CN116199257B - Separation and recovery method of chlorinated product in titanium tetrachloride production process - Google Patents
Separation and recovery method of chlorinated product in titanium tetrachloride production process Download PDFInfo
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- CN116199257B CN116199257B CN202310209174.8A CN202310209174A CN116199257B CN 116199257 B CN116199257 B CN 116199257B CN 202310209174 A CN202310209174 A CN 202310209174A CN 116199257 B CN116199257 B CN 116199257B
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000926 separation method Methods 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 24
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 75
- 239000007787 solid Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 29
- 229910000831 Steel Inorganic materials 0.000 claims description 26
- 239000010959 steel Substances 0.000 claims description 26
- 229960002089 ferrous chloride Drugs 0.000 claims description 20
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- 229910000838 Al alloy Inorganic materials 0.000 claims description 17
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 17
- 239000000428 dust Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000008247 solid mixture Substances 0.000 claims description 5
- 239000002912 waste gas Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000004537 pulping Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- 229910001510 metal chloride Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- 229910000545 Nickel–aluminium alloy Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- VZVLQKOGWNLVAC-UHFFFAOYSA-J tetrachlorotitanium vanadium Chemical compound [V].Cl[Ti](Cl)(Cl)Cl VZVLQKOGWNLVAC-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 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
- 239000004744 fabric Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
- B01D45/16—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C5/00—Apparatus in which the axial direction of the vortex is reversed
- B04C5/08—Vortex chamber constructions
-
- 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
- C01G23/024—Purification of tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a separation and recovery method of a chlorination product in a titanium tetrachloride production process, which comprises the following steps: a step of discharging the reactants and the offgas from the production process of titanium tetrachloride from the chlorination reaction device, and a step of separating and recovering the discharged reactants and the offgas into a plurality of steps, wherein the separating and recovering includes passing the discharged reactants and the offgas sequentially through a plurality of cyclone separators. The air flow separation process of the invention precisely controls the temperature of each stage, separates out corresponding substances by utilizing the forms of each component under different specific temperature conditions, and avoids the environmental protection problem of waste treatment caused by mixing, pulping and filtering the separated dust-collecting slag. Meanwhile, the cyclone separator used at high temperature is aimed and improved, the service life of equipment is prolonged, and good efficiency is exerted in the process by utilizing the equipment.
Description
Technical Field
The invention relates to the technical field of chemical industry, relates to production, separation and recovery of chemical raw materials, and in particular relates to a separation and recovery method of a chlorinated product in a titanium tetrachloride production process.
Background
At present, in the process of producing titanium pigment by a chlorination method, a titanium-containing raw material and chlorine react in the presence of a carbon reducing agent to generate titanium tetrachloride, and the titanium tetrachloride reacts at a high temperature. Titanium-rich raw materials such as rutile, ilmenite, high titanium slag and the like are mainly used as titanium-containing ores, and the components of the raw materials are mainly iron oxides except titanium oxides. Iron reacts with oxides of other metals such as titanium to form metal chlorides, which are separated. The main constituents in the chlorinator vent product gas stream are titanium tetrachloride and other metal chloride impurities, carbon monoxide and carbon dioxide gases, inert gases such as nitrogen, unreacted ore and coke solid particles. Metal chloride impurities relate to the chlorides of trace metals contained in iron products, other ores.
Existing processes and manufacturing facilities have been studied for the recovery and separation of titanium tetrachloride. For example, chinese patent publication CN1415547a discloses a technique and apparatus for treating titanium tetrachloride vanadium-containing slurry. According to the technical scheme, a submerged pump in a titanium tetrachloride vanadium-containing slurry storage tank is utilized to convey slurry into a mechanical rotary sprayer at the top of a first-stage gravity dust collector of a chlorination system through a pipeline, and due to the high-speed rotation of a nozzle in the sprayer, the slurry is sprayed into the dust collector to exchange heat with high-temperature mixed gas discharged from a chlorination furnace in a countercurrent manner, titanium tetrachloride fog drops or liquid drops in the slurry are gasified in the descending process, and most vanadium-containing solids are settled into a dust box at the bottom of the dust collector under the action of gravity.
