CN103896333B - Prepare the method for titanium dioxide - Google Patents
Prepare the method for titanium dioxide Download PDFInfo
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- CN103896333B CN103896333B CN201310664318.5A CN201310664318A CN103896333B CN 103896333 B CN103896333 B CN 103896333B CN 201310664318 A CN201310664318 A CN 201310664318A CN 103896333 B CN103896333 B CN 103896333B
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Abstract
The present invention relates to the method preparing titanium dioxide.The method comprises: titaniferous ore, reductive agent are supplied in chlorination reactor by (1), and to oxygen gas-supplying, air and chlorine in described chlorination reactor, there is chlorination reaction in described chlorination reactor; (2) chlorination reaction mixture obtained in step (1) is carried out gas solid separation process; (3) condensation process is carried out to the gaseous mixture containing titanium tetrachloride; (4) the described liquid crude titanium tetrachloride obtained in step (3) is stored in titanium tetrachloride storing device; (5) mineral oil is adopted to carry out except vanadium process to described liquid crude titanium tetrachloride; (6) refined titanic chloride obtained in step (5) and oxygen are supplied in oxidation reactor; And the oxidation mixtures obtained in step (6) is carried out gas solid separation by (7), to obtain solid titanium dioxide and chlorine respectively.Utilize the method effectively can prepare titanium dioxide.
Description
Technical field
The present invention relates to chemical field.More specifically, a kind of method preparing titanium dioxide is related to.
Background technology
The method of current production 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 preparing Rutile type Titanium Dioxide, it comprises 1), chlorination furnace is put into by after titanium slag and refinery coke Homogeneous phase mixing, pass into chlorine and carry out fluidizing chlorination at 800 ~ 900 DEG C of temperature, 2), separating-purifying removing is carried out to the rough titanium tetrachloride obtained after chlorination, magnesium, iron, the impurity such as silicon and vanadium, obtain refining titanic chloride, 3), obtained refining titanic chloride liquid is in vaporizer, be converted into gas phase, and be preheated to 450 ~ 800 DEG C, 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 DEG C of temperature, be less than in 0.1 second and carry out oxidizing reaction generation solid phase titanium dioxide, 5), rapidly titanium dioxide solids powder is shifted out reaction zone and reaction heat is being removed rapidly, collect titanium dioxide generation chlorine and return chlorination furnace, 6), the titanium dioxide granule powder of collection is beaten into liquid, through two-stage sorting, the fine particle titanium dioxide being less than 1 micron carries out aftertreatment again, coarse particles grinding and then classification, 7), used additives pH=7 ~ 8 at 50 ~ 70 DEG C of temperature are made to carry out coating aftertreatment, 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 DEG C of temperature, micronizing, product mean particle size accounts for 70% below 0.3 μm.
But the means preparing titanium dioxide at present still have much room for improvement.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.For this reason, one object of the present invention is to propose a kind of method and system effectively can preparing titanium dioxide.
In a first aspect of the present invention, the present invention proposes a kind of method preparing titanium dioxide.According to embodiments of the invention, the method comprises: titaniferous ore, reductive agent are supplied in chlorination reactor by (1), and to oxygen gas-supplying, air and chlorine in described chlorination reactor, there is chlorination reaction in described chlorination reactor, and the chlorination reaction mixture obtained containing 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 obtained in step (1) is carried out the first gas solid separation process, to obtain the gaseous mixture containing titanium tetrachloride; (3) condensation process is carried out, to obtain liquid crude titanium tetrachloride to the described gaseous mixture containing titanium tetrachloride; (4) the described liquid crude titanium tetrachloride obtained in step (3) is stored in titanium tetrachloride storing device; (5) adopt mineral oil to carry out except vanadium process to described liquid crude titanium tetrachloride, to refine described liquid crude titanium tetrachloride, to obtain through refining refined titanic chloride, wherein, in the titanium tetrachloride that described process is refined, the content of vanadium is below 3ppm; (6) refined titanic chloride obtained in step (5) and oxygen are supplied in oxidation reactor, there is oxidizing reaction in described oxidation reactor, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And the described oxidation mixtures obtained in step (6) is carried out the second gas solid separation by (7), to obtain solid titanium dioxide and chlorine respectively.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 be communicated with in described reaction chamber, solid materials import and deslagging air outlet, described deslagging air outlet is located at the upper end of described reaction chamber.Contriver finds, utilize the method effectively can prepare titanium dioxide, and then by carrying out coating process to titanium dioxide, effectively can 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 preparing titanium dioxide can also have following additional technical feature:
In one embodiment of the invention, described chlorination reaction is carried out at the temperature of 700 ~ 900 degrees Celsius.Preferably, chlorination reaction is carried out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, under 850 degrees Celsius, carry out chlorination reaction, can generate titanium tetrachloride with the efficiency being significantly better than other temperature.
