CN103896333A - Method for preparing titanium dioxide - Google Patents
Method for preparing titanium dioxide Download PDFInfo
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- CN103896333A CN103896333A CN201310664318.5A CN201310664318A CN103896333A CN 103896333 A CN103896333 A CN 103896333A CN 201310664318 A CN201310664318 A CN 201310664318A CN 103896333 A CN103896333 A CN 103896333A
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- titanium tetrachloride
- chlorination
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Abstract
The invention relates to a method for preparing titanium dioxide. The method comprises the following steps: (1) supplying titaniferous ores and a reducer into a chlorination reactor while supplying oxygen, air and chlorine into the chlorination reactor so as to carry out chlorination reaction in the chlorination reactor; (2) carrying out first gas-solid separation treatment on the chlorination reaction mixture obtained in the step (1); (3) carrying out condensation treatment on the gas mixture containing titanium tetrachloride; (4) storing the liquid crude titanium tetrachloride obtained in the step (3) in a titanium tetrachloride storage device; (5) carrying out vanadium removal treatment on the liquid crude titanium tetrachloride by using mineral oil; (6) supplying the fine titanium tetrachloride obtained in the step (5) and oxygen into an oxidation reactor; and (7) carrying out gas-solid separation on the oxidation reaction mixture obtained in the step (6) so as to respectively obtain solid titanium dioxide and chlorine. The method can be used for effectively preparing titanium dioxide.
Description
Technical field
The present invention relates to chemical field.More specifically, relate to a kind of method of preparing titanium dioxide.
Background technology
The method of producing at present titanium dioxide mainly contains sulfuric acid process and chlorination process.Due to the long flow path of sulfuric acid process, seriously polluted, poor product quality and be progressively chlorinated method replace.
CN1066043 discloses a kind of processing method of preparing Rutile type Titanium Dioxide, it comprises 1), after evenly being mixed with refinery coke, titanium slag puts into chlorination furnace, pass into chlorine and carry out fluidizing chlorination at 800～900 ℃ of temperature, 2), the rough titanium tetrachloride obtaining after chlorination is carried out to separating-purifying to be removed, magnesium, iron, the impurity such as silicon and vanadium, obtain refining titanic chloride, 3), the refining titanic chloride liquid making is in vaporizer, be converted into gas phase, and be preheated to 450～800 ℃, 4), gas phase titanium tetrachloride and a small amount of compound modifying agent gas phase aluminum chloride are mixed into oxidized still, oxygen enters oxidized still through plasma generator heating, at 1300～1500 ℃ of temperature, be less than and in 0.1 second, carry out oxidizing reaction and generate solid phase titanium dioxide, 5), rapidly titanium dioxide pressed powder is shifted out to reaction zone and reaction heat is being removed rapidly, collect titanium dioxide generation chlorine and return to chlorination furnace, 6), the titanium dioxide granule powder of collection is beaten into liquid, through two-stage sorting, the fine particle titanium dioxide that is less than 1 micron carries out aftertreatment again, coarse particles grinds and then classification, 7), make used additives carry out coating aftertreatment in pH=7～8 at 50～70 ℃ of temperature, 8), by titanium dioxide slurries after aftertreatment, through twice filtration, charging is moisture is less than 45%, discharging is moisture is less than 1%, 9) dry at 120～160 ℃ of temperature, micronizing, product mean particle size accounts for 70% below 0.3 μ m.
But the means of preparing at present titanium dioxide still have much room for improvement.
Summary of the invention
The present invention is intended at least solve one of technical problem existing in prior art.For this reason, one object of the present invention is to propose a kind of method and system that can effectively prepare titanium dioxide.
