CN103880077B - Prepare the method for titanium dioxide - Google Patents
Prepare the method for titanium dioxide Download PDFInfo
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- CN103880077B CN103880077B CN201310665479.6A CN201310665479A CN103880077B CN 103880077 B CN103880077 B CN 103880077B CN 201310665479 A CN201310665479 A CN 201310665479A CN 103880077 B CN103880077 B CN 103880077B
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- titanium tetrachloride
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Abstract
The invention discloses a kind of 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 chlorination reactor, there is chlorination reaction in chlorination reactor; (2) chlorination reaction mixture obtained in step (1) is carried out the first gas solid separation process; (3) condensation process is carried out to the gaseous mixture containing titanium tetrachloride; (4) the 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 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 the second gas solid separation process 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, specifically, the present invention relates to a kind of method preparing titanium dioxide.
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 magnesium is carried out to the rough titanium tetrachloride obtained after chlorination, 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 give heat 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 removed rapidly, collect titanium dioxide, generate 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 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) the described chlorination reaction mixture obtained in step (1) is carried out 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) the described 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 gas solid separation process by (7), to obtain solid titanium dioxide and chlorine respectively.Wherein, in step (5), mineral oil is adopted to carry out comprising further except vanadium process to described liquid crude titanium tetrachloride: in container for evaporation, by described liquid crude titanium tetrachloride and described mineral oil, wherein said mineral oil accounts for 1 % by weight of obtained mixture; And along with stirring, the mixture of obtained described liquid crude titanium tetrachloride and described mineral oil is heated, so that by the vanadium in described liquid crude titanium tetrachloride by lower boiling VOCl
3be converted into high boiling VOCl
2impurity, to realize being separated of vanadium and titanium tetrachloride, thus obtains the refining refined titanic chloride of described process.
In addition, the method preparing titanium dioxide according to the above embodiment of the present invention can also have following additional technical characteristic:
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 described oxidation reactor by the described 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 is preheated to is not less than 350 degrees Celsius in advance, in advance by described oxygen preheat to being not less than 1500 degrees Celsius.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, by oxygen preheat to being not less than 1500 degrees Celsius, can significantly effectively reducing the cost preparing titanium dioxide by being preheated to by refined titanic chloride.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, the described method preparing titanium dioxide comprises further: be back in step (1) by the described chlorine obtained in step (7) and carry out described 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, before by described liquid crude titanium tetrachloride and described mineral oil, utilize nitrogen in described container for evaporation, add a part for described mineral oil in advance.Thus, mineral oil carbonization can be prevented and blocking pipe.
In one embodiment of the invention, the pressure in described container for evaporation is 0.5 ~ 0.7MPa.Thus, dust removal rate can be improved further, to improve the quality of titanium dioxide.
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 schematic flow sheet preparing the method for titanium dioxide according to another embodiment of the present invention;
Fig. 3 is the system architecture schematic diagram for implementing the method preparing titanium dioxide according to an embodiment of the invention;
Fig. 4 is the system architecture schematic diagram preparing the method for titanium dioxide for implementing according to another embodiment of the present 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.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.
In addition, term " first ", " second " only for describing object, and can not be interpreted as instruction or hint relative importance or imply the quantity indicating indicated technical characteristic.Thus, be limited with " first ", the feature of " second " can express or impliedly comprise one or more these features.In describing the invention, the implication of " multiple " is two or more, unless otherwise expressly limited specifically.
In first of the present invention, the present invention proposes a kind of method preparing titanium dioxide.Below with reference to Fig. 1-2, the method preparing titanium dioxide of the embodiment of the present invention is described in detail.According to embodiments of the invention, the method comprises:
S100: chlorination reaction
Titaniferous ore, reductive agent are supplied in chlorination reactor, and to oxygen gas-supplying, air and chlorine in chlorination reactor, there is chlorination reaction in chlorination reactor, and the chlorination reaction mixture obtained containing titanium tetrachloride gases, wherein, reductive agent is refinery coke, and titaniferous ore is titanium slag or rutile titanium ore.According to a particular embodiment of the invention, carry out the temperature condition of chlorination reaction and be not particularly limited, according to concrete example of the present invention, chlorination reaction can be 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 this step, particularly, titanium ore (titanium slag or rutile) and 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, chlorine; And temperature (titanium slag or rutile) and chlorine 850 DEG C time recur, and reaction is lasting generates TiCl
4gas, reaction equation is: 2TiO
2+ 3C+4Cl
2=2TiCl
4+ 2CO+CO
2.Thus, effectively titanium dioxide in titanium ore can be converted to titanium tetrachloride gases, and then be beneficial to the high-quality titanium dioxide product of follow-up acquisition.
