CN110372033A - Titanium dioxide synthesis system - Google Patents
Titanium dioxide synthesis system Download PDFInfo
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- CN110372033A CN110372033A CN201910766167.1A CN201910766167A CN110372033A CN 110372033 A CN110372033 A CN 110372033A CN 201910766167 A CN201910766167 A CN 201910766167A CN 110372033 A CN110372033 A CN 110372033A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 97
- 239000010936 titanium Substances 0.000 claims abstract description 65
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 52
- 239000002893 slag Substances 0.000 claims abstract description 47
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 230000009467 reduction Effects 0.000 claims abstract description 35
- 230000007246 mechanism Effects 0.000 claims abstract description 20
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000001816 cooling Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 238000010828 elution Methods 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 21
- 239000002918 waste heat Substances 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 22
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 235000010215 titanium dioxide Nutrition 0.000 description 31
- 230000008569 process Effects 0.000 description 14
- 239000012535 impurity Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012445 acidic reagent Substances 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 206010003694 Atrophy Diseases 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of titanium dioxide synthesis systems.Above-mentioned synthesis system includes: ilmenite feeding mechanism, reduction melting unit, chlorination reaction unit and oxidation unit；Reduction melting unit is provided with feed opening and high titanium slag outlet, and feed opening is connected with ilmenite feeding mechanism；Chlorination reaction unit is provided with high titanium slag entrance, chlorine inlet and titanium tetrachloride outlet, and high titanium slag entrance is connected with high titanium slag outlet by high titanium slag transfer pipeline；And oxidation reaction unit is provided with titanium tetrachloride entrance and titanium dioxide outlet, titanium tetrachloride entrance is connected with titanium tetrachloride outlet by titanium tetrachloride transfer pipeline.The feature of environmental protection of technique can be greatly promoted using titanium dioxide synthesis system provided by the present application, while it also has many advantages, such as easily operated, short preparation period and at low cost.
Description
Technical field
The present invention relates to field of metallurgy, in particular to a kind of titanium dioxide synthesis system.
Background technique
China's titanium resource is relatively abundanter, in addition to a small amount of ferrotianium placer, mainly based on ilmenitite mine, but domestic ilmenitite mine
Grade is low, and impurity content is high, cannot directly meet requirement of the chloride process titanium dioxide to raw material, only be suitable for the original for making sulfate process titanium dioxide
Material.It largely is difficult to administer, pollute " three wastes " of environment due to generating in sulfate process titanium dioxide production process, in recent years global sulfuric acid process
Titanium dioxide capacity sharply atrophy.Therefore, seek economic, environmental protection, reasonable titanium material processing method, China's ilmenite abundant is provided
It is processed into the task of top priority that high-purity titanium dioxide is China's titanium white and titanium industry development in source.
Summary of the invention
The main purpose of the present invention is to provide a kind of titanium dioxide synthesis systems, existing using ilmenite as raw material to solve
The method for preparing titanium dioxide there are problems that not environmentally.
To achieve the goals above, a kind of titanium dioxide synthesis system, above-mentioned synthesis system packet are provided according to the present invention
It includes: ilmenite feeding mechanism, reduction melting unit, chlorination reaction unit and oxidation unit；Reduction melting unit is provided with charging
Mouth and high titanium slag outlet, feed opening are connected with ilmenite feeding mechanism；Chlorination reaction unit is provided with high titanium slag entrance, chlorine
Gas entrance and titanium tetrachloride outlet, high titanium slag entrance are connected with high titanium slag outlet by high titanium slag transfer pipeline；And oxygen
Change reaction member and be provided with titanium tetrachloride entrance and titanium dioxide outlet, titanium tetrachloride entrance passes through with titanium tetrachloride outlet
Titanium tetrachloride transfer pipeline is connected.
Further, reduction melting unit includes: reduction melting device and waste-heat recovery device, the setting of reduction melting device
There are feed opening, high titanium slag outlet, liquid metal outlet and exhanst gas outlet；Exhanst gas outlet is connected with waste-heat recovery device, with
Waste heat in recovered flue gas.
Further, reduction melting unit further includes the first cooling device, and the setting of the first cooling device is conveyed in high titanium slag
On pipeline.