In one embodiment of the invention, in step (3), comprise further: by a part for described liquid crude titanium tetrachloride and the described gas mixture contacts containing titanium tetrachloride, 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 degrees Celsius.Contriver finds, by this method of cooling, can effectively be cooled by the gaseous mixture containing titanium tetrachloride, thus realizes being further purified titanium tetrachloride.Wherein, for the first cooling process, the liquid crude titanium tetrachloride having obtained cooling can be effectively utilized cool, thus reduce the production cost producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degrees Celsius as refrigerant, is that contriver passes through a large amount of screening operation and surprisingly obtains, and find, it can play a role with the cooling medium being significantly better than other temperature and type.
In one embodiment of the invention, in step (6), before being supplied in oxidation reactor by the refined titanic chloride obtained in step (5) and oxygen, in advance described refined titanic chloride and oxygen are carried out thermal pretreatment respectively.In one embodiment of the invention, described refined titanic chloride and oxygen are preheated to respectively are not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance.Thus, the efficiency preparing titanium dioxide can be improved further, reduce the cost preparing titanium dioxide.Contriver finds, being not less than 350 degrees Celsius and be not less than 1500 degrees Celsius, can significantly effectively reducing the cost preparing titanium dioxide by described refined titanic chloride and oxygen being preheated to respectively.When temperature is too high, the cost required for preheating can significantly increase, and when the temperature is too low, then can consume too much energy in oxidation reactor.
In one embodiment of the invention, comprise further: the chlorine obtained in step (7) is back in step (1) and carries out chlorination reaction.Contriver finds, by the chlorine obtained after the second gas solid separation, can be directly used in chlorination reaction, thus reduces the cost producing titanium dioxide, decreases 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, heat insulating and corrosion coating is provided with between described high alumina brick and described outer steel shell.
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 form water curtain to cool the water screen generator of described transition section and described expanding reach in the outside wall surface at described reaction chamber.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 is the schematic flow sheet of the method preparing titanium dioxide according to an embodiment of the invention;
Fig. 2 is the structural representation of the system preparing titanium dioxide according to an embodiment of the invention; And
Fig. 3 is the structural representation of the reaction chamber of chlorination reactor according to an embodiment of the invention.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Being exemplary below by the embodiment be described with reference to the drawings, only for explaining the present invention, and can not limitation of the present invention being interpreted as.
The term used in the present invention " is connected " and should makes broad understanding, both can be direct connection, also can be indirect connection.
In a first aspect of the present invention, the present invention proposes a kind of method 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, there is chlorination reaction in described chlorination reactor, and the chlorination reaction mixture obtained containing titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore.Particularly, titanium ore (titanium slag or rutile), reducing substances (refinery coke) are mainly continuously added in the production of titanium tetrachloride gases in chlorination reactor, and continuously in reactor, pass into oxygen, pressurized air, Cl
2; And temperature is 850 DEG C time, titanium ore (titanium slag or rutile) and chlorine recur reaction to be continued 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 carried out at the temperature of 700 ~ 900 degrees Celsius.Preferably, chlorination reaction is carried out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, under 850 degrees Celsius, carry out chlorination reaction, can generate titanium tetrachloride with the efficiency being significantly better than other temperature.