In a first aspect of the present invention, the present invention proposes a kind of method of preparing titanium dioxide.According to embodiments of the invention, the method comprises: (1) is supplied to titaniferous ore, reductive agent in chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore; (2) chlorination reaction mixture obtaining in step (1) is carried out to the first gas solid separation processing, to obtain the gaseous mixture that contains titanium tetrachloride; (3) the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride; (4) the described liquid crude titanium tetrachloride obtaining in step (3) is stored in titanium tetrachloride storing device; (5) adopt mineral oil remove vanadium processing to described liquid crude titanium tetrachloride, to described liquid crude titanium tetrachloride is refined, to obtain the smart titanium tetrachloride through refining, wherein, in the refining titanium tetrachloride of described process, the content of vanadium is below 3ppm; (6) the smart titanium tetrachloride and the oxygen that in step (5), obtain are supplied in oxidation reactor, to there is oxidizing reaction in described oxidation reactor, to obtain the oxidation mixtures that contains titanium dioxide and chlorine; And the described oxidation mixtures obtaining in step (6) carries out the second gas solid separation by (7), to obtain respectively solid titanium dioxide and chlorine.Wherein, described chlorination reactor comprises reaction chamber, described reaction chamber has boiling section, transition section and expanding reach from bottom to up successively, and described reaction chamber is provided with and the chlorine inlet being communicated with in described reaction chamber, solid materials import and deslagging air outlet, and described deslagging air outlet is located at the upper end of described reaction chamber.Contriver finds, utilize the method can effectively prepare titanium dioxide, and then by titanium dioxide is carried out to coating processing, can effectively obtain the titanium dioxide of size-grade distribution excellence, and, the method in process of production reaction efficiency is higher, and " three wastes " that reaction produces are few, is a kind of production technique of clean, efficient, environmental protection.
According to embodiments of the invention, the above-mentioned method of preparing titanium dioxide can also have following additional technical feature:
In one embodiment of the invention, described chlorination reaction is to carry out at the temperature of 700～900 degrees Celsius.Preferably, chlorination reaction is to carry out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, carries out chlorination reaction under 850 degrees Celsius, can generate titanium tetrachloride with the efficiency that is significantly better than other temperature.
In one embodiment of the invention, in step (3), further comprise: by a part for described liquid crude titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture contact, to carry out the first cooling process; And utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid crude titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver find, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, for the first cooling process, can effectively utilize and obtain cooling liquid crude titanium tetrachloride and carry out cooling, thereby reduce the production cost of producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role with the cooling medium that is significantly better than other temperature and type.
In one embodiment of the invention, in step (6), in the smart titanium tetrachloride obtaining in step (5) and oxygen are supplied to oxidation reactor before, in advance described smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.In one embodiment of the invention, described smart titanium tetrachloride and oxygen are preheated to are respectively not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, is not less than 350 degrees Celsius and be not less than 1500 degrees Celsius by described smart titanium tetrachloride and oxygen are preheated to respectively, can significantly effectively reduce the cost of preparing titanium dioxide.In the time of excess Temperature, the needed cost of preheating can significantly increase, and in the time that temperature is too low, in oxidation reactor, can consume too much energy.
In one embodiment of the invention, further comprise: the chlorine obtaining in step (7) is back in step (1) and carries out chlorination reaction.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
In one embodiment of the invention, the inwall of described boiling section is provided with three layers of high alumina brick, and the inwall of described transition section is provided with two-layer high alumina brick.
In one embodiment of the invention, between described high alumina brick and described outer steel shell, be provided with heat insulating and corrosion coating.
The outer wall of described boiling section is provided with the watercooling jacket for cooling described boiling section, and described watercooling jacket has water jacket entrance and water jacket outlet.
Described reaction chamber also comprises for form the water screen generator of water curtain with cooling described transition section and described expanding reach in the outside wall surface of described reaction chamber.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination is understood becoming the description of embodiment obviously and easily, wherein:
Fig. 1 is the schematic flow sheet of preparing according to an embodiment of the invention the method for titanium dioxide;
Fig. 2 is the structural representation of preparing according to an embodiment of the invention the system of titanium dioxide; And
Fig. 3 is the structural representation of the reaction chamber of chlorination reactor according to an embodiment of the invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Be exemplary below by the embodiment being described with reference to the drawings, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
The term using in the present invention " is connected " and should makes broad understanding, can be both direct connection, can be also indirect connection.