Further, reduction melting unit further includes the second cooling device, and the second cooling device is used for from liquid metal
The liquid metal of outlet discharge is cooled down.
Further, chlorination reaction unit further include: chlorination reaction device, cleaner feeding mechanism and rectifier unit, chlorine
Change reaction unit and is provided with titanium tetrachloride entrance and titanium tetrachloride crude product outlet；And cleaner feeding mechanism is arranged by cleaning
Agent supply opening；And rectifier unit is provided with rectifying entrance, cleaner entrance and titanium dioxide outlet, cleaner entrance and removal of impurities
Agent supply opening is connected by cleaner transfer pipeline, and rectifying entrance is thick by titanium tetrachloride with titanium tetrachloride crude product outlet
Product transfer pipeline is connected, to remove the vanadium in titanium tetrachloride crude product.
Further, chlorination reaction device is gas-solid fluidized bed reactor.
Further, chlorination reaction unit further includes quenching apparatus, and quenching apparatus is arranged on titanium tetrachloride transfer pipeline.
Further, chlorination reaction unit further includes cyclone dust collector and elution device, cyclone dust collector and elution
Device is arranged on the titanium tetrachloride transfer pipeline between quenching apparatus and rectifier unit, and along the flow direction of material, rotation
The upstream of elution device is arranged in wind dust-extraction unit.
Further, chlorination reaction unit further includes cryogenic system, double-effect heat exchange device and tail gas elution device, deep cooling dress
It sets, double-effect heat exchange device and tail gas elution device are arranged at titanium tetrachloride transfer pipeline between elution device and rectifier unit
On, and along the flow direction of material, the upstream of double-effect heat exchange device is arranged in cryogenic system, and tail gas elution device is arranged in economic benefits and social benefits
The downstream of heat-exchanger rig is provided with -25 DEG C of refrigerant in cryogenic purification device.
Further, oxidation unit includes: oxidation reaction apparatus and alchlor reaction unit, oxidation reaction apparatus setting
There is titanium tetrachloride entrance；The pipeline between titanium tetrachloride outlet and titanium tetrachloride entrance is arranged in alchlor reaction unit
On, and alchlor reaction unit is used to prepare alchlor using aluminium and chlorine as raw material.
Further, alchlor reaction unit is provided with reaction chamber, the import phase of titanium tetrachloride outlet and reaction chamber
Even, and titanium tetrachloride entrance is connected with the outlet of reaction chamber；Or alchlor reaction unit be internally provided with reaction chamber and
Preheating channel, and being isolated between reaction chamber and preheating channel by heat transfer component, titanium tetrachloride outlet and preheating channel into
Mouth is connected, and titanium tetrachloride entrance is connected with the outlet of preheating channel；Reaction chamber is additionally provided with alchlor outlet, tri-chlorination
Aluminium outlet is connected with titanium tetrachloride entrance by alchlor entrance.
Further, oxidation unit further includes preheating device and oxygen supply device, oxygen supply device and oxidation reaction
Device is connected by oxygen supply pipeline, and preheating device is arranged on oxygen supply pipeline, in oxygen supply pipeline
Oxygen is preheated.
It applies the technical scheme of the present invention, above-mentioned synthesis system is used to prepare titanium dioxide product, in whole process not
It is related to the use of acid reagent, and does not also generate environmentally harmful waste；Simultaneously in reduction melting unit, titanium elements quilt
Enrichment, obtains the higher Ti-enriched slag of Ti content, carries out subsequent chlorination reaction and oxidation reaction using Ti-enriched slag, is conducive to shorten
Process cycle.The feature of environmental protection of technique, while its can be thus greatly promoted using titanium dioxide synthesis system provided by the present application
Also has many advantages, such as easily operated, short preparation period and at low cost.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
The structure that Fig. 1 shows the titanium dioxide synthesis system that a kind of typical embodiment according to the present invention provides is shown
It is intended to.
