CN103663549A - Preparation method for titanium dioxide - Google Patents
Preparation method for titanium dioxide Download PDFInfo
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- CN103663549A CN103663549A CN201310660270.0A CN201310660270A CN103663549A CN 103663549 A CN103663549 A CN 103663549A CN 201310660270 A CN201310660270 A CN 201310660270A CN 103663549 A CN103663549 A CN 103663549A
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- titanium tetrachloride
- titanium
- chlorination
- titanium dioxide
- slag
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 85
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 68
- 239000002893 slag Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 36
- 239000000460 chlorine Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 239000000428 dust Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002480 mineral oil Substances 0.000 claims abstract description 11
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 230000005494 condensation Effects 0.000 claims abstract description 9
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 239000003570 air Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 58
- 230000008569 process Effects 0.000 claims description 32
- 239000000571 coke Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 239000008246 gaseous mixture Substances 0.000 claims description 15
- 230000002829 reductive effect Effects 0.000 claims description 13
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003507 refrigerant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002826 coolant Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000009997 thermal pre-treatment Methods 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000006210 lotion Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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Abstract
The invention discloses a preparation method for titanium dioxide. The preparation method comprises the following steps: (1) feeding titanium-containing ore and a reducing agent to a chlorination reactor and supplying oxygen, air and chlorine to the chlorination reactor so as to allow a chlorination reaction to be carried out in the chlorination reactor; (2) subjecting a chlorination reaction mixture obtained in the step (1) to primary gas-solid separation; (3) subjecting a gas mixture containing titanium tetrachloride to condensation; (4) storing liquid crude titanium tetrachloride obtained in the step (3) in a titanium tetrachloride storage device; (5) removing vanadium in liquid crude titanium tetrachloride by using mineral oil; (6) supplying refined titanium tetrachloride obtained in the step (5) and oxygen to an oxidation reactor so as to allow an oxidation reaction to be carried out in the oxidation reactor; (7) subjecting an oxidation reaction mixture obtained in the step (6) to secondary gas-solid separation; and (8) treating chlorinated dust slag.
Description
Technical field
The present invention relates to chemical field, particularly, the present invention relates 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 the method that is progressively chlorinated replaces.
CN 1066043 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 give heat 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 pulled an oar 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.
Yet 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 that can effectively prepare titanium dioxide.
In one aspect of the 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) the described chlorination reaction mixture obtaining in step (1) is carried out to the first gas solid separation processing, to obtain the gaseous mixture and the chlorination dust slag that contain titanium tetrachloride; (3) the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride; (4) resulting described liquid crude titanium tetrachloride in step (3) is stored in titanium tetrachloride storing device; (5) adopting mineral oil to remove vanadium to described liquid crude titanium tetrachloride processes, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the smart titanium tetrachloride that described process is refined, the content of vanadium is below 3ppm; (6) the described 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; (7) the described oxidation mixtures obtaining in step (6) is carried out to the second gas solid separation processing, to obtain respectively solid titanium dioxide and chlorine; And process described chlorination dust slag through the following steps (8): (8-1) described chlorination dust slag is carried out to slurrying, press filtration, washing and filtration, to remove the soluble metal muriate in described chlorination dust slag, and obtain the solid slag that contains titanium dioxide and refinery coke, wherein, by described chlorination dust slag is washed, iron protochloride in described chlorination dust slag is dissolved, thereby obtain the washing water that contain iron protochloride; (8-2) the described solid slag that contains titanium dioxide and refinery coke is carried out to carbon successively and roughly select and carbon choosing, to obtain refinery coke and titanium dioxide titanium slag; (8-3) described titanium dioxide titanium slag is carried out to titanium gravity treatment, to obtain titanium dioxide solid; (8-4) washing water that contain iron protochloride described in making contact with described chlorinated exhaust, to remove the chlorine in described chlorinated exhaust.
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 distribution excellence, and can effectively to chloride slag, recycle, meanwhile, by contacting of washing water and chlorinated exhaust, can remove the chlorine in chlorinated exhaust, thereby reduce the pollution to environment.
In addition, the method for preparing titanium dioxide according to the above embodiment of the present invention can also have following additional technical characterictic:
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 to be significantly better than the efficiency of 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 finds, 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 reduced 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 to be significantly better than the cooling medium of 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, in advance described smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, by described oxygen preheat to being not less than 1500 degrees Celsius.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, by smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, oxygen preheat, to being not less than 1500 degrees Celsius, can be reduced to the cost of preparing titanium dioxide significantly effectively.When excess Temperature, the needed cost of preheating can significantly increase, and when 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.