However, the prior art has the problems that the slurry can only be utilized at low temperature (temperature of 60-80 ℃), the dust and slag consist of unreacted ore and coke particles and solid parts of high boiling point metal chlorides and refined slurry, these water-soluble and water-insoluble mixtures are slurried together and then separated by press filtration, the literature describes a method for preparing water purifier solutions and crystals from the filtrate, the preparation of crystals requires evaporation concentration of the primary filtrate obtained, but a large amount of energy is required, the treatment cost is too high, and the economy is unreasonable, if the solution is prepared, the concentration is too low, the concentration is required to have the utilization value, if high grade titanium ore is used, the iron content is less, the concentration of ferric chloride is lower, and the cost required to increase the concentration of ferric chloride is higher. In addition, ferric trichloride can be converted into ferric hydroxide flocculent precipitate after primary filtrate neutralization, and the precipitate is easy to block filter cloth filter holes.
Disclosure of Invention
From the above related art, there is a need for improved processes and apparatus for the separation and recovery of chlorinated products in titanium tetrachloride production processes.
The invention relates to a separation process of a gas flow of a product discharged from a chlorination furnace, which is characterized in that different temperatures are controlled, corresponding substances are separated by utilizing the forms of components under different temperature conditions, the environmental protection problem of waste treatment caused by mixing, pulping and filtering separated dust-collecting slag in the traditional process is avoided, and various chlorination products are accurately controlled and collected. Meanwhile, the cyclone separator used at high temperature is aimed and improved, so that the service life of equipment is prolonged, and good efficiency is exerted in the specific process by utilizing the equipment.
The invention provides a separation and recovery method of a chlorination product in a titanium tetrachloride production process, which comprises the following steps:
a step of discharging the reactants and the off-gas from the chlorination reaction device in the titanium tetrachloride production process, and a step of separating and recovering the discharged reactants and off-gas into a plurality of steps,
the separation and recovery into a plurality of steps includes passing the discharged reactants and exhaust gas sequentially through a plurality of cyclone separators.
According to an alternative technical solution, the method comprises the following steps:
step 1): discharging a mixed stream of reactants and exhaust gas from the top of the chlorination reactor, the mixed stream carrying the reactants and exhaust gas having a temperature of 800 to 1000 ℃, the mixed stream entering a first cyclone separator to separate a solid phase portion from a gas phase; the solid phase part is discharged through an underflow discharge channel of the first cyclone separator and enters a first dust collection buffer tank;
step 2): introducing the gas exiting the upper portion of said first cyclone into a second cyclone while simultaneously introducing titanium tetrachloride refining slurry, said titanium tetrachloride refining slurry having a temperature of not less than 700 ℃, said slurry carrying a gaseous stream through said second cyclone, wherein an underflow solids portion exits the lower outlet of said second cyclone;
step 3): discharging the gaseous stream passing through the second cyclone from the top thereof;
step 4): spraying titanium tetrachloride liquid into the gaseous stream discharged in the step 3) so that the temperature of the gaseous stream is reduced to 500-550 ℃, thereby precipitating ferrous chloride crystals; introducing the gas-solid mixture carrying the ferrous chloride crystals into a third cyclone separator, so that the ferrous chloride crystals flow out from the bottom of the third cyclone separator;
step 5): re-spraying titanium tetrachloride liquid into the gas stream discharged in the step 4) so that the temperature of the gas stream is reduced to 150-270 ℃ to separate out ferric trichloride solids, and injecting the gaseous stream carrying the ferric trichloride solids into a fourth cyclone separator so that the ferric trichloride flows out from the bottom of the fourth cyclone separator;
step 6) the gaseous stream is withdrawn from the top of the fourth cyclone in said step 5), and the crude titanium tetrachloride liquid is obtained by further cooling.
According to an alternative embodiment, the method further satisfies one or more of the following process conditions:
a) The temperature of the mixed stream carrying reactants and exhaust gas in step 1) is 850 to 950 ℃;
b) The temperature of the titanium tetrachloride refining slurry in step 2) is 700 to 800 ℃, preferably equal to about 800 ℃;
c) The temperature of the gaseous stream in step 4) is reduced to 530-540 ℃, more preferably to 535 ℃;
d) The temperature of the gas stream in step 5) is reduced to 170 to 250 ℃, preferably to about 240 ℃;
e) The temperature of the gas stream exiting the top of the fourth cyclone is 150 ℃ to 160 ℃.
According to an alternative solution, the first cyclone separator used in said step 1) is a cyclone separator provided with a high temperature and corrosion resistant coating material.
According to an alternative solution, wherein the first cyclone used in said step 1) is a cyclone provided with a high temperature and corrosion resistant coating material, and said cyclone comprises: the cyclone unit is provided with a steel surface, and the steel surface is coated with nickel-aluminum alloy; and a collection chamber.
According to an alternative technical scheme, the nickel-aluminum alloy coated on the surface of the steel comprises the following components in percentage by mass: al:4% -6%; 3 to 4% of Fe; rare earth elements Gd, yb, ce, each accounting for about 0.1% w to 0.3%; the balance being Ni.