Wherein, the above drawings include the following reference numerals:
10, ilmenite feeding mechanism；
20, reduction melting unit；21, reduction melting device；22, waste-heat recovery device；23, the first cooling device；24,
Two cooling devices；30, chlorination reaction unit；31, chlorination reaction device；32, quenching apparatus；33, cyclone dust collector；34, it drenches
Cleaning device；35, cryogenic system；36, double-effect heat exchange device；37, tail gas elution device；38, rectifier unit；39, cleaner is supplied
Device；40, oxidation unit；41, oxidation reaction apparatus；42, alchlor reaction unit；43, preheating device；44, oxygen supply
Device；45, dechlorination device；46, dioxygen water supply.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, the existing method for preparing titanium dioxide as raw material using ilmenite exists not environmentally
The problem of.In order to solve the above-mentioned technical problem, this application provides a kind of titanium dioxide synthesis systems, as shown in Figure 1, the synthesis
System includes: ilmenite feeding mechanism 10, reduction melting unit 20, chlorination reaction unit 30 and oxidation unit 40.Reduction melting
Unit 20 is provided with feed opening and high titanium slag outlet, and feed opening is connected with ilmenite feeding mechanism 10；Chlorination reaction unit
30 are provided with high titanium slag entrance, chlorine inlet and titanium tetrachloride outlet, and high titanium slag entrance and high titanium slag outlet pass through high titanium
Slag transfer pipeline is connected；And oxidation reaction unit is provided with titanium tetrachloride entrance and titanium dioxide outlet, titanium tetrachloride enters
Mouth is connected with titanium tetrachloride outlet by titanium tetrachloride transfer pipeline.
The reaction principle of above-mentioned preparation method are as follows: ilmenite is delivered to reduction melting device 21 by ilmenite feeding mechanism 10
Ferro element in ilmenite is restored, and existed in liquid form by middle progress reduction melting process, this can make ilmenite
In titanium elements carry out enrichment form solid Ti-enriched slag.Point of metal phase and Ti-enriched slag can be realized by simply separating
From.Then the higher Ti-enriched slag of titanium elements content and chlorine in chlorination reaction device 31 to that chlorination reaction occur prepare four chlorinations
Titanium.It will be finally delivered in oxidation unit 40 by titanium tetrachloride obtained in chlorination reaction unit 30 and carry out oxidation reaction, obtained
Required titanium dioxide.
Above-mentioned synthesis system is used to prepare titanium dioxide product, is not related to the use of acid reagent in whole process, and
Environmentally harmful waste is not generated yet；Simultaneously in reduction melting unit 20, titanium elements are enriched with, and it is higher to obtain Ti content
Ti-enriched slag, carry out subsequent chlorination reaction and oxidation reaction using Ti-enriched slag, be conducive to shorten process cycle.Thus using this
The titanium dioxide synthesis system that application provides can greatly promote the feature of environmental protection of technique, while it also has easily operated, preparation
The advantages that period is short and at low cost.
In a preferred embodiment, as shown in Figure 1, reduction melting unit 20 includes: 21 He of reduction melting device
Waste-heat recovery device 22.Reduction melting device 21 is provided with feed opening, high titanium slag outlet, liquid metal outlet and flue gas and goes out
Mouthful；Exhanst gas outlet is connected with waste-heat recovery device 22, with the waste heat in recovered flue gas.
The reduction melting reaction carried out in reduction melting device 21 usually carries out at a higher temperature, thus restores
The flue gas being discharged in fusion process heat with higher.By the exhanst gas outlet of reduction melting device 21 and waste-heat recovery device 22
It is connected, is conducive to the heat recovery in flue gas, to be conducive to lower energy loss, improves energy utilization rate.Preferably,
Above-mentioned waste-heat recovery device 22 is waste heat boiler.
In a preferred embodiment, as shown in Figure 1, reduction melting unit 20 further includes the first cooling device 23,
First cooling device 23 is arranged on high titanium slag transfer pipeline.The first cooling device 23 is arranged on high titanium slag transfer pipeline can
The high titanium slag Ti-enriched slag of output is cooled down, above-mentioned first cooling device 23 preferably water spray elution device 34.This can be real
The purpose being now quickly cooled down.Preferably, it by above-mentioned Ti-enriched slag after the processing of crushing device and grinding device, then is conveyed
To subsequent chlorination reaction unit 30.