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 obviously and is easily understood becoming the description of embodiment, 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 schematic flow sheet of the method for preparing titanium dioxide of another embodiment according to the present 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.Below by the embodiment being described with reference to the drawings, be exemplary, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In addition, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".In description of the invention, the implication of " a plurality of " is two or more, unless otherwise expressly limited specifically.
In one aspect of the invention, the present invention proposes a kind of method of preparing titanium dioxide.With reference to Fig. 1-2, 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, to there is chlorination reaction in chlorination reactor, and obtain the chlorination reaction mixture that contains 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 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 to be significantly better than the efficiency of other temperature.Particularly, the production of titanium tetrachloride gases is mainly in chlorination reactor, continuously to add titanium ore (titanium slag or rutile) and reducing substances (refinery coke), and continuously in reactor, passes into oxygen, pressurized air, chlorine; And temperature (titanium slag or rutile) and chlorine in the time of 850 ℃ recur reaction and continue to generate TiCl
4gas, reaction equation is: 2TiO
2+ 3C+4Cl
2=2TiCl
4+ 2CO+CO
2.Thus, can effectively titanium dioxide in titanium ore be converted to titanium tetrachloride gases, and then be beneficial to the high-quality titanium dioxide product of follow-up acquisition.
According to embodiments of the invention, the add-on by chlorine and titanium slag in control chlorination reactor, remains that titanium slag is excessive, thus, can obviously improve the reactivity of chlorine.Meanwhile, in chlorination reaction process, producing a large amount of CO gas, therefore make to keep reducing atmosphere in reactor, is FeCl thereby make Fe Element generation in titanium slag
2.
S200: the first gas solid separation
Resulting chlorination reaction mixture in preceding step is carried out to the first gas solid separation processing, thereby can obtain the gaseous mixture that contains titanium tetrachloride.In this step, the titanium tetrachloride gases producing by chlorination reaction, carbon monoxide, carbonic acid gas be mingled with some solid matters that some unreacted refinery cokes, titanium ore and reaction generate and leaving together chlorination reactor and enter the first gas-solid separating device, realized the separated of titanium tetrachloride gases and solid waste.According to embodiments of the invention, the method for carrying out the first gas solid separation processing can be any known means in this area.
S300: condensation process
The gaseous mixture that contains titanium tetrachloride of gained is carried out to condensation process, thereby can obtain liquid crude titanium tetrachloride.Particularly, condensation process comprises: a part for liquid crude titanium tetrachloride is contacted with the gaseous mixture that contains 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 can obtain liquid crude titanium tetrachloride, wherein, refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver finds, 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, in the first cooling process process, can effectively utilize and obtain cooling liquid crude titanium tetrachloride and carry out cooling to the gaseous mixture that contains titanium tetrachloride, thereby significantly reduced the production cost of 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 to be significantly better than the cooling medium of other temperature and type.Meanwhile, adopt the condensation process mode in this step, can be by 99% the horizontal liquid of titanium tetrachloride gases condensation in gas.
S400: storage
In this step, the resulting liquid crude titanium tetrachloride of condensation process step is stored in titanium tetrachloride storing device above.
S500: except vanadium is processed
In this step, adopt mineral oil to remove vanadium to liquid crude titanium tetrachloride and process, to liquid crude titanium tetrachloride is refined, thereby can obtain through refining smart titanium tetrachloride, wherein, in the smart titanium tetrachloride that process is refined, the content of vanadium is below 3ppm.Particularly, adopting mineral oil to remove vanadium processing to liquid crude titanium tetrachloride comprises: in container for evaporation, by liquid crude titanium tetrachloride and mineral oil, its mineral oil in fluid accounts for 1 % by weight of resulting mixture; And along with stirring, the mixture of resulting 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 the separated of vanadium and titanium tetrachloride, thereby obtains through refining smart titanium tetrachloride.In this step, before liquid crude titanium tetrachloride is mixed with mineral oil, utilize in advance nitrogen to a part that adds mineral oil in container for evaporation, 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, remove vanadium and process and can refine and obtain smart titanium tetrachloride to be significantly better than other pressure under 0.5～0.7MPa pressure.Thus, can significantly improve the quality of the titanium dioxide product of follow-up acquisition.
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 oxidation reactor in preceding step
4+ O
2=TiO
2+ 2Cl
2, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.