According to an alternative technical scheme, the steel surface of the cyclone unit is the surface of No. 35 steel.
A second aspect of the present invention provides an apparatus for carrying out the above method, the apparatus comprising:
a chlorination reaction furnace;
a plurality of cyclone separators; wherein the method comprises the steps of
One or more of the plurality of cyclones comprises a cyclone unit, the surface of which is coated with nickel aluminium alloy.
According to an optional technical scheme, the nickel-aluminum alloy comprises the following components in percentage by mass: al:4% to 6%; 3 to 4% of Fe; rare earth elements Gd, yb, ce, each accounting for about 0.1% w to 0.3%; the balance being Ni;
preferably, the nickel-aluminum alloy comprises the following components in percentage by mass: al:4.5%; 4% of Fe; gd:0.1%, yb:0.1%, ce:0.1% and the balance of Ni; or (b)
The nickel-aluminum alloy comprises the following components in percentage by mass: al:5.5%; 4% of Fe; gd:0.1%, yb:0.1%, ce:0.3% and the balance Ni.
The technical scheme and advantages of the present invention will be explained and illustrated in more detail below with reference to the detailed description. It should be understood that the matters presented in the description and the detailed description are only for clearly illustrating the technical solution of the present invention and the advantages thereof, and do not limit the scope of the present invention. Based on the disclosure of the specification, a person skilled in the art can obtain various changed technical solutions for various reasonable changes, and as long as the spirit of the invention is not deviated, all the changed technical solutions should be understood to be included in the protection scope of the invention.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosed embodiments and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain, without limitation, the disclosed embodiments.
FIG. 1 is a schematic diagram of an apparatus for the product and off-gas separation process of the present invention;
FIG. 2 is a schematic view of a cyclone separator employed in an embodiment of the present invention;
figure 3 shows a schematic cross-sectional view and 400 x metallographic pictures of the surface of a steel material coated with a cyclone unit of the coating of the invention.
Reference numerals illustrate:
1-a high titanium slag reservoir; 2-petroleum coke storage; 3-chlorine storage tank; a 4-chlorination reactor; 5-quenching conveying pipe;
11-a first cyclone; 12-a first dust collection buffer tank; 21-a second cyclone; 22-a second dust collection buffer tank; 31-a third cyclone; 32-a third dust collection buffer tank; 41-fourth cyclone separator; 42-fourth buffer tank; 111-cyclone unit, 112-collection chamber.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the invention.
Before the description of the specific embodiments, it is to be noted that those skilled in the art, based on the teachings and teachings of the present disclosure, are able to select appropriate raw materials, and perform the relevant tests using the relevant test equipment and obtain the corresponding results, and that those skilled in the art, for raw materials not specifying a particular manufacturer or route, are able to select raw materials meeting the corresponding needs as reaction starting materials based on the disclosure and needs of the present specification. It will also be appreciated from the present disclosure that the reaction feeds for the process portion compounds are derived from the primary product synthesized in the preamble of the present disclosure, and that the "plurality" as present in the present disclosure indicates a meaning of greater than one, such as two, three, four or more.
Example 1
Step 1): referring to fig. 1, the process for producing titanium tetrachloride proceeds with the reactants and off-gases being withdrawn from the top of the chlorination reactor 4. The composition of the reaction off-gas material mainly comprises inert gas, metal chloride steam, unreacted titanium ore and coke solid particles, and the temperature of the reaction off-gas carrying the reactants is controlled between 800 and 1000 ℃, preferably between 850 and 950 ℃. Unreacted titanium ore and coke solid particles are directly fed into the first cyclone 11 to be separated from the gas phase. Here, the first cyclone 11 applied is a material provided with a high temperature and corrosion resistant coating, which will be described in more detail below. The solids fraction is discharged through the underflow discharge channel of the first cyclone 11 and into the first dust collection buffer tank 12, and the discharge device may be any suitable device, in this embodiment, a rotary blanking valve is preferably used, an air lock valve with nitrogen cooling and air locking functions is preferably used, a double-valve structure may be adopted, nitrogen is introduced between the two valves, and the stream gas is replaced by the nitrogen. The gas lock valve with nitrogen cooling and gas locking functions can effectively reduce the amount of gas carried in solid materials. The solid material in the underflow part of said first cyclone 11 mainly contains titanium ore and coke. This portion of the solids may be returned to the chlorination furnace after treatment or used for other purposes.