In a preferred embodiment, as shown in Figure 1, reduction melting unit 20 further includes the second cooling device 24,
Second cooling device 24 is for cooling down the liquid metal being discharged from liquid metal outlet.Preferably, the second cooling device
24 be copper water jacket cooling device, and the copper water jacket cooling device is arranged in metal phase outlet.It preferably, will be through the second cooling dress
It sets 24 metal phases after cooling and carries out ingot casting.
Due to containing more oxide impurity in high titanium slag, such as the oxide of calcium oxide, magnesium oxide and silicon, in life
Calcium oxide, magnesium oxide can be separated with product titanium tetrachloride during production, and the chloride of silicon can enter tetrachloro
Change in titanium products, causes bigger difficulty to the purification of titanium tetrachloride product, produced Molten salt chlorination furnace in fused salt chlorimation
In journey can not long-period stable operation, especially cause difficulty to subsequent titanium white production.And the application is by going back ilmenite
Former smelting apparatus 21 carries out reduction melting, to make titanium elements be enriched with, while impurity content also further drops in Ti-enriched slag
It is low, in favor of the progress of subsequent chlorination reaction.
In a preferred embodiment, as shown in Figure 1, chlorination reaction unit 30 further include chlorination reaction device 31,
Cleaner feeding mechanism 39 and rectifier unit 38.Chlorination reaction device 31 is provided with titanium tetrachloride entrance and titanium tetrachloride crude product
Outlet；And cleaner feeding mechanism 39 is arranged by cleaner supply opening；And rectifier unit 38 is provided with rectifying entrance, cleaner
Entrance and titanium dioxide outlet, cleaner entrance are connected with cleaner supply opening by cleaner transfer pipeline, and rectifying enters
Mouth is connected with titanium tetrachloride crude product outlet by titanium tetrachloride crude product transfer pipeline, to remove titanium tetrachloride crude product
In vanadium.Preferably, above-mentioned cleaner feeding mechanism 39 is mineral oil feeding mechanism or vegetable oil feeding mechanism.
In chlorination reaction device 31, chlorination reaction occurs for Ti-enriched slag and chlorine, obtains titanium tetrachloride crude product.Cleaner
It is mixed by being delivered in cleaner feeding mechanism 39 in chlorination reaction device 31 with above-mentioned titanium tetrachloride crude product, this can
Make impurity and cleaner in titanium tetrachloride crude product that complex reaction occur, forms macromolecular complex object.Then it will be complexed anti-
Should after obtained reaction system be delivered in rectifier unit 38 and carry out rectification process, above-mentioned macromolecular complex object is removed.
Preferably, chlorination reaction device 31 is gas-solid fluidized bed reactor.
Ti-enriched slag and chlorine are subjected to chlorination reaction in gas-solid fluidized bed reactor, on the one hand can be improved Ti-enriched slag
With the contact area of chlorine, reaction rate is improved；On the other hand the titanium tetrachloride of generation can also be removed in time, to inhibit
The generation of side reaction improves the purity of titanium tetrachloride and the purity of subsequent titanium chloride product.
In a preferred embodiment, as shown in Figure 1, chlorination reaction unit 30 further includes quenching apparatus 32.Chilling
Device 32 is arranged on titanium tetrachloride transfer pipeline.
As the titanium tetrachloride crude product temperature with higher obtained in the chlorination reaction device 31, it is passed into chlorination
After the quenching apparatus 32 being arranged in reaction member 30, connect in the spray liquid of lower temperature and the titanium tetrachloride crude product of higher temperature
During touching, the titanium tetrachloride in titanium tetrachloride crude product can form titanium tetrachloride gases by evaporation, to make tetrachloro
Change titanium crude product to be purified, obtains primary purification gas, and play the effect of cooling.Furthermore the dust in titanium tetrachloride crude product
After the spray process of quenching apparatus 32, it can return and continue to participate in reaction in chlorination reaction device 31.