In a first aspect of the present invention, the present invention proposes a kind of method of preparing titanium dioxide.With reference to figure 1, according to embodiments of the invention, the method comprises:
S100: chlorination reaction
In this step, titaniferous ore, reductive agent are supplied in chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore.Particularly, the production of titanium tetrachloride gases is mainly in chlorination reactor, continuously to add titanium ore (titanium slag or rutile), reducing substances (refinery coke), and continuously in reactor, passes into oxygen, pressurized air, Cl
2; And temperature is in the time of 850 ℃, and titanium ore (titanium slag or rutile) and chlorine recur reaction and continues to generate TiCl
4gas, reaction equation is: 2TiO
2+ 3C+4Cl
2=2TiCl
4+ 2CO+CO
2.In one embodiment of the invention, described chlorination reaction is to carry out at the temperature of 700～900 degrees Celsius.Preferably, chlorination reaction is to carry out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, carries out chlorination reaction under 850 degrees Celsius, can generate titanium tetrachloride with the efficiency that is significantly better than other temperature.
S200: the first gas solid separation
In this step, the chlorination reaction mixture obtaining is carried out to gas solid separation processing, to obtain the gaseous mixture that contains titanium tetrachloride in preceding step.According to embodiments of the invention, the method and apparatus that carries out the first gas solid separation can be any known means in this area.
S300: condensation process
In this step, the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride.In one embodiment of the invention, in this step, further comprise: by a part for described liquid crude titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture contact, to carry out the first cooling process; And utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid crude titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver find, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, for the first cooling process, can effectively utilize and obtain cooling liquid crude titanium tetrachloride and carry out cooling, thereby reduce the production cost of producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role with the cooling medium that is significantly better than other temperature and type.
S400: storage
In this step, the described liquid crude titanium tetrachloride that preceding step is obtained is stored in titanium tetrachloride storing device.
S500: except vanadium processing
In this step, adopt mineral oil remove vanadium processing to described liquid crude titanium tetrachloride, to described liquid crude titanium tetrachloride is refined, to obtain the smart titanium tetrachloride through refining, wherein, by by lower boiling VOCl
2be converted into high boiling VOCl
3remove, in the refining titanium tetrachloride of described process, the content of vanadium is below 3ppm.Thus, can significantly improve the quality of the titanium dioxide preparing.
S600: oxidizing reaction
In this step, the smart titanium tetrachloride and the oxygen that obtain are supplied in oxidation reactor, to there is oxidizing reaction TiCl in described oxidation reactor in preceding step
4+ O
2=TiO
2+ 2Cl
2, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.In one embodiment of the invention, in obtained smart titanium tetrachloride and oxygen are supplied to oxidation reactor before, in advance described smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.In one embodiment of the invention, described smart titanium tetrachloride and oxygen are preheated to are respectively not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, is not less than 350 degrees Celsius and be not less than 1500 degrees Celsius by described smart titanium tetrachloride and oxygen are preheated to respectively, can significantly effectively reduce the cost of preparing titanium dioxide.In the time of excess Temperature, the needed cost of preheating can significantly increase, and in the time that temperature is too low, in oxidation reactor, can consume too much energy.
S700: the second gas solid separation
The described oxidation mixtures obtaining in preceding step is carried out to gas solid separation, to obtain respectively solid titanium dioxide and chlorine.Contriver finds, utilizes the method can effectively prepare titanium dioxide, and then by titanium dioxide is carried out to coating processing, can effectively obtain the titanium dioxide of size-grade distribution excellence.In one embodiment of the invention, further comprise: the chlorine obtaining in preceding step is back to and in chlorination reaction step, carries out chlorination reaction.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
, describe with reference to the accompanying drawings the chlorination reactor for the production of titanium tetrachloride (being TiCl4) of the embodiment of the present invention in detail below, this chlorination reactor comprises reaction chamber 1.