Step 2): the gaseous fraction discharged from the upper part of the first cyclone 11 is fed via a high temperature pipe (not shown in fig. 1) to the next cyclone (the second cyclone 21), during which process titanium tetrachloride refining slurry is fed via a high temperature pipe (not shown in fig. 1) at a controlled temperature of not less than 700 c (preferably 800 c or higher, in this embodiment, the slurry temperature is 800 c), the slurry is fed in an atomized state (called atomized slurry), the titanium tetrachloride in the titanium tetrachloride refining slurry is rapidly vaporized and then combined into a material gas stream, the main component in the slurry comprises vanadium oxide which dries into a solid fraction, the gaseous stream carrying the solid vanadium oxide is fed via the second cyclone 21, the underflow solid fraction is fed from the lower outlet of the second cyclone to the second dust collecting buffer tank 22, the gas locking device uses the same rotary blanking valve as in step 1), and the collected vanadium oxide-containing solid can be used for extracting vanadium such as vanadium pentoxide by sodium oxidation.
In step 2), alternatively, the unreacted titanium slag and petroleum coke dust are directly separated without cooling the refined slurry of the refined vanadium-containing titanium tetrachloride. In this process, the second cyclone 21 may use the same equipment as the first cyclone 11.
Step 3) the top gas of the second cyclone 21 is mainly a gas stream free of solid impurities, which mainly comprises inert gases (such as carbon monoxide, carbon dioxide, nitrogen, etc.) which cannot be liquefied, and also comprises product metal chloride vapor (mainly titanium tetrachloride) and impurity metal chloride vapor.
In the process of the invention, the boiling points of the metal chlorides are different, so that different metal chloride products can be separated by controlling different temperatures, and the aim of purifying the titanium tetrachloride product is also achieved.
The inventor finds that the metal chloride steam is mainly iron chloride except the titanium tetrachloride product under the condition of a large-scale production line process, other metals are trace, if a high-grade titanium-containing raw material is used, the content of other metal chlorides is less, and the metal chlorides which can be separated out mainly comprise ferrous chloride and ferric trichloride.
The chemical reaction formula related to the iron element is as follows:
FeO+TiO 2 +3C+7/2Cl 2 ＝FeCl 3 +3CO+TiCl 4
when the temperature is cooled to 500-550 ℃, the following reactions will rapidly tend to occur, for example, in an inert environment:
FeCl 3 ←→FeCl 2 +1/2Cl 2
ferrous chloride crystals are formed, and ferrous chloride crystal products can be isolated in this temperature range.
Under the further research of the inventor according to the technological parameters, the melting point of the ferric trichloride is 306 ℃ and the boiling point is 315 ℃; thus, when the temperature is reduced to a range of 150 to 270 ℃, a portion of the ferric trichloride solid product may be separated out in this temperature range.
From the above findings, the applicant devised steps 4) and 5).
Step 4) separating ferrous chloride
The gas discharged in step 3) (gas stream substantially free of solid particles) is injected into the crude titanium tetrachloride liquid (temperature 90 ℃ to 100 ℃, preferably around 90 ℃) so that the gas stream temperature is reduced to 500-550 ℃, preferably 530-540 ℃, the present embodiment sets 535 ℃, ferrous chloride crystals are separated out, the gas-solid mixture enters the third cyclone 31, the solid fraction flowing out from the bottom of the third cyclone 31 mainly contains ferrous chloride, and the gas locking device is preferably used the same as the aforementioned step 1) and step 2), and the effluent enters the third dust collection buffer tank 32. Under the conditions set in the step 4), particles in a stable crystalline state of ferrous chloride can be obtained.
Step 5) the gas stream substantially free of solid particles from step 4) is again sprayed with a crude titanium tetrachloride liquid (titanium tetrachloride liquid temperature 40 to 50 ℃) and the temperature is reduced to 150 to 270 ℃, preferably 170 to 250 ℃, in this example around 240 ℃, at which time ferric trichloride solids are precipitated, the gas-solid mixture enters the fourth cyclone 41, the solid fraction exiting the bottom of the fourth cyclone being essentially composed of ferric trichloride, the gas lock and in the process being the same as in step 1), step 2), step 3) and/or step 4) described above.
Step 6) the gas stream exiting the top of the fourth cyclone 41 in step 5) above mainly comprises titanium tetrachloride vapor (titanium tetrachloride boiling point around 135 c) and an inert gas mixture, liquefied by a condenser into a crude titanium tetrachloride liquid, which is fed into a fourth buffer tank 42 where refined vanadium removal may be added, the product being refined titanium tetrachloride. In a subsequent optional step, the titanium tetrachloride may be used as a feedstock for the next step of producing titanium dioxide or titanium metal, and the vanadium-containing slurry may be returned to the chlorination furnace effluent stream for treatment as previously described.