In a preferred embodiment, as shown in Figure 1, chlorination reaction unit 30 further includes 33 He of cyclone dust collector
Elution device 34, along the flow direction of material, cyclone dust collector 33 and elution device 34 are arranged at quenching apparatus 32 and essence
On titanium tetrachloride transfer pipeline between distillation unit 38, and along the flow direction of material, the setting of cyclone dust collector 33 is being eluted
The upstream of device 34.Cyclone dust collector is set on titanium tetrachloride transfer pipeline between quenching apparatus 32 and rectifier unit 38
33 and elution device 34, the dust in primary purification gas can further be removed, to obtain double purification gas.
In a preferred embodiment, as shown in Figure 1, chlorination reaction unit 30 further includes cryogenic system 35, economic benefits and social benefits
Heat-exchanger rig 36 and tail gas elution device 37, cryogenic system 35, double-effect heat exchange device 36 and tail gas elution device 37 are arranged at
On titanium tetrachloride transfer pipeline between quenching apparatus 32 and rectifier unit 38, and along the flow direction of material, double-effect heat exchange dress
36 upstream is set, the downstream of double-effect heat exchange device 36 is arranged in tail gas elution device 37, be provided in above-mentioned cryogenic purification device-
25 DEG C of refrigerant.
Double-effect heat exchanger is a kind of heat exchanger that can contain cold and hot medium simultaneously.Double purification gas is passed through into cryogenic system
35 carry out subzero treatments, and the double purification gas after deep cooling has certain cooling capacity, using double-effect heat exchange device 36 with mix
Gas exchanges heat, and recycles the cooling capacity in double purification gas, finally will treated that gas send drenches to tail gas through double-effect heat exchange device
Cleaning device 37, further to be washed dust removal process.
In a preferred embodiment, as shown in Figure 1, oxidation unit 40 includes oxidation reaction apparatus 41 and tri-chlorination
Reactive aluminum device 42, oxidation reaction apparatus 41 are provided with titanium tetrachloride entrance, and titanium tetrachloride entrance and titanium tetrachloride outlet are logical
It crosses titanium tetrachloride transfer pipeline to be connected, alchlor reaction unit 42 is arranged in titanium tetrachloride outlet and titanium tetrachloride entrance
Between pipeline on, and alchlor reaction unit 42 is used to using aluminium and chlorine as raw material prepare alchlor.
It is exothermic reaction that chlorine and metallic aluminium, which react and generate the reaction of alchlor,.And oxidation reaction is in higher temperature
Degree is lower to carry out, by alchlor react in the reaction heat released be used to heat titanium tetrachloride, this can be by above-mentioned reaction
Heat is for preheating titanium tetrachloride, additionally it is possible to the reaction heat that effective recycling alchlor reaction process obtains, in turn
Save the heat loss in oxidation reaction process.
Specifically, in a kind of preferred embodiment, alchlor reaction unit 42 is provided with reaction chamber, titanium tetrachloride row
Outlet is connected with the import of reaction chamber, and titanium tetrachloride entrance is connected with the outlet of reaction chamber.
Titanium tetrachloride outlet is connected with the import of reaction chamber, alchlor outlet leads to titanium tetrachloride entrance and is connected
It is logical, alchlor can be added into oxidation reaction apparatus 41, and the addition of alchlor advantageously reduces titanium dioxide product
Partial size, improve its dispersion degree.
In a kind of preferred embodiment, alchlor reaction unit 42 is internally provided with reaction chamber and preheating channel,
And be isolated between reaction chamber and preheating channel by heat transfer component, titanium tetrachloride outlet is connected with the import of preheating channel, and
Titanium tetrachloride entrance is connected with the outlet of preheating channel；Reaction chamber is additionally provided with alchlor outlet, alchlor outlet
It is connected with titanium tetrachloride entrance by alchlor entrance.Preferably, it is thermally conductive to can be the energy such as metal partion (metp) for heat transfer component
Device.