S200: the first gas solid separation
The chlorination reaction mixture obtained in preceding step is carried out the first gas solid separation process, thus the gaseous mixture containing titanium tetrachloride can be obtained.In this step, the titanium tetrachloride gases produced by chlorination reaction, carbon monoxide, carbonic acid gas are mingled with some solid matters that some unreacted refinery cokes, titanium ore and reaction generate and leave chlorination reactor together and enter the first gas-solid separating device, achieve being separated of titanium tetrachloride gases and solid waste.According to embodiments of the invention, the method for carrying out the first gas solid separation process can be any known means in this area.
S300: condensation process
The gaseous mixture containing titanium tetrachloride of gained is carried out condensation process, thus liquid crude titanium tetrachloride can be obtained.Particularly, condensation process comprises: by a part for liquid crude titanium tetrachloride and the 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, thus liquid crude titanium tetrachloride can be obtained, wherein, 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 in the first cooling process process, the liquid crude titanium tetrachloride having obtained cooling can be effectively utilized cool the gaseous mixture containing titanium tetrachloride, thus significantly reduce the production cost of 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.Meanwhile, adopt the condensation process mode in this step, can by gas 99% titanium tetrachloride gases be condensed into liquid.
S400: store
In this step, the liquid crude titanium tetrachloride that condensation process step obtains above is stored in titanium tetrachloride storing device.
S500: except vanadium process
In this step, adopt mineral oil to carry out except vanadium process to liquid crude titanium tetrachloride, to refine liquid crude titanium tetrachloride, thus can obtain through refining refined titanic chloride, wherein, in refining refined titanic chloride, the content of vanadium is below 3ppm.Particularly, mineral oil is adopted to carry out comprising except vanadium process to liquid crude titanium tetrachloride: in container for evaporation, by liquid crude titanium tetrachloride and mineral oil, its mineral oil in fluid accounts for 1 % by weight of obtained mixture; And along with stirring, the mixture of obtained liquid crude titanium tetrachloride and mineral oil is heated, so that by the vanadium in liquid crude titanium tetrachloride by lower boiling VOCl
3be converted into high boiling VOCl
2impurity, to realize being separated of vanadium and titanium tetrachloride, thus obtains through refining refined titanic chloride.In this step, before being mixed with mineral oil by liquid crude titanium tetrachloride, utilize nitrogen in container for evaporation, add a part for mineral oil in advance, to prevent mineral oil carbonization blocking pipeline.According to embodiments of the invention, the pressure in container for evaporation is also not particularly limited, and according to a particular embodiment of the invention, the pressure in container for evaporation can be 0.5 ~ 0.7MPa.Contriver surprisingly finds through great many of experiments, carries out except vanadium process can other pressure is refining obtains refined titanic chloride to be significantly better than under 0.5 ~ 0.7MPa pressure.Thus, the quality of the titanium dioxide product of follow-up acquisition can be significantly improved.
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 oxidation reactor
4+ O
2=TiO
2+ 2Cl
2, to obtain the oxidation mixtures containing titanium dioxide and chlorine.
S700: the second gas solid separation
The oxidation mixtures obtained in preceding step is carried out the second gas solid separation process, to obtain solid titanium dioxide and chlorine respectively.According to embodiments of the invention, the method for carrying out the second gas solid separation process can be any known means in this area.Contriver finds, oxidation mixtures, through the second gas solid separation process, can prepare titanium dioxide effectively, and then by carrying out coating process to titanium dioxide, effectively can obtain the titanium dioxide of size-grade distribution excellence.According to embodiments of the invention, the chlorine obtained is back in chlorination reaction step carries out chlorination reaction in this step.Contriver finds, by the chlorine obtained after the second gas solid separation process, can be directly used in chlorination reaction, thus significantly reduces the cost producing titanium dioxide, decreases pollution.
With reference to figure 2, the method preparing titanium dioxide according to the embodiment of the present invention comprises further:
S800: thermal pretreatment
Before being supplied in oxidation reactor by obtained refined titanic chloride and oxygen, in advance refined titanic chloride and oxygen are carried out thermal pretreatment respectively.According to embodiments of the invention, in advance refined titanic chloride and oxygen are carried out the temperature of thermal pretreatment and be not particularly limited, according to a particular embodiment of the invention, refined titanic chloride can be preheated to and be not less than 350 degrees Celsius, by oxygen preheat to being not less than 1500 degrees Celsius.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, by oxygen preheat to being not less than 1500 degrees Celsius, can significantly effectively reducing the cost preparing titanium dioxide by being preheated to by refined titanic chloride.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.