S700: the second gas solid separation
The oxidation mixtures obtaining in preceding step is carried out to the second gas solid separation processing, to obtain respectively solid titanium dioxide and chlorine.According to embodiments of the invention, the method for carrying out the second gas solid separation processing can be any known means in this area.Contriver's discovery, oxidation mixtures is processed through the second gas solid separation, 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.According to embodiments of the invention, the chlorine obtaining in this step is back to and in chlorination reaction step, carries out chlorination reaction.Contriver's discovery, the chlorine obtaining after processing by the second gas solid separation, can be directly used in chlorination reaction, thereby significantly reduce the cost of producing titanium dioxide, has reduced pollution.
S800: chloride slag is processed
In aforementioned chlorination reaction, the raw material of producing titanium dioxide is mainly titanium slag, in titanium slag except principal element Ti, also there is a large amount of Fe element (8% left and right), if tail gas directly discharges after chlorination reaction, certainly will cause severe contamination to environment, therefore need to be further processed chloride slag.
According to embodiments of the invention, by the slurrying of gained chlorination dust slag, press filtration, washing and filtration, to remove the soluble metal muriate in chlorination dust slag, thereby can obtain the solid slag that contains titanium dioxide and refinery coke, wherein, by chlorination dust slag is carried out to lotion, can be so that the iron protochloride in chlorinated powder dirt slag dissolve, thus can obtain the lotion water that contains iron protochloride.Particularly, in pulping tank, add process water to carry out stirring pulping, slurries are delivered to plate-and-frame filter press and carry out press filtration, press filtration finishes with process water, filter cake to be washed afterwards, finally obtains solid slag.
According to embodiments of the invention, the solid slag that gained is contained to titanium dioxide and refinery coke carries out carbon successively to be roughly selected and carbon choosing, thereby can obtain respectively refinery coke and titanium dioxide titanium slag.According to embodiments of the invention, resulting titanium dioxide titanium slag is carried out to titanium gravity treatment, thereby can obtain titanium dioxide solid.Concrete, chlorination residues is delivered to tripping device (as shaking table etc.), utilize refinery coke different with titanium slag density, by Gravity separation, go out refinery coke and titanium slag.Titanium slag is by further selected separation such as shaking table, hydrocyclones.
According to embodiments of the invention, selected resulting TiO
2titanium dioxide due to granularity is too little can not be for boiling chloridizing furnace as raw material, and fused salt chlorimation is thinner to the granularity requirements of titanium dioxide, the titanium dioxide of separating meets the requirement of fused salt chlorimation, therefore the titanium dioxide of separating is delivered to dehumidification system and is dried, be dried and can adopt the modes such as natural air drying, expansion drying, microwave drying, common drying machine are dried, dry be sent to molten salt furnace as raw material after reaching requirement, refinery coke is directly delivered to boiler house as fuel.
According to embodiments of the invention, gained is contained with chlorinated exhaust and contacted, thereby can remove the chlorine in chlorinated exhaust.Particularly, the lotion water that contains iron protochloride is added from the upper end of lotion tower, and chlorinated exhaust adds from lotion tower from lotion tower bottom, and iron protochloride is contacted with containing unreacted chlorine in tail gas, reacts: 2FeCl
2+ Cl
2→ 2FeCl
3, and by the constantly circulation in lotion tower of lotion liquid, thereby can be by the Cl in tail gas
2remove, making the chlorine content in chlorinated exhaust is 1% left and right, with meet the requirement of environmental protection.In addition, removed the Cl in tail gas with use alkaline reagents in the past
2compare, the present invention, by the iron protochloride in chlorination reaction dust slag is made to lotion liquid, can effectively remove the Cl in tail gas
2thereby, obviously reduce vent gas treatment cost.
Thus, by adopting the method for preparing titanium dioxide of the embodiment of the present invention, the effective prepared sizes excellent titanium dioxide product that distributes, simultaneously by titanium dioxide in chloride slag and refinery coke are recycled, can obviously improve raw material availability, thereby significantly reduce titanium dioxide production cost, in addition, by the iron protochloride in chlorination reaction dust slag is made to lotion liquid, can effectively remove the Cl in tail gas
2thereby, obviously reduce vent gas treatment cost.
With reference to figure 2, according to the method for preparing titanium dioxide of the embodiment of the present invention, further comprise:
S900: thermal pretreatment
Before in resulting smart titanium tetrachloride and oxygen are supplied to oxidation reactor, in advance smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.According to embodiments of the invention, in advance smart titanium tetrachloride and oxygen are carried out the temperature of thermal pretreatment and be not particularly limited, according to a particular embodiment of the invention, can in advance smart titanium tetrachloride be preheated to and be not less than 350 degrees Celsius, by oxygen preheat to being not less than 1500 degrees Celsius.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, by smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, oxygen preheat, to being not less than 1500 degrees Celsius, can be reduced to the cost of preparing titanium dioxide significantly effectively.When excess Temperature, the needed cost of preheating can significantly increase, and when temperature is too low, in oxidation reactor, can consume too much energy.
