CN103693686A - Method for preparing titanium dioxide - Google Patents
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- CN103693686A CN103693686A CN201310662644.2A CN201310662644A CN103693686A CN 103693686 A CN103693686 A CN 103693686A CN 201310662644 A CN201310662644 A CN 201310662644A CN 103693686 A CN103693686 A CN 103693686A
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- titanium tetrachloride
- chlorination
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Abstract
The invention discloses a method for preparing titanium dioxide. The method comprises the following steps: (1) supplying titaniferous ores and a reducer into a chlorination reactor while supplying oxygen, air and chlorine into the chlorination reactor so as to generate chlorination reaction in the chlorination reactor; (2) carrying out first gas-solid separation treatment on the chlorination reaction mixture obtained in the step (1); (3) carrying out condensation treatment on the gas mixture containing titanium tetrachloride; (4) storing the liquid crude titanium tetrachloride obtained in the step (3) in a titanium tetrachloride storage device; (5) carrying out vanadium removal treatment on the liquid crude titanium tetrachloride by using mineral oil; (6) supplying the fine titanium tetrachloride obtained in the step (5) and oxygen into an oxidation reactor so as to generate oxidation reaction in the oxidation reactor; (7) carrying out second gas-solid separation treatment on the oxidation reaction mixture obtained in the step (6); and (8) carrying out treatment on chlorination dust slag.
Description
Technical field
The present invention relates to chemical field, particularly, the present invention relates to a kind of method of preparing titanium dioxide.
Background technology
The method of producing at present titanium dioxide mainly contains sulfuric acid process and chlorination process.Due to the long flow path of sulfuric acid process, seriously polluted, poor product quality and the method that is progressively chlorinated replaces.
CN1066043 discloses a kind of processing method of preparing Rutile type Titanium Dioxide, it comprises 1), after evenly being mixed with refinery coke, titanium slag puts into chlorination furnace, pass into chlorine and carry out fluidizing chlorination at 800～900 ℃ of temperature, 2), the rough titanium tetrachloride obtaining after chlorination is carried out to separating-purifying to be removed, magnesium, iron, the impurity such as silicon and vanadium, obtain refining titanic chloride, 3), the refining titanic chloride liquid making is in vaporizer, be converted into gas phase, and give heat to 450～800 ℃, 4), gas phase titanium tetrachloride and a small amount of compound modifying agent gas phase aluminum chloride are mixed into oxidized still, oxygen enters oxidized still through plasma generator heating, at 1300～1500 ℃ of temperature, be less than and in 0.1 second, carry out oxidizing reaction and generate solid phase titanium dioxide, 5), rapidly titanium dioxide pressed powder is shifted out to reaction zone and reaction heat is being removed rapidly, collect titanium dioxide generation chlorine and return to chlorination furnace, 6), the titanium dioxide granule powder of collection is pulled an oar into liquid, through two-stage sorting, the fine particle titanium dioxide that is less than 1 micron carries out aftertreatment again, coarse particles grinds and then classification, 7), make used additives carry out coating aftertreatment in pH=7～8 at 50～70 ℃ of temperature, 8), by titanium dioxide slurries after aftertreatment, through twice filtration, charging is moisture is less than 45%, discharging is moisture is less than 1%, 9) dry at 120～160 ℃ of temperature, micronizing, product mean particle size accounts for 70% below 0.3 μ m.
Yet the means of preparing at present titanium dioxide still have much room for improvement.
Summary of the invention
The present invention is intended at least solve one of technical problem existing in prior art.For this reason, one object of the present invention is to propose a kind of method that can effectively prepare titanium dioxide.
In one aspect of the invention, the present invention proposes a kind of method of preparing titanium dioxide.According to embodiments of the invention, the method comprises: (1) is supplied to titaniferous ore, reductive agent in chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore; (2) the described chlorination reaction mixture obtaining in step (1) is carried out to the first gas solid separation processing, to obtain the gaseous mixture and the chlorination dust slag that contain titanium tetrachloride; (3) the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride; (4) resulting described liquid crude titanium tetrachloride in step (3) is stored in titanium tetrachloride storing device; (5) adopting mineral oil to remove vanadium to described liquid crude titanium tetrachloride processes, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the smart titanium tetrachloride that described process is refined, the content of vanadium is below 3ppm; (6) the described smart titanium tetrachloride and the oxygen that in step (5), obtain are supplied in oxidation reactor, to there is oxidizing reaction in described oxidation reactor, to obtain the oxidation mixtures that contains titanium dioxide and chlorine; (7) the described oxidation mixtures obtaining in step (6) is carried out to the second gas solid separation processing, to obtain respectively solid titanium dioxide and chlorine; And process described chlorination dust slag through the following steps (8): (8-1) described chlorination dust slag is carried out to slurrying, press filtration, washing and filtration, to remove the soluble metal muriate in described chlorination dust slag, and obtain the solid slag that contains titanium dioxide and refinery coke; (8-2) the described solid slag that contains titanium dioxide and refinery coke is carried out to carbon successively and roughly select and carbon choosing, to obtain refinery coke and titanium dioxide titanium slag; And (8-3) described titanium dioxide titanium slag is carried out to titanium gravity treatment, to obtain titanium dioxide solid.