Thus, by adopting the method preparing titanium dioxide of the embodiment of the present invention, by lower boiling VOCl in liquid crude titanium tetrachloride
3be converted into high boiling VOCl
2, thus effectively removes the impact of impurity vanadium on titanium dioxide product quality, finally obtain high-quality titanium dioxide product, this automation technolo degree is high, stable and be convenient to control simultaneously.
Above the method preparing titanium dioxide of the embodiment of the present invention being described in detail, conveniently understanding, below with reference to Fig. 3-4, the system preparing the method for titanium dioxide for implementing the embodiment of the present invention being described in detail.According to embodiments of the invention, this system comprises:
Chlorination reactor 100: 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 chlorination reactor, and to oxygen gas-supplying, air and chlorine in chlorination reactor, there is chlorination reaction in chlorination reactor, thus the chlorination reaction mixture that can obtain containing titanium tetrachloride gases, wherein, reductive agent is refinery coke, and titaniferous ore is titanium slag or rutile titanium ore.According to embodiments of the invention, carry out the temperature condition of chlorination reaction and be not particularly limited, according to a particular embodiment of the invention, chlorination reaction can be 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.Particularly, titanium ore (titanium slag or rutile) and 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, chlorine; And temperature (titanium slag or rutile) and chlorine 850 DEG C time recur, and reaction is lasting generates TiCl
4gas, reaction equation is: 2TiO
2+ 3C+4Cl
2=2TiCl
4+ 2CO+CO
2.Thus, effectively titanium dioxide in titanium ore can be converted to titanium tetrachloride gases, and then be beneficial to the high-quality titanium dioxide product of follow-up acquisition.
First gas-solid separating device 200: the first gas-solid separating device 200 is connected with chlorination reactor 100, for carrying out gas solid separation process to the chlorination reaction mixture of gained, thus can obtain the gaseous mixture containing titanium tetrachloride.In this step, the titanium tetrachloride gases produced by chlorination reaction, carbon monoxide, carbonic acid gas are mingled with some solid matters that some unreacted refinery cokes, titanium ore and reaction generate and leave chlorination reactor together and enter the first gas-solid separating device, achieve being separated of titanium tetrachloride gases and solid waste.According to embodiments of the invention, the first gas-solid separating device can be any known device in this area.
Condensing works 300: condensing works 300 is connected with the first gas-solid separating device 200, for carrying out condensation process to the gaseous mixture containing titanium tetrachloride of gained, thus can obtain liquid crude titanium tetrachloride.Particularly, condensing works comprises: adverse current cooling unit, adverse current cooling unit is provided with chlorination reaction mixture entrance and liquid crude titanium tetrachloride entrance, so that by a part for liquid crude titanium tetrachloride and the described gaseous mixture counter current contact containing titanium tetrachloride in adverse current cooling unit, to carry out the first cooling process; And tubular heat exchanger, tubular heat exchanger is connected with adverse current cooling unit, and utilizes refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain liquid crude titanium tetrachloride, wherein, refrigerant is the R507 cooling medium of temperature-23 degrees Celsius.Contriver finds, adopts this refrigerating unit, 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.Meanwhile, adopt this condensing works, can by gas 99% titanium tetrachloride gases be condensed into liquid.
Titanium tetrachloride storing device 400: titanium tetrachloride storing device 400 is connected with condensing works 300, for storage of liquids crude titanic chloride.
Except vanadium device 500: except vanadium device 500 is connected with titanium tetrachloride storing device 400, and be suitable for adopting mineral oil to carry out except vanadium process to liquid crude titanium tetrachloride, to refine liquid crude titanium tetrachloride, thus can obtain through refining refined titanic chloride, wherein, in refining titanium tetrachloride, the content of vanadium is below 3ppm.Particularly, adopt except vanadium device 500 pairs of crude titanic chlorides carry out comprising except vanadium process: in container for evaporation, by liquid crude titanium tetrachloride and mineral oil, its mineral oil in fluid accounts for 1 % by weight of obtained mixture; And along with stirring, the mixture of obtained liquid crude titanium tetrachloride and mineral oil is heated, so that by the vanadium in liquid crude titanium tetrachloride by lower boiling VOCl
3be converted into high boiling VOCl
2impurity, to realize being separated of vanadium and titanium tetrachloride, thus obtains through refining refined titanic chloride.In this step, before liquid crude titanium tetrachloride is mixed with mineral oil, utilize nitrogen in container for evaporation, add a part for mineral oil in advance, to prevent mineral oil carbonization blocking pipeline, according to embodiments of the invention, pressure in container for evaporation is also not particularly limited, and according to a particular embodiment of the invention, the pressure in container for evaporation can be 0.5 ~ 0.7MPa.Contriver surprisingly finds through great many of experiments, carries out to obtain refined titanic chloride to be significantly better than other pressure except vanadium process under 0.5 ~ 0.7MPa pressure.