Step 7) sub-cooling titanium tetrachloride and collecting gas (optional step)
The main constituents of the still uncondensed gases after the treatment of step 6) are carbon monoxide, small amounts of titanium tetrachloride, nitrogen and other inert gases, these gases being subjected to cryogenic cooling at-15 ℃ to further condense the trace amounts of titanium tetrachloride contained therein (apparatus not shown). The carbon monoxide in the rest waste gas is valuable toxic gas and cannot be directly discharged, the waste gas enters an RTO regenerative oxidation furnace device (not shown), the carbon monoxide as a main component is further oxidized into carbon dioxide gas and heat energy is recovered, and finally the gas reaches the standard and is discharged into the atmosphere.
Example 1'
This example illustrates in more detail the first cyclone 11 of material with a high temperature and corrosion resistant coating applied in example 1. It should be noted that the first cyclone 11 in embodiment 1' may be applied to the second cyclone 21, the third cyclone 31, and/or the fourth cyclone 41.
As described in example 1, the composition of the reaction off-gas material in the first step mainly comprises inert gas, metal chloride vapor, unreacted titanium ore and coke solid particles, and the reaction off-gas carrying the reactants has a minimum temperature of around 850 ℃ and causes a large thermal shock to the cyclone device, particularly the cyclone unit in the cyclone device.
Accordingly, the inventors have made research and experimental attempts to employ improved cyclonic separating apparatus in embodiments of the present invention.
The cyclone used in example 1 of the present invention is shown in fig. 2 as an internal schematic diagram (which may represent the first cyclone 11, or the second, third, and/or fourth cyclones). In fig. 2, the outermost housing of the first cyclone 11 is removed from the schematic view, exposing the cyclone unit 111, and the collection chamber 112. The inventors have found that the cyclone unit 111 of the cyclone separator employed in the present invention is made of 35 gauge steel, which has a certain thermal shock resistance, but under the impact of a long-term high-temperature high-flow-rate steam flow, surface pits and spots appear after a certain period of use (e.g., 1 month), reducing the life of steel parts, and even affecting the separation efficiency.
The inventor finds that the No. 35 steel part has good adhesion with nickel-aluminum alloy, and the nickel-aluminum alloy coating can effectively ensure the integrity of the steel surface of the cyclone unit 111.
Thus, in a preferred version of the invention, the surfaces of the cyclone units of one or more of the first cyclone 11, the second cyclone, the third cyclone, and the fourth cyclone are coated with nickel-aluminium alloy.
The nickel aluminum alloy coating may be applied to the steel surface of cyclone unit 111 prior to the cyclone being started up in the production line. The collection chamber 112 may also be coated with the same coating. Alternatively, for cost reasons, the collection chamber 112 may maintain the surface of the original steel material without coating the corresponding alloy material. The nickel aluminum alloy may be applied to the surface of the cyclone unit by a spraying process known in the art.
In a typical embodiment, the nickel aluminum alloy coating has a composition of (mass percent) Al:4-6%; 3-4% of Fe; rare earth elements Gd, yb, ce, each accounting for about 0.1% w to 0.3%; the balance being nickel (Ni).
Fig. 3 shows a schematic cross-sectional view and 400 x metallographic pictures of the steel surface of a cyclone unit 111 coated with the coating according to the invention.
It can be seen from fig. 3 that the surface of steel No. 35 is well bonded to the nickel-aluminum alloy coating of the present invention (light-colored portion in the left half of the right metallographic photograph of fig. 3), and there is almost no defect in the middle caused by poor bonding.
Table 1 shows cyclone unit surface lifetime statistics obtained with steel surfaces of different cyclone units:
table 1: cyclone unit surface life obtained from the surfaces of different cyclone units
From the above comparison, it can be seen that the alloy surface with the improved cyclone unit of the present invention has a significantly improved working surface and can be operated continuously for a long period of time under high temperature impact. While it can be seen in the comparison of examples 1-1 and 1-2 that the properly increased Al content and rare earth Ce content further contribute to the improvement of the high temperature working surface. Compared with the exposed surface of No. 35 steel, the improved alloy surface of the cyclone unit improves the working efficiency and the safety production coefficient, and correspondingly improves the separation accuracy and purity of the product.
