments, a second regulating valve 331 is provided on the ninth pipe 330 to control the circulation flow rate of the mixed liquid.
According to a second aspect of the present invention, an embodiment of the present invention discloses a method for refining crude titanium tetrachloride by using the crude titanium tetrachloride vanadium removal refining system according to any one of the embodiments above, comprising the steps of:
firstly adding unheated crude titanium tetrachloride liquid into a reaction tank 210, wherein the volume of the crude titanium tetrachloride liquid accounts for 30-50% of the volume of the reaction tank;
introducing the crude titanium tetrachloride liquid at a first predetermined pressure into the crude titanium tetrachloride heating unit 100, and introducing the heated crude titanium tetrachloride liquid at a second predetermined pressure of 150 to 160 ℃ into the reaction tank 210 through the crude titanium tetrachloride heating unit;
the organic matters are led into the reaction tank 210 in proportion;
when the temperature at the top of the rectifying tower 400 reaches more than 130 ℃, the reflux spraying of a reflux pipeline is started, and the heat balance of the system is established;
when the total volume of the mixed liquid in the reaction tank 210 exceeds 80% of the total volume of the reaction tank 210, mud is discharged through the mud discharging unit 300;
detecting the impurity content in the titanium tetrachloride in the refined titanium tank 500, and outputting the refined titanium tetrachloride when the impurity content meets the requirement.
In the above embodiment, a part of the titanium tetrachloride in the refined titanium tank 500 is used for reflux of the rectifying tower, and after the titanium tetrachloride in the refined titanium tank 500 is detected to be qualified, a valve arranged on a pipeline is opened to enable the titanium tetrachloride in the other part of the refined titanium tank 500 to be sent to a subsequent system.
In summary, the system and the method for refining the crude titanium tetrachloride for removing vanadium provided by the embodiment of the invention are independently arranged through the first pipeline connectionThe heating unit and the reaction tank are arranged to separate the heating section and the reaction section of the crude titanium tetrachloride, so that the problem of serious scaling of heating equipment caused by the increase of solid matters generated by the vanadium removal reaction is avoided, and the problems of reduced heat efficiency of the heating section and time-consuming scaling cleaning are solved. In addition, when the crude titanium tetrachloride is heated by the crude titanium tetrachloride heating unit, tiCl is contained in the crude titanium tetrachloride 4 、VOCl 3 And other substances which are easy to evaporate into gas are evaporated to leave solid residues in the heating equipment, so that the heating equipment is also scaled, and the crude titanium tetrachloride is still in a liquid state after being heated by the crude titanium tetrachloride heating unit in the refining system, so that the scaling problem of the heating equipment when the crude titanium tetrachloride is heated by the crude titanium tetrachloride heating unit is avoided, and further the problems of reduced heat exchange efficiency and time-consuming cleaning of the heating equipment are avoided. According to the crude titanium tetrachloride vanadium removal refining system and method provided by the invention, the heating section and the reaction section of the crude titanium tetrachloride are separated, so that the scaling rate of the heating section is reduced, and the system operation efficiency is greatly improved.
It should be noted that, each component or step in each embodiment may be intersected, replaced, added, and deleted, and therefore, the combination formed by these reasonable permutation and combination transformations shall also belong to the protection scope of the present invention, and shall not limit the protection scope of the present invention to the embodiments.
The foregoing is an exemplary embodiment of the present disclosure, and the order in which the embodiments of the present disclosure are disclosed is merely for the purpose of description and does not represent the advantages or disadvantages of the embodiments. It should be noted that the above discussion of any of the embodiments is merely exemplary and is not intended to suggest that the scope of the disclosure of embodiments of the invention (including the claims) is limited to these examples and that various changes and modifications may be made without departing from the scope of the invention as defined in the claims. The functions, steps and/or actions of the method claims in accordance with the disclosed embodiments described herein need not be performed in any particular order. Furthermore, although elements of the disclosed embodiments may be described or claimed in the singular, the plural is contemplated unless limitation to the singular is explicitly stated.
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 (10)
1. A crude titanium tetrachloride vanadium removal refining system comprising:
a crude titanium tetrachloride heating unit for heating a crude titanium tetrachloride liquid of a first predetermined pressure to a predetermined temperature;
the crude titanium tetrachloride reaction unit comprises a reaction tank, the reaction tank is connected with the crude titanium tetrachloride heating unit through a first pipeline, the first pipeline is used for conveying crude titanium tetrachloride liquid heated to a second preset pressure of the preset temperature into the reaction tank, the second preset pressure is smaller than the first preset pressure, and the reaction tank is connected with a second pipeline which is used for conveying organic matters;
and the mud discharging unit is connected with the bottom of the reaction tank through a pipeline.
2. The crude titanium tetrachloride vanadium removal refining system of claim 1, wherein the crude titanium tetrachloride heating unit comprises a steam heat exchanger connected to a third conduit for delivering the crude titanium tetrachloride liquid at the first predetermined pressure and a fourth conduit for delivering superheated steam, respectively.
