CN103663549B - Prepare the method for titanium dioxide - Google Patents
Prepare the method for titanium dioxide Download PDFInfo
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- CN103663549B CN103663549B CN201310660270.0A CN201310660270A CN103663549B CN 103663549 B CN103663549 B CN 103663549B CN 201310660270 A CN201310660270 A CN 201310660270A CN 103663549 B CN103663549 B CN 103663549B
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- chlorination
- titanium tetrachloride
- titanium dioxide
- slag
- titanium
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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
- 238000000034 method Methods 0.000 title claims abstract description 62
- 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 70
- 239000002893 slag Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000000460 chlorine Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 31
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000000428 dust Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002480 mineral oil Substances 0.000 claims abstract description 11
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 11
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 230000005494 condensation Effects 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 239000000571 coke Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 15
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing 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
- 238000007670 refining Methods 0.000 claims description 8
- 239000003507 refrigerant Substances 0.000 claims description 8
- 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
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 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
- 239000006210 lotion Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 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
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 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
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 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
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent 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
- 238000000227 grinding Methods 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
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000004064 recycling Methods 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
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, there is oxidizing reaction in oxidation reactor; (7) oxidation mixtures obtained in step (6) is carried out the second gas solid separation process; And (8) are by processing chlorination dust slag.
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 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 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 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 effectively can preparing titanium dioxide.
In one aspect of the 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 the first gas solid separation process, so that the gaseous mixture obtained containing titanium tetrachloride and chlorination dust slag; (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; (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; And (8) process described chlorination dust slag through the following steps: (8-1) carries out slurrying, press filtration, washing and filtration to described chlorination dust slag, to remove the soluble metal muriate in described chlorination dust slag, and the solid slag obtained containing titanium dioxide and refinery coke, wherein, by washing described chlorination dust slag, iron protochloride in described chlorination dust slag is dissolved, thus obtains the washing water containing iron protochloride; (8-2) carry out carbon successively to the described solid slag containing titanium dioxide and refinery coke to roughly select and carbon choosing, to obtain refinery coke and titanium dioxide titanium slag; (8-3) titanium gravity treatment is carried out, to obtain titanium dioxide solids to described titanium dioxide titanium slag; (8-4) the described washing water containing iron protochloride are contacted, to remove the chlorine in described chlorinated exhaust with described chlorinated exhaust.
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 distribution excellence, and can effectively recycle chloride slag, meanwhile, by the contact of washing water and chlorinated exhaust, the chlorine in chlorinated exhaust can be removed, thus reduce the pollution to environment.
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 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 is preheated to is not less than 350 degrees Celsius 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, 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.
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.
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 one aspect of the invention, the present invention proposes a kind of method 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, 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.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.
According to embodiments of the invention, by controlling the add-on of chlorine and titanium slag in chlorination reactor, remaining that titanium slag is excessive, thus, the reactivity of chlorine can be significantly improved.Meanwhile, in chlorination reaction process, produce a large amount of CO gas, therefore make to keep reducing atmosphere in reactor, thus make Fe Element generation in titanium slag be FeCl
2.
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% the horizontal liquid of titanium tetrachloride gases condensation.
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.
S800: chloride slag process
In aforementioned chlorination reaction, the raw material producing titanium dioxide is mainly titanium slag, in titanium slag except principal element Ti, also there is a large amount of Fe elements (about 8%), if tail gas directly discharges after chlorination reaction, severe contamination certainly will be caused 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, thus the solid slag that can obtain containing titanium dioxide and refinery coke, wherein, by carrying out lotion to chlorination dust slag, the iron protochloride in chlorination dust slag can be made to dissolve, thus the lotion water containing iron protochloride can be obtained.Particularly, add process water and carry out stirring pulping in pulping tank, slurries are delivered to plate-and-frame filter press and carry out press filtration, press filtration terminates rear process water and washs filter cake, finally obtains solid slag.
According to embodiments of the invention, the solid slag containing titanium dioxide and refinery coke to gained carries out carbon successively and roughly selects and carbon choosing, thus can obtain refinery coke and titanium dioxide titanium slag respectively.According to embodiments of the invention, titanium gravity treatment is carried out to obtained titanium dioxide titanium slag, thus can titanium dioxide solids be obtained.Concrete, chlorination residues is delivered to tripping device (as shaking table etc.), utilizes refinery coke different with titanium slag density, go out refinery coke and titanium slag by Gravity separation.Titanium slag is by the further selected separation such as shaking table, hydrocyclone.
According to embodiments of the invention, selected obtained TiO
2titanium dioxide can not be used for boiling chloridizing furnace as raw material because granularity is too little, and the granularity requirements of fused salt chlorimation to titanium dioxide is thinner, the titanium dioxide separated meets the requirement of fused salt chlorimation, therefore the titanium dioxide separated is delivered to dehumidification system and is carried out drying, drying can adopt the mode such as natural air drying, expansion drying, microwave drying, common dryer drying, drying is sent to molten salt furnace as raw material after reaching requirement, and refinery coke directly delivers to boiler house as fuel.