Example 2
Example 2 the same process flow as in example 1 was carried out, except that in step 4 and step 5 of example 2, the temperature of the different crude titanium tetrachloride liquid and the temperature of the whole gas stream were adjusted to effect different separation of ferrous chloride and ferric trichloride. The experimental results are presented in table 2.
From example 2 shown in Table 2, the temperature of the crude titanium tetrachloride liquid injected in step 4) can effectively adjust and optimize the product ratio of the ferric iron product and the ferrous chloride, and efficiently separate the ferrous iron product and the ferric chloride. When the injected mud temperature in step 4) is too low and results in a lower gas stream temperature, ferrous chloride may be overproduced not enough to allow separation in the cyclone step of step 4), allowing the excess ferrous product to flow to the next step; the temperature in step 4) is preferably between 530℃and 540℃and preferably around 535 ℃.
According to the embodiments and technical content described in the specification of the present invention, the present invention can provide at least the following technical solutions: although the present disclosure includes specific embodiments, it will be obvious to those skilled in the art that various substitutions and modifications may be made in form and detail without departing from the spirit and scope of the present claims and their equivalents. The embodiments described herein should be considered in an illustrative sense only and not for the purpose of limitation. The description of features and aspects in each embodiment is considered to apply to similar features and aspects in other embodiments. Therefore, the scope of the present disclosure should not be limited by the specific description, but by the claims, and all changes within the scope of the claims and the equivalents thereof are to be construed as being included in the technical solutions of the present disclosure.
The invention at least provides the following technical scheme:
scheme 1: a method for separating and recovering a chlorinated product in a titanium tetrachloride production process, which comprises the following steps:
a step of discharging the reactants and the off-gas from the chlorination reaction device in the titanium tetrachloride production process, and a step of separating and recovering the discharged reactants and off-gas into a plurality of steps,
the separation and recovery into a plurality of steps includes passing the discharged reactants and exhaust gas sequentially through a plurality of cyclone separators.
Scheme 2: the method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to scheme 1, wherein the method specifically comprises the following steps:
step 1): discharging a mixed stream of reactants and exhaust gas from the top of the chlorination reactor, the mixed stream carrying the reactants and exhaust gas having a temperature of 800 to 1000 ℃, the mixed stream entering a first cyclone separator to separate a solid phase portion from a gas phase; the solid phase part is discharged through an underflow discharge channel of the first cyclone separator and enters a first dust collection buffer tank;
step 2): introducing the gas exiting the upper portion of said first cyclone into a second cyclone while simultaneously introducing titanium tetrachloride refining slurry, said titanium tetrachloride refining slurry having a temperature of not less than 700 ℃, said slurry carrying a gaseous stream through said second cyclone, wherein an underflow solids portion exits the lower outlet of said second cyclone;
step 3): discharging the gaseous stream passing through the second cyclone from the top thereof;
step 4): spraying titanium tetrachloride liquid into the gaseous stream discharged in the step 3) so that the temperature of the gaseous stream is reduced to 500-550 ℃, thereby precipitating ferrous chloride crystals; introducing the gas-solid mixture carrying the ferrous chloride crystals into a third cyclone separator, so that the ferrous chloride crystals flow out from the bottom of the third cyclone separator;
step 5): re-spraying titanium tetrachloride liquid into the gas stream discharged in the step 4) so that the temperature of the gas stream is reduced to 150-270 ℃ to separate out ferric trichloride solids, and injecting the gaseous stream carrying the ferric trichloride solids into a fourth cyclone separator so that the ferric trichloride flows out from the bottom of the fourth cyclone separator;
step 6) the gaseous stream is withdrawn from the top of the fourth cyclone in said step 5), and the crude titanium tetrachloride liquid is obtained by further cooling.
Scheme 3: a method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to the foregoing aspect, wherein the method further satisfies one or more of the following process conditions:
a) The temperature of the mixed stream carrying reactants and exhaust gas in step 1) is 850 to 950 ℃;
b) The temperature of the titanium tetrachloride refining slurry in step 2) is 700 to 800 ℃, preferably equal to about 800 ℃;
c) The temperature of the gaseous stream in step 4) is reduced to 530-540 ℃, more preferably to 535 ℃;
d) The temperature of the gas stream in step 5) is reduced to 170 to 250 ℃, preferably to about 240 ℃;
e) The temperature of the gas stream exiting the top of the fourth cyclone is 150 ℃ to 160 ℃.
Scheme 4: the method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to any one of the foregoing aspects, wherein,
the first cyclone used in said step 1) is a cyclone provided with a high temperature and corrosion resistant coating material.