As shown in Figure 3, according to the reaction chamber 1 for the production of titanium tetrachloride of the embodiment of the present invention, reaction chamber 1 has boiling section 11, transition section 12 and expanding reach 13 from bottom to up successively, and reaction chamber 1 is provided with and the interior chlorine inlet being communicated with 101 of reaction chamber 1, solid materials import 102 and deslagging air outlet 103, and deslagging air outlet 103 is located at the upper end of reaction chamber 1.Chlorine passes in reaction chamber 1 from chlorine inlet 101, solid materials passes into reaction chamber 1 from solid materials import 102 imports, solid materials and chlorine react and generate titanium tetrachloride at the boiling section 11 of reaction chamber 1, the titanium tetrachloride generating is discharged from the deslagging air outlet 103 that is positioned at reaction chamber 1 upper end, and the solid slag that reaction generates is discharged from deslagging air outlet 103 under the effect of the raising force of gas.
According to the reaction chamber 1 for the production of titanium tetrachloride of the embodiment of the present invention, the upper end of reaction chamber 1 is provided with deslagging air outlet 103, in the uphill process of gas, reaction chamber 1 solid slag is blowed to deslagging air outlet 103, and solid slag is discharged from deslagging air outlet 103.Thus, be convenient to discharge the solid slag in reaction chamber 1, a good reaction environment is provided to chlorine and solid materials, improve the production efficiency of titanium tetrachloride, and solid slag is discharged from the upper end of reaction chamber 1, avoid solid slag to discharge and cause the situation that needs stopped reaction the process of discharging solid slag from the lower end of reaction chamber 1, the reaction in reaction chamber 1 can be carried out continuously.
As shown in Figure 1, in some embodiments of the invention, chlorine inlet 101 is spaced apart multiple on the sidewall of boiling section 11, chlorine can enter reaction chamber 1 from these multiple chlorine inlets 101, thus, has increased the contact area of chlorine and solid materials, and avoid using gas distribution grid, thereby avoid the susceptible to plugging phenomenon of gas distribution grid, improved further the production efficiency of titanium tetrachloride, and be convenient to safeguard.
Particularly, multiple chlorine inlets 101 on the sidewall of boiling section 11 along the vertical direction and circumferentially interval arrange.Or multiple chlorine inlets 101 are arranged to row along the above-below direction of boiling section 11, and along the circumferential interval equipment multiple row chlorine inlet 101 of boiling section 11.
One of ordinary skill in the art will appreciate that multiple chlorine inlets 101 can distribute according to practical condition, the present invention does not limit the distribution form of multiple chlorine inlets 101.
Further, chlorine inlet 101 is for being horizontally disposed with.
As shown in Figure 3, in some embodiments of the invention, reaction chamber 1 has outer steel shell 14.Thus, improve structural strength and the temperature capacity of reaction chamber 1, increased the work-ing life of reaction chamber 1, thereby reduced costs, improved production efficiency.
Described outer steel shell 14 is shaped steel.
Further, as shown in Figure 3, on the inwall of boiling section 11 and transition section 12, all there is high alumina brick 15.Thus, improve further the heat-resistant anticorrosive ability of reaction chamber 1, increased further the work-ing life of reaction chamber 1.
Advantageously, the inwall of boiling section 11 is provided with three layers of high alumina brick 15, and the inwall of transition section 12 is provided with two-layer high alumina brick 15.Thus, improve the reaction environment of reaction chamber 1, thereby improved the production efficiency of titanium tetrachloride.
Further, between high alumina brick 15 and outer steel shell, be provided with heat insulating and corrosion coating.Thus, improve further the temperature capacity of reaction chamber 1, increased the work-ing life of reaction chamber 1.
Advantageously, as shown in Figure 3, the outer wall of boiling section 11 is provided with the watercooling jacket 16 for cooling boiling section 11, and watercooling jacket 16 has water jacket entrance 161 and water jacket outlet 162, can, to the water coolant that passes into circulation in watercooling jacket 16, be convenient to boiling section 11 to carry out cooling.Thus, improve the cooling efficiency to boiling section 11, and made chlorine and solid materials there is good reaction environment, improved the production efficiency of titanium tetrachloride.
One of ordinary skill in the art will appreciate that and can make water jacket entrance 161 and water jacket outlet 162 in same level; Or make water jacket outlet 162 higher than water jacket entrance 161; Or make water jacket entrance 161 higher than water jacket outlet 162.