In a preferred embodiment, as shown in Figure 1, oxidation unit 40 further includes preheating device 43 and oxygen supply
Device 44, the oxygen supply device 44 are connected with the oxidation reaction apparatus 41 by oxygen supply pipeline, the preheating
Device 43 is arranged on the oxygen supply pipeline, to preheat to the oxygen in oxygen supply pipeline.Preferably, above-mentioned pre-
Thermal 43 is fuel gas buring boiler.Oxygen can be warming up to 900~960 DEG C by preheating device 43, then reabsorb oxygen
Change the heat discharged in toluene combustion process in reactor, to be allowed to warm to 1700~1800 DEG C.Then by four after preheating
Titanium chloride and preheating after oxygen carry out oxidation reaction, obtain solid-state containing titanium dioxide, chlorine, oxygen gas-solid mixture.So
The chlorine in above-mentioned gas-solid mixture is removed in dechlorination device 45 afterwards, obtains required titanium dioxide product.
Preferably, as shown in Figure 1, oxidation unit 40 further includes dioxygen water supply 46, dioxygen water supply 46 is used
In supplying hydrogen peroxide into dechlorination device 45, to remove remaining chlorine by oxidation reaction.
Embodiment 1
Titanium dioxide is prepared using device shown in FIG. 1.
Ilmenite and coke press 7:1 mass and carry out reduction melting than ingredient, obtain Ti-enriched slag and ferrous metal phase, melting flue gas
It burns byproduct steam through waste heat boiler, the flue gas cool-down of burning to 170 DEG C of qualified discharges after bagroom gathers dust.Ti-enriched slag
Middle Ti content is 93wt%, titanium recovery rate 98%.
Than ingredient and chlorine chlorination reaction occurs in a fluidized bed reactor for Ti-enriched slag and coke by 3:1 mass, and chlorination is anti-
The reaction temperature answered is 950~1050 DEG C, and reaction pressure is 110~150KPa.React the gaseous mixture containing titanium tetrachloride generated
Titanium tetrachloride liquid crude product is obtained after chilling elution, dedusting, cooling condensation.The yield of chlorination reaction is 95%.
Titanium tetrachloride crude product carries out rectifying, titanium tetrachloride crude product and mine after slab oil (Wuhan Hua Tai) is except vanadium
The weight ratio of object oil is 1:0.001~0.003, and content of vanadium is 5ppm in refining titanic chloride.
Enter oxidation reaction in furnace with alchlor, potassium chloride, high-temperature oxygen after the heated vaporization of refining titanic chloride, instead
Answering temperature is 1400 DEG C, and the gas-solid mixture after reaction obtains titanium dioxide after processing.Oxidation reaction yield is 99%.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Above-mentioned synthesis system is used to prepare titanium dioxide product, is not related to the use of acid reagent in whole process, and
Environmentally harmful waste is not generated yet；Simultaneously in reduction melting unit, titanium elements are enriched with, and it is higher to obtain Ti content
Ti-enriched slag carries out subsequent chlorination reaction and oxidation reaction using Ti-enriched slag, is conducive to shorten process cycle.Thus use this Shen
The titanium dioxide synthesis system that please be provided can greatly promote the feature of environmental protection of technique, while it also has easily operated, preparation week
The advantages that phase is short and at low cost.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of titanium dioxide synthesis system, which is characterized in that the synthesis system includes:
Ilmenite feeding mechanism (10)；
Reduction melting unit (20), the reduction melting unit (20) are provided with feed opening and high titanium slag outlet, the charging
Mouth is connected with the ilmenite feeding mechanism (10)；
Chlorination reaction unit (30), the chlorination reaction unit (30) are provided with high titanium slag entrance, chlorine inlet and titanium tetrachloride
Outlet, the high titanium slag entrance are connected with the high titanium slag outlet by high titanium slag transfer pipeline；And
Oxidation unit (40), the oxidation reaction unit are provided with titanium tetrachloride entrance and titanium dioxide outlet, the tetrachloro
Change titanium entrance to be connected with the titanium tetrachloride outlet by titanium tetrachloride transfer pipeline.
2. synthesis system according to claim 1, which is characterized in that the reduction melting unit (20) includes:
Reduction melting device (21), the reduction melting device (21) are provided with the feed opening, the high titanium slag outlet, liquid
State metal outlet and exhanst gas outlet；
Waste-heat recovery device (22), the exhanst gas outlet is connected with the waste-heat recovery device (22), in recovered flue gas
Waste heat.
3. synthesis system according to claim 2, which is characterized in that the reduction melting unit (20) further includes first cold
But device (23), first cooling device (23) are arranged on the high titanium slag transfer pipeline.