Scheme 5. The method for separating and recovering chlorinated products in the titanium tetrachloride production process according to any one of the previous schemes, wherein,
the first cyclone used in said step 1) is a cyclone provided with a high temperature and corrosion resistant coating material and said cyclone comprises:
the cyclone unit is provided with a steel surface, and the steel surface is coated with nickel-aluminum alloy; and
a collection chamber.
Scheme 6. The method for separating and recovering the chlorinated product in the titanium tetrachloride production process according to any one of the previous schemes, wherein,
the nickel-aluminum alloy coated on the surface of the steel comprises the following components in percentage by mass: al:4% -6%; 3 to 4% of Fe; rare earth elements Gd, yb, ce, each accounting for about 0.1% w to 0.3%; the balance being Ni.
Scheme 7. The method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to any one of the foregoing schemes, wherein the steel surface of the cyclone unit is the surface of steel No. 35.
Scheme 8. An apparatus for carrying out the above method, the apparatus comprising:
a chlorination reaction furnace;
a plurality of cyclone separators; wherein the method comprises the steps of
One or more of the plurality of cyclones comprises a cyclone unit, the surface of which is coated with nickel aluminium alloy.
Scheme 9. According to any one of the preceding schemes, wherein the nickel aluminium alloy has the following composition in mass percent: al:4% to 6%; 3 to 4% of Fe; rare earth elements Gd, yb, ce, each accounting for about 0.1% w to 0.3%; the balance being Ni;
preferably, the nickel-aluminum alloy comprises the following components in percentage by mass: al:4.5%; 4% of Fe; gd:0.1%, yb:0.1%, ce:0.1% and the balance of Ni; or (b)
The nickel-aluminum alloy comprises the following components in percentage by mass: al:5.5%; 4% of Fe; gd:0.1%, yb:0.1%, ce:0.3% and the balance Ni.
Scheme 9: according to any of the preceding schemes, wherein the above step 1), step 2), step 3), and step 4) employ cyclone separators that are identical to or different from each other.
Scheme 10: the process according to any of the preceding claims, wherein the discharge device in step 1) uses a rotary blanking valve, preferably an airlock valve with nitrogen cooling and with airlock function, wherein a double valve structure is employed.
Scheme 11: according to any of the preceding claims, wherein the main component of the slurry in step 2) comprises vanadium oxide, the gaseous stream carrying the solid vanadium oxide is passed through a second cyclone, the underflow solids fraction is discharged from the lower outlet of the second cyclone into a second dust collection buffer tank 22, and the gas lock means uses the same rotary blanking valve as in step 1).
Scheme 12: according to any one of the preceding claims, wherein the solid fraction flowing out of the bottom of the third cyclone in step 4) comprises mainly ferrous chloride, and the effluent enters the third dust collection buffer tank.
Scheme 13: according to any one of the preceding claims, wherein the gas stream exiting the top of the fourth cyclone in step 5) above comprises mainly a mixture of titanium tetrachloride vapor and inert gas, liquefied by a condenser into a crude titanium tetrachloride liquid, which is fed into a fourth buffer tank, to which a refining agent is added for removing vanadium; the titanium tetrachloride is used as a raw material for the next production of titanium dioxide or titanium metal, and the vanadium-containing slurry is returned to the chlorination furnace exhaust stream for treatment in the manner set forth in the scheme or step described above.
Scheme 14: according to any one of the preceding schemes, further comprising step 7): cryogenic titanium tetrachloride and collection gas:
after the treatment of the step 6), the gas which is not condensed still contains carbon monoxide, titanium tetrachloride and nitrogen, and the titanium tetrachloride contained in the gas is further condensed by deep cooling at the temperature of less than 0 ℃; and (3) enabling carbon monoxide in the residual waste gas to enter an RTO regenerative oxidation furnace device, oxidizing the carbon monoxide in the residual waste gas into carbon dioxide gas, recovering heat energy, and finally discharging the gas to the atmosphere after reaching the standard.