Contriver finds, can effectively prepare titanium dioxide, and then by titanium dioxide is carried out to coating processing, can obtain the titanium dioxide of size-grade distribution excellence according to the method for preparing titanium dioxide of the embodiment of the present invention.And, can effectively realize chloride slag is recycled, wherein, the titanium dioxide reclaiming can be for molten salt furnace, and resulting refinery coke can be used as boiler oil.
In addition, the method for preparing titanium dioxide according to the above embodiment of the present invention can also have following additional technical characterictic:
In one embodiment of the invention, described chlorination reaction is to carry out at the temperature of 700～900 degrees Celsius.Preferably, chlorination reaction is to carry out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, carries out chlorination reaction under 850 degrees Celsius, can generate titanium tetrachloride to be significantly better than the efficiency of other temperature.
In one embodiment of the invention, in step (3), further comprise: by a part for described liquid crude titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture contact, to carry out the first cooling process; And utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid crude titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver finds, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, for the first cooling process, can effectively utilize and obtain cooling liquid crude titanium tetrachloride and carry out cooling, thereby reduced the production cost of titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role to be significantly better than the cooling medium of other temperature and type.
In one embodiment of the invention, in step (6), in the described smart titanium tetrachloride obtaining in step (5) and oxygen are supplied to oxidation reactor before, in advance described smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.Thus, can significantly improve the oxidation efficiency of titanium tetrachloride.
In one embodiment of the invention, in advance described smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, in advance by described oxygen preheat to being not less than 1500 degrees Celsius.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, by smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, oxygen preheat, to being not less than 1500 degrees Celsius, can be reduced to the cost of preparing titanium dioxide significantly effectively.When excess Temperature, the needed cost of preheating can significantly increase, and when temperature is too low, in oxidation reactor, can consume too much energy.
In one embodiment of the invention, further comprise: the described chlorine obtaining in step (7) is back in step (1) and carries out chlorination reaction.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 is the schematic flow sheet of preparing according to an embodiment of the invention the method for titanium dioxide;
Fig. 2 is the schematic flow sheet of the method for preparing titanium dioxide of another embodiment according to the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In addition, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".In description of the invention, the implication of " a plurality of " is two or more, unless otherwise expressly limited specifically.
According to an aspect of the present invention, the present invention proposes a kind of method of preparing titanium dioxide.Below with reference to Fig. 1-2, the method for preparing titanium dioxide of the embodiment of the present invention is described in detail.According to embodiments of the invention, the method comprises:
S100: chlorination reaction
Titaniferous ore, reductive agent are supplied in chlorination reactor, and to oxygen gas-supplying, air and chlorine in chlorination reactor, to there is chlorination reaction in chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, reductive agent is refinery coke, and titaniferous ore is titanium slag or rutile titanium ore.According to a particular embodiment of the invention, carry out the temperature condition of chlorination reaction and be not particularly limited, according to concrete example of the present invention, chlorination reaction can be carried out at the temperature of 700～900 degrees Celsius, preferably, chlorination reaction is to carry out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, carries out chlorination reaction under 850 degrees Celsius, can generate titanium tetrachloride to be significantly better than the efficiency of other temperature.In this step, particularly, the production of titanium tetrachloride gases is mainly in chlorination reactor, continuously to add titanium ore (titanium slag or rutile) and reducing substances (refinery coke), and continuously in reactor, passes into oxygen, pressurized air, chlorine; And temperature (titanium slag or rutile) and chlorine in the time of 850 ℃ recur reaction and continue to generate TiCl
4gas, reaction equation is: 2TiO
2+ 3C+4Cl
2=2TiCl
4+ 2CO+CO
2.Thus, can effectively titanium dioxide in titanium ore be converted to titanium tetrachloride gases, and then be beneficial to the high-quality titanium dioxide product of follow-up acquisition.
S200: the first gas solid separation
Resulting chlorination reaction mixture in preceding step is carried out to the first gas solid separation processing, thereby can obtain the gaseous mixture that contains titanium tetrachloride.In this step, the titanium tetrachloride gases producing by chlorination reaction, carbon monoxide, carbonic acid gas be mingled with some solid matters that some unreacted refinery cokes, titanium ore and reaction generate and leaving together chlorination reactor and enter the first gas-solid separating device, realized the separated of titanium tetrachloride gases and solid waste.According to embodiments of the invention, the method for carrying out the first gas solid separation processing can be any known means in this area.