S200: the first gas solid separation
In this step, the chlorination reaction mixture obtained in preceding step is carried out gas solid separation process, to obtain the gaseous mixture containing titanium tetrachloride.According to embodiments of the invention, the method and apparatus carrying out the first gas solid separation can be any known means in this area.
S300: condensation process
In this step, condensation process is carried out, to obtain liquid crude titanium tetrachloride to the described gaseous mixture containing titanium tetrachloride.In one embodiment of the invention, in this step, comprise further: by a part for described liquid crude titanium tetrachloride and the described gas mixture contacts containing titanium tetrachloride, 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 degrees Celsius.Contriver finds, by this method of cooling, can effectively be cooled by the gaseous mixture containing titanium tetrachloride, thus realizes being further purified titanium tetrachloride.Wherein, for the first cooling process, the liquid crude titanium tetrachloride having obtained cooling can be effectively utilized cool, thus reduce the production cost producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degrees Celsius as refrigerant, is that contriver passes through a large amount of screening operation and surprisingly obtains, and find, it can play a role with the cooling medium being significantly better than other temperature and type.
S400: store
In this step, described liquid crude titanium tetrachloride preceding step obtained is stored in titanium tetrachloride storing device.
S500: except vanadium process
In this step, mineral oil is adopted to carry out except vanadium process to described liquid crude titanium tetrachloride, to refine described liquid crude titanium tetrachloride, to obtain through refining refined titanic chloride, wherein, by by lower boiling VOCl
2be converted into high boiling VOCl
3removing, in the titanium tetrachloride that described process is refined, the content of vanadium is below 3ppm.Thereby, it is possible to significantly improve the quality of the titanium dioxide prepared.
S600: oxidizing reaction
In this step, the refined titanic chloride obtained in preceding step and oxygen are supplied in oxidation reactor, there is oxidizing reaction TiCl in described oxidation reactor
4+ O
2=TiO
2+ 2Cl
2, to obtain the oxidation mixtures containing titanium dioxide and chlorine.In one embodiment of the invention, before being supplied in oxidation reactor by obtained refined titanic chloride and oxygen, in advance described refined titanic chloride and oxygen are carried out thermal pretreatment respectively.In one embodiment of the invention, described refined titanic chloride and oxygen are preheated to respectively are not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance.Thus, the efficiency preparing titanium dioxide can be improved further, reduce the cost preparing titanium dioxide.Contriver finds, being not less than 350 degrees Celsius and be not less than 1500 degrees Celsius, can significantly effectively reducing the cost preparing titanium dioxide by described refined titanic chloride and oxygen being preheated to respectively.When temperature is too high, the cost required for preheating can significantly increase, and when the temperature is too low, then can consume too much energy in oxidation reactor.
S700: the second gas solid separation
The described oxidation mixtures obtained in preceding step is carried out gas solid separation, to obtain solid titanium dioxide and chlorine respectively.Contriver finds, utilizes the method effectively can prepare titanium dioxide, and then by carrying out coating process to titanium dioxide, effectively can obtain the titanium dioxide of size-grade distribution excellence.In one embodiment of the invention, comprise further: the chlorine obtained in preceding step is back in chlorination reaction step and carries out chlorination reaction.Contriver finds, by the chlorine obtained after the second gas solid separation, can be directly used in chlorination reaction, thus reduces the cost producing titanium dioxide, decreases pollution.
Below, describe the chlorination reactor for the production of titanium tetrachloride (i.e. TiCl4) of the embodiment of the present invention with reference to the accompanying drawings in detail, 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 chlorine inlet 101 be communicated with in reaction chamber 1, solid materials import 102 and deslagging air outlet 103, 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 import, solid materials and chlorine carry out reaction at the boiling section 11 of reaction chamber 1 and generate titanium tetrachloride, the titanium tetrachloride generated is discharged from the deslagging air outlet 103 being 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 and discharge from the lower end of reaction chamber 1 situation needing stopped reaction the process causing and discharge solid slag, 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 this multiple chlorine inlet 101, thus, adds the contact area of chlorine and solid materials, and avoid using gas distribution grid, thus avoid the susceptible to plugging phenomenon of gas distribution grid, further increasing the production efficiency of titanium tetrachloride, and be convenient to safeguard.