According to embodiments of the invention, gained is contained and contacts with chlorinated exhaust, thus the chlorine in chlorinated exhaust can be removed.Particularly, the lotion water containing iron protochloride is added from the upper end of lotion tower, and chlorinated exhaust adds from lotion tower from lotion tower bottom, iron protochloride is contacted containing unreacted chlorine with tail gas, reacts: 2FeCl
2+ Cl
2→ 2FeCl
3, and lotion liquid is constantly circulated in lotion tower, thus can by the Cl in tail gas
2remove, make the chlorine content in chlorinated exhaust be about 1%, with meet the requirement of environmental protection.In addition, Cl in tail gas is removed with using alkaline reagents in the past
2compare, the present invention, by the iron protochloride in chlorination reaction dust slag is made lotion liquid, effectively can remove the Cl in tail gas
2, thus obviously reduce vent gas treatment cost.
Thus, by adopting the method preparing titanium dioxide of the embodiment of the present invention, can titanium dioxide product that effectively prepared sizes distribution is excellent, simultaneously by recycling titanium dioxide in chloride slag and refinery coke, can raw material availability be significantly improved, thus significantly reduce titanium dioxide production cost, in addition, by the iron protochloride in chlorination reaction dust slag is made lotion liquid, the Cl in tail gas effectively can be removed
2, thus obviously reduce vent gas treatment cost.
With reference to figure 2, the method preparing titanium dioxide according to the embodiment of the present invention comprises further:
S900: 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, in advance 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.
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 (2)
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, so that the gaseous mixture obtained containing titanium tetrachloride and chlorination dust slag;
(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;
(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; And
(8) through the following steps described chlorination dust slag is processed:
(8-1) slurrying, press filtration, washing and filtration are carried out to described chlorination dust slag, to remove the soluble metal muriate in described chlorination dust slag, and the solid slag obtained containing titanium dioxide and refinery coke, wherein, by washing described chlorination dust slag, iron protochloride in described chlorination dust slag is dissolved, thus obtains the washing water containing iron protochloride;
(8-2) carry out carbon successively to the described solid slag containing titanium dioxide and refinery coke to roughly select and carbon choosing, to obtain refinery coke and titanium dioxide titanium slag;
(8-3) titanium gravity treatment is carried out, to obtain titanium dioxide solids to described titanium dioxide titanium slag;
(8-4) the described washing water containing iron protochloride are contacted with described chlorinated exhaust, to remove the chlorine in described chlorinated exhaust,
Wherein, step (3) comprises 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, described refrigerant is the R507 cooling medium of temperature-23 degrees Celsius,
In step (6), before the refined titanic chloride obtained in step (5) and oxygen are supplied in 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, 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,
Describedly carry out in container for evaporation except vanadium process, the 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 chlorine obtained in step (7) and carry 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 |
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| CN108191105B (en) * | 2017-12-28 | 2021-08-13 | 攀枝花钢企欣宇化工有限公司 | A resin purification treatment method for chlorinated tail gas leaching wastewater |
| CN109174057B (en) * | 2018-09-18 | 2021-06-29 | 渤海大学 | Method for preparing bifunctional adsorption material based on organic matter removing vanadium residue |
| 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 |
| CN111893322B (en) * | 2020-08-11 | 2025-01-28 | 洛阳双瑞万基钛业有限公司 | A low titanium slag dry treatment device and dry treatment process |
| 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 |
| CN113634357B (en) * | 2021-08-23 | 2024-02-13 | 云南国钛金属股份有限公司 | Recovery method of titanium tetrachloride dust collection slag |
| CN114014358B (en) * | 2021-12-20 | 2022-08-26 | 昆明理工大学 | Method for processing titanium-containing slag material to enrich rutile |
Citations (4)
| 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 |
| US5266108A (en) * | 1992-04-22 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Using compacted titanium dioxide pigment particles in the cooling section of the chloride process for making TiO2 |
| CN1199385A (en) * | 1996-07-25 | 1998-11-18 | 科尔－麦克基化学有限责任公司 | Method and apparatus for producing titanium dioxide |
| CN1371340A (en) * | 1999-08-30 | 2002-09-25 | 昭和电工株式会社 | Titanium oxide particles and method for production threof |
-
2013
- 2013-12-09 CN CN201310660270.0A patent/CN103663549B/en active Active
Patent Citations (4)
| 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 |
| US5266108A (en) * | 1992-04-22 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Using compacted titanium dioxide pigment particles in the cooling section of the chloride process for making TiO2 |
| CN1199385A (en) * | 1996-07-25 | 1998-11-18 | 科尔－麦克基化学有限责任公司 | Method and apparatus for producing titanium dioxide |
| CN1371340A (en) * | 1999-08-30 | 2002-09-25 | 昭和电工株式会社 | Titanium oxide particles and method for production threof |
Non-Patent Citations (2)
| Title |
|---|
| 四氯化钛生产工艺探讨;刘立文;《无机盐工业》;20130228;第45卷(第2期);第38页 * |
| 四氯化钛的生产和市场研究;顾荣良;《上海化工》;20080131;第33卷(第1期);第35-38页 * |
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