Further, reaction chamber 1 also comprises for forming the water screen generator of water curtain with cooled transition section 12 and expanding reach 13 in the outside wall surface at reaction chamber 1.In other words, water screen generator for forming mobile water in the outside wall surface of transition section 12 and expanding reach 13.Thus, be convenient to transition section 12 and expanding reach 13 to carry out temperature control, improved the reaction efficiency in reaction chamber 1.
As shown in Figure 3, in some embodiments of the invention, the bottom of reaction chamber 1 is provided with access hole 104, and reacts in the process of producing titanium tetrachloride at reaction chamber 1, and access hole 104 is closed.Thus, the processing of easy access and Special Circumstances.
Reaction chamber 1 strong adaptability for the production of titanium tetrachloride of the embodiment of the present invention, can react with chlorine with the solid materials such as natural rutile, titanium slag and generate titanium tetrachloride.
Reaction chamber of the present invention is roughly cylindrical shape.
According to the production unit of the titanium tetrachloride of the embodiment of the present invention, comprise the reaction chamber 1 for the production of titanium tetrachloride of the previous embodiment according to the present invention.
According to the production unit of the titanium tetrachloride of the embodiment of the present invention, there is the reaction chamber 1 for the production of titanium tetrachloride of the previous embodiment according to the present invention.Thus, be convenient to the solid slag in device for transferring, a good reaction environment is provided to chlorine and solid materials, improve the production efficiency of titanium tetrachloride, and solid slag is discharged from the upper end of reaction chamber 1, avoid solid slag to discharge and cause the situation that needs stopped reaction the process of discharging solid slag from the lower end of reaction chamber 1, the reaction in equipment can be carried out continuously.
In a second aspect of the present invention, the present invention proposes a kind of system of preparing titanium dioxide.With reference to figure 2, according to embodiments of the invention, this system comprises: chlorination reactor 100, the first gas-solid separating device 200, condensing works 300, titanium tetrachloride storing device 400, refining plant 500, oxidation reactor 600 and the second gas-solid separating device 700.According to embodiments of the invention, chlorination reactor 100 is provided with titanium ore entrance, reductive agent entrance, oxygen intake, gas inlet and chlorine entrance, to titaniferous ore, reductive agent are supplied in described chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore.The first gas-solid separating device 200 is connected with chlorination reactor 100, for described chlorination reaction mixture is carried out to gas solid separation processing, to obtain the gaseous mixture that contains titanium tetrachloride.Condensing works 300 is connected with the first gas solid separation 200 devices, for the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride.Titanium tetrachloride storing device 400 is connected with condensing works 300, for storing described liquid crude titanium tetrachloride.Refining plant 500 is connected with titanium tetrachloride storing device 400, and be suitable for adopting mineral oil to remove vanadium processing to described liquid crude titanium tetrachloride, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the refining titanium tetrachloride of described process, the content of vanadium is below 3ppm.Oxidation reactor 600 is connected with refining plant 500, and be provided with oxygen intake, for described smart titanium tetrachloride and oxygen are supplied to oxidation reactor 600, to there is oxidizing reaction in oxidation reactor 600, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.The second gas-solid separating device 700 is connected with oxidation reactor 600, for oxidation mixtures is carried out to gas solid separation, to obtain respectively solid titanium dioxide and chlorine.Utilize this system, can effectively implement the aforementioned method of preparing titanium dioxide, and reaction efficiency is high in process of production, device capbility is large, produces " three wastes " few.
In one embodiment of the invention, described condensing works further comprises: adverse current cooling unit, described adverse current cooling unit is provided with chlorination reaction mixture entrance and liquid titanium tetrachloride entrance, so that in described adverse current cooling unit by a part for described liquid crude titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture counter current contact, to carry out the first cooling process; And tubular heat exchanger, described tubular heat exchanger is connected with described adverse current cooling unit, and utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid crude titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver find, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, for the first cooling process, can effectively utilize and obtain cooling liquid crude titanium tetrachloride and carry out cooling, thereby reduce the production cost of producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role with the cooling medium that is significantly better than other temperature and type.