Specifically, multiple chlorine inlet 101 on the sidewall of boiling section 11 along the vertical direction and circumferential interval arrange.Or multiple chlorine inlet 101 is arranged to row along the above-below direction of boiling section 11, and along the circumferential spacing devices multiple row chlorine inlet 101 of boiling section 11.
One of ordinary skill in the art will appreciate that multiple chlorine inlet 101 can distribute according to practical condition, the present invention does not limit the distribution form of multiple chlorine inlet 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, add the work-ing life of reaction chamber 1, thus reduce costs, improve production efficiency.
Described outer steel shell 14 is shaped steel.
Further, as shown in Figure 3, the inwall of boiling section 11 and transition section 12 all has high alumina brick 15.Thus, further increasing the heat-resistant anticorrosive ability of reaction chamber 1, further increase 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, thus improve the production efficiency of titanium tetrachloride.
Further, heat insulating and corrosion coating is provided with between high alumina brick 15 and outer steel shell.Thus, further increasing the temperature capacity of reaction chamber 1, increase 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, the water coolant of circulation can be passed in watercooling jacket 16, be convenient to cool boiling section 11.Thus, improve the cooling efficiency to boiling section 11, and make chlorine and solid materials have good reaction environment, improve 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 export 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 and in the outside wall surface at reaction chamber 1, to form water curtain with the water screen generator of cooled transition section 12 and expanding reach 13.In other words, water screen generator forms the water of flowing in the outside wall surface at transition section 12 and expanding reach 13.Thus, be convenient to carry out temperature control to transition section 12 and expanding reach 13, improve 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 carries out at reaction chamber 1 reacting in the process of production titanium tetrachloride, and access hole 104 is closed.Thus, the process 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 carry out reaction with the solid materials such as natural rutile, titanium slag and chlorine 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 according to previous embodiment of 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 according to previous embodiment of 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 and discharge from the lower end of reaction chamber 1 situation needing stopped reaction the process causing and discharge solid slag, 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 preparing titanium dioxide.With reference to figure 2, according to embodiments of the invention, this system comprises: chlorination reactor 100, 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 inlet, titaniferous ore, reductive agent are supplied in described chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, there is chlorination reaction in described chlorination reactor, and the chlorination reaction mixture obtained containing titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore.First gas-solid separating device 200 is connected with chlorination reactor 100, for carrying out gas solid separation process to described chlorination reaction mixture, to obtain the gaseous mixture containing titanium tetrachloride.Condensing works 300 is connected with the first gas solid separation 200 device, for carrying out condensation process, to obtain liquid crude titanium tetrachloride to the described gaseous mixture containing 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 carry out except vanadium process to described liquid crude titanium tetrachloride, to refine described liquid crude titanium tetrachloride, to obtain through refining refined titanic chloride, wherein, in the titanium tetrachloride refined 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 refined titanic chloride and oxygen are supplied in oxidation reactor 600, there is oxidizing reaction in oxidation reactor 600, to obtain the oxidation mixtures containing titanium dioxide and chlorine.Second gas-solid separating device 700 is connected with oxidation reactor 600, for carrying out gas solid separation to oxidation mixtures, to obtain solid titanium dioxide and chlorine respectively.Utilize this system, effectively can implement the aforementioned method 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 comprises further: adverse current cooling unit, described adverse current cooling unit is provided with chlorination reaction mixture entrance and liquid titanium tetrachloride entrance, so that by a part for described liquid crude titanium tetrachloride and the described gaseous mixture counter current contact containing titanium tetrachloride in described adverse current cooling unit, 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 degrees Celsius.Contriver finds, by this method of cooling, can effectively be cooled by the gaseous mixture containing titanium tetrachloride, thus realizes being further purified titanium tetrachloride.Wherein, for the first cooling process, the liquid crude titanium tetrachloride having obtained cooling can be effectively utilized cool, thus reduce the production cost producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degrees Celsius as refrigerant, is that contriver passes through a large amount of screening operation and surprisingly obtains, and find, it can play a role with the cooling medium being significantly better than other temperature and type.