Claims (6)
1. A method for separating and recovering a chlorinated product in a titanium tetrachloride production process, which comprises the following steps:
a step of discharging the reactants and the off-gas from the chlorination reaction device in the titanium tetrachloride production process, and a step of separating and recovering the discharged reactants and off-gas into a plurality of steps,
the separation and recovery of the discharged reactants and the discharged waste gas by a plurality of cyclone separators in sequence; and
wherein the method specifically comprises the following steps:
step 1): discharging a mixed stream of reactants and exhaust gas from the top of the chlorination reactor, the mixed stream carrying the reactants and exhaust gas having a temperature of 800 to 1000 ℃, the mixed stream entering a first cyclone separator to separate a solid phase portion from a gas phase; the solid phase part is discharged from an underflow discharge channel of the first cyclone separator and enters a first dust collection buffer tank;
step 2): introducing the gas exiting the upper portion of said first cyclone into a second cyclone while simultaneously introducing titanium tetrachloride refining slurry, said titanium tetrachloride refining slurry having a temperature of not less than 700 ℃, said slurry carrying a gaseous stream through said second cyclone, wherein an underflow solids portion exits the lower outlet of said second cyclone;
step 3): discharging the gaseous stream passing through the second cyclone from the top thereof;
step 4): spraying titanium tetrachloride liquid into the gaseous stream discharged in the step 3) so that the temperature of the gaseous stream is reduced to 500-550 ℃, thereby precipitating ferrous chloride crystals; introducing the gas-solid mixture carrying the ferrous chloride crystals into a third cyclone separator, so that the ferrous chloride crystals flow out from the bottom of the third cyclone separator;
step 5): re-spraying titanium tetrachloride liquid into the gas stream discharged in the step 4) so that the temperature of the gas stream is reduced to 150-270 ℃ to separate out ferric trichloride solids, and injecting the gaseous stream carrying the ferric trichloride solids into a fourth cyclone separator so that the ferric trichloride flows out from the bottom of the fourth cyclone separator;
step 6) the gaseous stream is withdrawn from the top of the fourth cyclone in said step 5), and the crude titanium tetrachloride liquid is obtained by further cooling.
2. The method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to claim 1, wherein the method further satisfies one or more of the following process conditions:
a) The temperature of the mixed stream carrying reactants and exhaust gas in step 1) is 850 to 950 ℃;
b) The temperature of the titanium tetrachloride refined slurry in the step 2) is 700 to 800 ℃;
c) The temperature of the gaseous stream in step 4) is reduced to 530-540 ℃;
d) The temperature of the gas stream in step 5) is reduced to 170 to 250 ℃;
e) The temperature of the gas stream exiting the top of the fourth cyclone is 150 ℃ to 160 ℃.
3. The method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to claim 1, wherein,
the first cyclone used in said step 1) is a cyclone provided with a high temperature and corrosion resistant coating material.
4. The method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to claim 1, wherein,
the first cyclone used in said step 1) is a cyclone provided with a high temperature and corrosion resistant coating material and said cyclone comprises:
the cyclone unit is provided with a steel surface, and the steel surface is coated with nickel-aluminum alloy; and
a collection chamber.
5. The method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to claim 4, wherein,
the nickel-aluminum alloy coated on the surface of the steel comprises the following components in percentage by mass: al:4% -6%; 3 to 4% of Fe; rare earth elements Gd, yb and Ce accounting for 0.1 to 0.3 percent respectively; the balance being Ni.
6. The method for separating and recovering a chlorinated product in a titanium tetrachloride production process according to claim 4, wherein the surface of the steel material of the cyclone unit is the surface of steel material No. 35.
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| US3261664A (en) * | 1963-11-21 | 1966-07-19 | Du Pont | Process for the production and separation of titanium tetrachloride from crystalline ferrous chloride |
| CN106587143A (en) * | 2016-12-05 | 2017-04-26 | 东华工程科技股份有限公司 | Improvement on chlorination dedusting technology used for chloride process titanium dioxide apparatus |
| CN108793237A (en) * | 2018-07-20 | 2018-11-13 | 东华工程科技股份有限公司 | A kind of processing system and method for high temperature titanium tetrachloride dusty gas |
| CN218516289U (en) * | 2022-08-29 | 2023-02-24 | 河南佰利联新材料有限公司 | Gas-solid high-efficiency separation and ore-coke fine powder recovery system for furnace gas discharged from boiling chlorination furnace |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3261664A (en) * | 1963-11-21 | 1966-07-19 | Du Pont | Process for the production and separation of titanium tetrachloride from crystalline ferrous chloride |
| CN106587143A (en) * | 2016-12-05 | 2017-04-26 | 东华工程科技股份有限公司 | Improvement on chlorination dedusting technology used for chloride process titanium dioxide apparatus |
| CN108793237A (en) * | 2018-07-20 | 2018-11-13 | 东华工程科技股份有限公司 | A kind of processing system and method for high temperature titanium tetrachloride dusty gas |
| CN218516289U (en) * | 2022-08-29 | 2023-02-24 | 河南佰利联新材料有限公司 | Gas-solid high-efficiency separation and ore-coke fine powder recovery system for furnace gas discharged from boiling chlorination furnace |
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