3. The crude titanium tetrachloride vanadium removal refining system of claim 2, wherein a crude titanium flowmeter and a crude titanium regulating valve are provided on the third conduit to regulate the flow of crude titanium tetrachloride liquid into the steam heat exchanger; and a steam flowmeter and a steam regulating valve are arranged on the fourth pipeline to regulate the flow of the superheated steam entering the steam heat exchanger.
4. The crude titanium tetrachloride vanadium removal refining system of claim 1, wherein the predetermined temperature is 150-160 ℃, the first predetermined pressure is 400-500 kPa, the second predetermined pressure is 200-300 kPa, an orifice plate is disposed on a pipe in the first pipe near the feed inlet of the reaction tank, and a thermometer and a pressure gauge are disposed on the first pipe.
5. The crude titanium tetrachloride vanadium removal refining system of claim 1, wherein a stirrer is disposed in the reaction tank, an insulation layer is disposed outside the reaction tank, and a liquid level gauge is disposed in the reaction tank.
6. The crude titanium tetrachloride vanadium removal refining system as recited in claim 1, wherein an organic flow meter and an organic matter regulating valve are provided on the second conduit to regulate the flow of organic matter into the reaction tank, the ratio of the total mass of organic matter flowing into the reaction tank to the total mass of vanadium element in the total refined crude titanium tetrachloride being 1:1.5 to 1:3.
7. The crude titanium tetrachloride vanadium removal refining system of claim 1, further comprising: the rectifying tower is connected with the reaction tank through a fifth pipeline, a sixth pipeline connected with the reaction tank is further arranged at the bottom of the rectifying tower, the rectifying tower is connected with the rectifying titanium tank through a seventh pipeline, a condenser is arranged on the seventh pipeline between the rectifying tower and the rectifying titanium tank, a pipeline-connected rectifying titanium pump and a reflux pipeline are further arranged between the upper portion of the rectifying tower and the rectifying titanium tank so as to feed part of titanium tetrachloride in the rectifying titanium tank into the rectifying tower to control the temperature of the upper portion of the rectifying tower to be 120-130 ℃, and a reflux flowmeter and a reflux regulating valve are arranged on the reflux pipeline, and one end of the reflux pipeline extends to the upper portion of the rectifying tower and is provided with a spray head.
8. The crude titanium tetrachloride vanadium removal refining system of claim 7, wherein the reflux ratio in the reflux line is from 1:10 to 1:15, the reflux ratio being the mass of total refluxed titanium tetrachloride to the mass of total refined crude titanium tetrachloride.
9. The crude titanium tetrachloride vanadium removal refining system according to claim 1, wherein the slurry discharging unit comprises a circulation pump, an eighth pipe, a ninth pipe and a tenth pipe, the circulation pump is connected to the bottom of the reaction tank through the eighth pipe, the tenth pipe is connected to the circulation pump, a first regulating valve is provided on the tenth pipe to discharge slurry by opening the regulating valve, one end of the ninth pipe is connected to the tenth pipe, and the other end of the ninth pipe is connected to the upper portion of the reaction tank.
10. A method for refining crude titanium tetrachloride by using the crude titanium tetrachloride vanadium removal refining system as recited in any one of claims 1-9, comprising the steps of:
firstly adding unheated crude titanium tetrachloride liquid into a reaction tank, wherein the volume of the crude titanium tetrachloride liquid accounts for 30-50% of the volume of the reaction tank;
introducing the crude titanium tetrachloride liquid with the first preset pressure into a crude titanium tetrachloride heating unit, and introducing the heated crude titanium tetrachloride liquid with the second preset pressure at 150-160 ℃ into the reaction tank through the crude titanium tetrachloride heating unit;
the organic matters are led into the reaction tank in proportion;
when the temperature of the top of the rectifying tower reaches more than 130 ℃, opening reflux spraying of a reflux pipeline, and establishing heat balance of the system;
when the total volume of the mixed liquid in the reaction tank exceeds 80% of the volume of the reaction tank, discharging slurry through a slurry discharging unit;
detecting the impurity content in the titanium tetrachloride in the refined titanium tank, and outputting the refined titanium tetrachloride after the impurity content meets the requirement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310486111.7A CN116588970A (en) | 2023-04-28 | 2023-04-28 | System and method for refining crude titanium tetrachloride by removing vanadium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310486111.7A CN116588970A (en) | 2023-04-28 | 2023-04-28 | System and method for refining crude titanium tetrachloride by removing vanadium |
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| Publication Number | Publication Date |
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| CN116588970A true CN116588970A (en) | 2023-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310486111.7A Pending CN116588970A (en) | 2023-04-28 | 2023-04-28 | System and method for refining crude titanium tetrachloride by removing vanadium |
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| Country | Link |
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| CN (1) | CN116588970A (en) |
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2023
- 2023-04-28 CN CN202310486111.7A patent/CN116588970A/en active Pending
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