In one embodiment of the invention, comprise further: refined titanic chloride primary heater unit, described refined titanic chloride primary heater unit is connected with described oxidation unit with described refining plant, in advance described refined titanic chloride is carried out thermal pretreatment; Oxygen preheat equipment, described oxygen preheat equipment is connected with described oxidation unit, to carry out thermal pretreatment to described oxygen in advance.Thus, the efficiency preparing titanium dioxide can be improved further, reduce the cost preparing titanium dioxide.Contriver finds, being not less than 350 degrees Celsius and be not less than 1500 degrees Celsius, can significantly effectively reducing the cost preparing titanium dioxide by described refined titanic chloride and oxygen being preheated to respectively.When temperature is too high, the cost required for preheating can significantly increase, and when the temperature is too low, then can consume too much energy in oxidation reactor.
In one embodiment of the invention, described second gas-solid separating device is connected with described chlorination reactor, carries out chlorination reaction for being back in described chlorination reactor by obtained chlorine.Contriver finds, by the chlorine obtained after the second gas solid separation, can be directly used in chlorination reaction, thus reduces the cost producing titanium dioxide, decreases pollution.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (9)
1. prepare a method for titanium dioxide, it 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, there is chlorination reaction in described chlorination reactor, and the chlorination reaction mixture obtained containing 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 obtained in step (1) is carried out the first gas solid separation process, to obtain the gaseous mixture containing titanium tetrachloride;
(3) condensation process is carried out, to obtain liquid crude titanium tetrachloride to the described gaseous mixture containing titanium tetrachloride;
(4) the described liquid crude titanium tetrachloride obtained in step (3) is stored in titanium tetrachloride storing device;
(5) mineral oil is adopted to carry out except vanadium process to described liquid crude titanium tetrachloride, to refine described liquid crude titanium tetrachloride, to obtain through refining refined titanic chloride, wherein, in the refined titanic chloride that described process is refined, the content of vanadium is below 3ppm;
(6) refined titanic chloride obtained in step (5) and oxygen are supplied in oxidation reactor, there is oxidizing reaction in described oxidation reactor, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And
(7) the described oxidation mixtures obtained in step (6) is carried out the second gas solid separation, to obtain solid titanium dioxide and chlorine respectively,
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 be communicated with in described reaction chamber, solid materials import and deslagging air outlet, described deslagging air outlet is located at the upper end of described reaction chamber
In step (3), comprise further:
By a part for described liquid crude titanium tetrachloride and the described gas mixture contacts containing titanium tetrachloride, 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 degrees Celsius.
2. method according to claim 1, is characterized in that, described chlorination reaction is carried out at the temperature of 700 ~ 900 degrees Celsius.
3. method according to claim 1, it is characterized in that, in step (6), before being supplied in oxidation reactor by the refined titanic chloride obtained in step (5) and oxygen, in advance described refined titanic chloride and oxygen are carried out thermal pretreatment respectively.
4. method according to claim 3, is characterized in that, described refined titanic chloride and oxygen is preheated to respectively in advance and is not less than 350 degrees Celsius and be not less than 1500 degrees Celsius.
5. method according to claim 1, is characterized in that, comprises further: be back in step (1) by the chlorine obtained in step (7) and carry out chlorination reaction.
6. 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.
7. method according to claim 6, is characterized in that, described chlorination reactor comprises outer steel shell, is provided with heat insulating and corrosion coating between described high alumina brick and described outer steel shell.
8. 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.
9. method according to claim 1, is characterized in that, described reaction chamber also comprises form water curtain to cool the water screen generator of described transition section and described expanding reach in the outside wall surface at described reaction chamber.
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Address after: 650100 Kunming, Xishan District, Yunnan Spring Road, No. 913 Patentee after: Yunnan metallurgy Xin Litai industry company limited Address before: 650100 Kunming, Xishan District, Yunnan Spring Road, No. 913 Patentee before: Yunnan Xinli Nonferrous Metal Co., Ltd. |