In one embodiment of the invention, further comprise: smart titanium tetrachloride primary heater unit, described smart titanium tetrachloride primary heater unit is connected with described oxidation unit with described refining plant, in advance described smart titanium tetrachloride is carried out to thermal pretreatment; Oxygen preheat device, described oxygen preheat device is connected with described oxidation unit, in advance described oxygen is carried out to thermal pretreatment.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, is not less than 350 degrees Celsius and be not less than 1500 degrees Celsius by described smart titanium tetrachloride and oxygen are preheated to respectively, can significantly effectively reduce the cost of preparing titanium dioxide.In the time of excess Temperature, the needed cost of preheating can significantly increase, and in the time that temperature is too low, in oxidation reactor, can consume too much energy.
In one embodiment of the invention, described the second gas-solid separating device is connected with described chlorination reactor, carries out chlorination reaction for obtained chlorine is back to described chlorination reactor.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And specific features, structure, material or the feature of description can be with suitable mode combination in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. a method of preparing titanium dioxide, is characterized in that, comprising:
(1) titaniferous ore, reductive agent are supplied in chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore;
(2) chlorination reaction mixture obtaining in step (1) is carried out to the first gas solid separation processing, to obtain the gaseous mixture that contains titanium tetrachloride;
(3) the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride;
(4) the described liquid crude titanium tetrachloride obtaining in step (3) is stored in titanium tetrachloride storing device;
(5) adopt mineral oil remove vanadium processing to described liquid crude titanium tetrachloride, to described liquid crude titanium tetrachloride is refined, to obtain the smart titanium tetrachloride through refining, wherein, in the refining titanium tetrachloride of described process, the content of vanadium is below 3ppm;
(6) the smart titanium tetrachloride and the oxygen that in step (5), obtain are supplied in oxidation reactor, to there is oxidizing reaction in described oxidation reactor, to obtain the oxidation mixtures that contains titanium dioxide and chlorine; And
(7) the described oxidation mixtures obtaining in step (6) is carried out to the second gas solid separation, to obtain respectively solid titanium dioxide and chlorine,
Wherein, described chlorination reactor comprises reaction chamber, described reaction chamber has boiling section, transition section and expanding reach from bottom to up successively, and described reaction chamber is provided with and the chlorine inlet being communicated with in described reaction chamber, solid materials import and deslagging air outlet, and described deslagging air outlet is located at the upper end of described reaction chamber.
2. method according to claim 1, is characterized in that, described chlorination reaction is to carry out at the temperature of 700～900 degrees Celsius.
3. method according to claim 1, is characterized in that, in step (3), further comprises:
By a part for described liquid crude titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture contact, to carry out the first cooling process; And
Utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid crude titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.
4. method according to claim 1, is characterized in that, in step (6), in the smart titanium tetrachloride obtaining in step (5) and oxygen are supplied to oxidation reactor before, in advance described smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.
5. method according to claim 4, is characterized in that, described smart titanium tetrachloride and oxygen is preheated to is respectively not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance.
6. method according to claim 1, is characterized in that, further comprises: the chlorine obtaining in step (7) is back in step (1) and carries out chlorination reaction.
7. method according to claim 1, is characterized in that, the inwall of described boiling section is provided with three layers of high alumina brick, and the inwall of described transition section is provided with two-layer high alumina brick.
8. method according to claim 7, is characterized in that, between described high alumina brick and described outer steel shell, is provided with heat insulating and corrosion coating.
9. method according to claim 1, is characterized in that, the outer wall of described boiling section is provided with the watercooling jacket for cooling described boiling section, and described watercooling jacket has water jacket entrance and water jacket outlet.
10. method according to claim 1, is characterized in that, described reaction chamber also comprises for form the water screen generator of water curtain with cooling described transition section and described expanding reach in the outside wall surface of described reaction chamber.
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| CN105984894A (en) * | 2015-02-02 | 2016-10-05 | 云南新立有色金属有限公司 | Method and system for preparing refined titanium tetrachloride |
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