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 the specific features of description, structure, material or feature can be with suitable mode combinations 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 (6)
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) the described chlorination reaction mixture obtaining in step (1) is carried out to the first gas solid separation processing, to obtain the gaseous mixture and the chlorination dust slag that contain titanium tetrachloride;
(3) the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride;
(4) resulting described liquid crude titanium tetrachloride in step (3) is stored in titanium tetrachloride storing device;
(5) adopting mineral oil to remove vanadium to described liquid crude titanium tetrachloride processes, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the smart titanium tetrachloride that described process is refined, the content of vanadium is below 3ppm;
(6) the described 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;
(7) the described oxidation mixtures obtaining in step (6) is carried out to the second gas solid separation processing, to obtain respectively solid titanium dioxide and chlorine; And
(8) through the following steps described chlorination dust slag is processed:
(8-1) described chlorination dust slag is carried out to slurrying, press filtration, washing and filtration, to remove the soluble metal muriate in described chlorination dust slag, and obtain the solid slag that contains titanium dioxide and refinery coke, wherein, by described chlorination dust slag is washed, iron protochloride in described chlorination dust slag is dissolved, thereby obtain the washing water that contain iron protochloride;
(8-2) the described solid slag that contains titanium dioxide and refinery coke is carried out to carbon successively and roughly select and carbon choosing, to obtain refinery coke and titanium dioxide titanium slag;
(8-3) described titanium dioxide titanium slag is carried out to titanium gravity treatment, to obtain titanium dioxide solid;
(8-4) washing water that contain iron protochloride described in making contact with described chlorinated exhaust, to remove the chlorine in described chlorinated exhaust.
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, in advance described smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, by described oxygen preheat to being not less than 1500 degrees Celsius.
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.
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| CN103950974A (en) * | 2014-04-16 | 2014-07-30 | 沈阳化工大学 | A method for preparing rutile type high-purity TiO2 powder by distillation hydrolysis |
| CN106477625A (en) * | 2016-09-18 | 2017-03-08 | 云南冶金新立钛业有限公司 | Process the system of oxidized tail gas in titanium white production |
| CN107758738A (en) * | 2017-11-29 | 2018-03-06 | 广西雅照钛白有限公司 | A kind of titanium dioxide chloridising production technology |
| CN107777725A (en) * | 2017-11-29 | 2018-03-09 | 广西雅照钛白有限公司 | A kind of new titanium white production technique |
| CN107954472A (en) * | 2017-11-29 | 2018-04-24 | 广西雅照钛白有限公司 | A kind of titanium white production technique |
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| CN109174057A (en) * | 2018-09-18 | 2019-01-11 | 渤海大学 | Based on organic matter except the method for alum waste residue preparation bifunctional adsorbent material |
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| CN112211029A (en) * | 2020-09-26 | 2021-01-12 | 沪本新材料科技（上海）有限公司 | Novel nanoscale liquid titanium dioxide for papermaking |
| CN112744862A (en) * | 2019-10-31 | 2021-05-04 | 新疆硅基新材料创新中心有限公司 | Titanium dioxide preparation method and titanium tetrachloride and titanium dioxide prepared by method |
| CN113634357A (en) * | 2021-08-23 | 2021-11-12 | 禄丰新立钛业有限公司 | Method for recovering titanium tetrachloride dust collecting slag |
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| CN107758738A (en) * | 2017-11-29 | 2018-03-06 | 广西雅照钛白有限公司 | A kind of titanium dioxide chloridising production technology |
| CN107777725A (en) * | 2017-11-29 | 2018-03-09 | 广西雅照钛白有限公司 | A kind of new titanium white production technique |
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| CN112744862B (en) * | 2019-10-31 | 2023-04-28 | 新疆硅基新材料创新中心有限公司 | Titanium dioxide preparation method, titanium tetrachloride prepared by same and titanium dioxide |
| CN112744862A (en) * | 2019-10-31 | 2021-05-04 | 新疆硅基新材料创新中心有限公司 | Titanium dioxide preparation method and titanium tetrachloride and titanium dioxide prepared by method |
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| CN114014358B (en) * | 2021-12-20 | 2022-08-26 | 昆明理工大学 | Method for processing titanium-containing slag material to enrich rutile |
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