Oxidation reactor 600: oxidation reactor 600 is connected with except vanadium device 500, and be provided with oxygen intake, for 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.In this step, the refined titanic chloride obtained in preceding step and oxygen are supplied in oxidation reactor, in oxidation reactor, oxidizing reaction TiCl occur
4+ O
2=TiO
2+ 2Cl
2, thus the oxidation mixtures containing titanium dioxide and chlorine can be obtained.
Second gas-solid separating device 700: the second gas-solid separating device 700 is connected with oxidation reactor 600, for carrying out the second gas solid separation process to oxidation mixtures, thus can obtain solid titanium dioxide and chlorine respectively.According to embodiments of the invention, the second gas solid separation treatment unit can be any known means in this area.Contriver finds, oxidation mixtures, through the second gas solid separation process, can prepare titanium dioxide effectively, and then by carrying out coating process to titanium dioxide, effectively can obtain the titanium dioxide of size-grade distribution excellence.According to embodiments of the invention, the chlorine obtained is back in chlorination reactor carries out chlorination reaction in this step.Contriver finds, by the chlorine obtained after the second gas solid separation process, can be directly used in chlorination reaction, thus significantly reduces the cost producing titanium dioxide, decreases pollution.Adopt this system thus, effectively can implement the aforementioned method preparing titanium dioxide.
With reference to figure 4, the system according to an embodiment of the invention for implementing the method preparing titanium dioxide comprises further:
Refined titanic chloride primary heater unit 800: refined titanic chloride primary heater unit 800 is connected with oxidation reactor 600, in advance refined titanic chloride is carried out thermal pretreatment with except vanadium device 500;
Oxygen preheat equipment 900: oxygen preheat equipment 900 is connected with oxidation reactor 600, to carry out thermal pretreatment to oxygen in advance.
According to a particular embodiment of the invention, in advance refined titanic chloride and oxygen are carried out the temperature of preheating and be not particularly limited, according to concrete example of the present invention, in advance refined titanic chloride can be preheated to more than 350 degrees Celsius, in advance by more than oxygen preheat to 1500 degree Celsius.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, by oxygen preheat to being not less than 1500 degrees Celsius, can significantly effectively reducing the cost preparing titanium dioxide by being preheated to by refined titanic chloride.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.Thus, the efficiency preparing titanium dioxide can be improved further, reduce the cost preparing titanium dioxide.
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 (3)
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) the described 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) the described 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 process, to obtain solid titanium dioxide and chlorine respectively,
Wherein, in step (5), mineral oil is adopted to carry out comprising further except vanadium process to described liquid crude titanium tetrachloride:
In container for evaporation, by described liquid crude titanium tetrachloride and described mineral oil, wherein said mineral oil accounts for 1 % by weight of obtained mixture;
Along with stirring, the mixture of obtained described liquid crude titanium tetrachloride and described mineral oil is heated, so that by the vanadium in described liquid crude titanium tetrachloride by lower boiling VOCl
3be converted into high boiling VOCl
2impurity, to realize being separated of vanadium and titanium tetrachloride, thus obtains the refining refined titanic chloride of described process,
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,
In step (6), before the described refined titanic chloride obtained in step (5) and oxygen are supplied in described oxidation reactor, in advance described refined titanic chloride and oxygen are carried out thermal pretreatment respectively, in advance described refined titanic chloride is preheated to and is not less than 350 degrees Celsius, in advance by described oxygen preheat to being not less than 1500 degrees Celsius
Described chlorination reaction is carried out at the temperature of 850 degrees Celsius,
Pressure in described container for evaporation is 0.5 ~ 0.7MPa.
2. method according to claim 1, is characterized in that, comprises further: be back in step (1) by the described chlorine obtained in step (7) and carry out chlorination reaction.
3. method according to claim 1, is characterized in that, before by described liquid crude titanium tetrachloride and described mineral oil, utilizes nitrogen in described container for evaporation, add a part for described mineral oil in advance.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
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