4. synthesis system according to claim 3, which is characterized in that the reduction melting unit (20) further includes second cold
But device (24), second cooling device (24) are used to carry out the liquid metal being discharged from the liquid metal outlet cold
But.
5. synthesis system according to any one of claim 1 to 4, which is characterized in that the chlorination reaction unit (30)
Further include:
Chlorination reaction device (31), the chlorination reaction device (31) is provided with the titanium tetrachloride entrance and titanium tetrachloride slightly produces
Product outlet；And
Cleaner feeding mechanism (39), the cleaner feeding mechanism (39) are arranged by cleaner supply opening；And
Rectifier unit (38), the rectifier unit (38) are provided with rectifying entrance, cleaner entrance and titanium dioxide discharge
Mouthful, the cleaner entrance is connected with the cleaner supply opening by cleaner transfer pipeline, the rectifying entrance and institute
It states titanium tetrachloride crude product outlet to be connected by titanium tetrachloride crude product transfer pipeline, to remove in titanium tetrachloride crude product
Vanadium.
6. synthesis system according to claim 5, which is characterized in that the chlorination reaction device (31) is gas-solid fluidized bed
Reactor.
7. synthesis system according to claim 5, which is characterized in that the chlorination reaction unit (30) further includes chilling dress
It sets (32), the quenching apparatus (32) is arranged on the titanium tetrachloride transfer pipeline.
8. synthesis system according to claim 7, which is characterized in that the chlorination reaction unit (30) further includes that whirlwind removes
Dirt device (33) and elution device (34), the cyclone dust collector (33) and the elution device (34) are arranged at the urgency
On the titanium tetrachloride transfer pipeline between device for cooling (32) and the rectifier unit (38), and along the flow direction of material,
Upstream of cyclone dust collector (33) setting in the elution device (34).
9. synthesis system according to claim 8, which is characterized in that the chlorination reaction unit (30) further includes deep cooling dress
Set (35), double-effect heat exchange device (36) and tail gas elution device (37), the cryogenic system (35), double-effect heat exchange device (36) and
Tail gas elution device (37) is arranged at the titanium tetrachloride between the elution device (34) and the rectifier unit (38)
On transfer pipeline, and along the flow direction of material, the cryogenic system (35) is arranged in the upper of the double-effect heat exchange device (36)
Trip, tail gas elution device (37) setting are set in the downstream of the double-effect heat exchange device (36), the cryogenic purification device
It is equipped with -25 DEG C of refrigerant.
10. synthesis system according to claim 5, which is characterized in that the oxidation unit (40) includes:
Oxidation reaction apparatus (41), the oxidation reaction apparatus (41) are provided with the titanium tetrachloride entrance；
Alchlor reaction unit (42), the alchlor reaction unit (42) are arranged in the titanium tetrachloride outlet and institute
It states on the pipeline between titanium tetrachloride entrance, and the alchlor reaction unit (42) is used to prepare using aluminium and chlorine as raw material
Alchlor.
11. synthesis system according to claim 10, which is characterized in that
The alchlor reaction unit (42) is provided with reaction chamber, the import of the titanium tetrachloride outlet and the reaction chamber
It is connected, and the titanium tetrachloride entrance is connected with the outlet of the reaction chamber；Or
The alchlor reaction unit (42) is internally provided with reaction chamber and preheating channel, and the reaction chamber and described pre-
It is isolated between the passage of heat by heat transfer component, the titanium tetrachloride outlet is connected with the import of the preheating channel, and described
Titanium tetrachloride entrance is connected with the outlet of the preheating channel；The reaction chamber is additionally provided with alchlor outlet, and described three
Aluminium chloride outlet is connected with the titanium tetrachloride entrance by alchlor entrance.
12. synthesis system according to claim 11, which is characterized in that the oxidation unit (40) further includes preheating device
(43) and oxygen supply device (44), the oxygen supply device (44) and the oxidation reaction apparatus (41) pass through oxygen supply
Pipeline is connected, and the preheating device (43) is arranged on the oxygen supply pipeline, in the oxygen supply pipeline
Oxygen is preheated.
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