S300: condensation process
The gaseous mixture that contains titanium tetrachloride of gained is carried out to condensation process, thereby can obtain liquid crude titanium tetrachloride.Particularly, condensation process comprises: a part for liquid crude titanium tetrachloride is contacted with the gaseous mixture that contains titanium tetrachloride, to carry out the first cooling process; And utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, thus can obtain liquid crude titanium tetrachloride, wherein, refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver finds, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, in the first cooling process process, can effectively utilize and obtain cooling liquid crude titanium tetrachloride and carry out cooling to the gaseous mixture that contains titanium tetrachloride, thereby significantly reduced the production cost of titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role to be significantly better than the cooling medium of other temperature and type.Meanwhile, adopt the condensation process mode in this step, can be by 99% the horizontal liquid of titanium tetrachloride gases condensation in gas.
S400: storage
In this step, the resulting liquid crude titanium tetrachloride of condensation process step is stored in titanium tetrachloride storing device above.
S500: except vanadium is processed
In this step, adopt mineral oil to remove vanadium to liquid crude titanium tetrachloride and process, to liquid crude titanium tetrachloride is refined, thereby can obtain through refining smart titanium tetrachloride, wherein, in the smart titanium tetrachloride that process is refined, the content of vanadium is below 3ppm.Particularly, adopting mineral oil to remove vanadium processing to liquid crude titanium tetrachloride comprises: in container for evaporation, by liquid crude titanium tetrachloride and mineral oil, its mineral oil in fluid accounts for 1 % by weight of resulting mixture; And along with stirring, the mixture of resulting liquid crude titanium tetrachloride and mineral oil is heated so that by the vanadium in liquid crude titanium tetrachloride by lower boiling VOCl
3be converted into high boiling VOCl
2impurity, to realize the separated of vanadium and titanium tetrachloride, thereby obtains through refining smart titanium tetrachloride.In this step, before liquid crude titanium tetrachloride is mixed with mineral oil, utilize in advance nitrogen to a part that adds mineral oil in container for evaporation, to prevent mineral oil carbonization blocking pipeline.According to embodiments of the invention, the pressure in container for evaporation is also not particularly limited, and according to a particular embodiment of the invention, the pressure in container for evaporation can be 0.5～0.7MPa.Contriver surprisingly finds through great many of experiments, remove vanadium and process and can refine and obtain smart titanium tetrachloride to be significantly better than other pressure under 0.5～0.7MPa pressure.Thus, can significantly improve the quality of the titanium dioxide product of follow-up acquisition.
S600: oxidizing reaction
In this step, the smart titanium tetrachloride and the oxygen that obtain are supplied in oxidation reactor, to there is oxidizing reaction TiCl in oxidation reactor in preceding step
4+ O
2=TiO
2+ 2Cl
2, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.
S700: the second gas solid separation
The oxidation mixtures obtaining in preceding step is carried out to the second gas solid separation processing, to obtain respectively solid titanium dioxide and chlorine.According to embodiments of the invention, the method for carrying out the second gas solid separation processing can be any known means in this area.Contriver's discovery, oxidation mixtures is processed through the second gas solid separation, can effectively prepare titanium dioxide, and then by titanium dioxide is carried out to coating processing, can effectively obtain the titanium dioxide of size-grade distribution excellence.According to embodiments of the invention, the chlorine obtaining in this step is back to and in chlorination reaction step, carries out chlorination reaction.Contriver's discovery, the chlorine obtaining after processing by the second gas solid separation, can be directly used in chlorination reaction, thereby significantly reduce the cost of producing titanium dioxide, has reduced pollution.
S800: chloride slag is processed
In aforementioned chlorination reaction, titanium slag, refinery coke, chlorine enter in the chloride slag that chlorination furnace carries out producing in chlorination reaction process and contain the unreacted titanium dioxide of part and refinery coke, therefore need to be further processed chloride slag.
According to embodiments of the invention, by the slurrying of gained chlorination dust slag, press filtration, washing and filtration, to remove the soluble metal muriate in chlorination dust slag, thereby can obtain the solid slag that contains titanium dioxide and refinery coke.Particularly, in pulping tank, add process water to carry out stirring pulping, slurries are delivered to plate-and-frame filter press and carry out press filtration, press filtration finishes with process water, filter cake to be washed afterwards, finally obtains solid slag.
According to embodiments of the invention, the solid slag that gained is contained to titanium dioxide and refinery coke carries out carbon successively to be roughly selected and carbon choosing, thereby can obtain respectively refinery coke and titanium dioxide titanium slag.According to embodiments of the invention, resulting titanium dioxide titanium slag is carried out to titanium gravity treatment, thereby can obtain titanium dioxide solid.Concrete, chlorination residues is delivered to tripping device (as shaking table etc.), utilize refinery coke different with titanium slag density, by Gravity separation, go out refinery coke and titanium slag.Titanium slag is by further selected separation such as shaking table, hydrocyclones.
According to embodiments of the invention, selected resulting TiO
2titanium dioxide due to granularity is too little can not be for boiling chloridizing furnace as raw material, and fused salt chlorimation is thinner to the granularity requirements of titanium dioxide, the titanium dioxide of separating meets the requirement of fused salt chlorimation, therefore the titanium dioxide of separating is delivered to dehumidification system and is dried, be dried and can adopt the modes such as natural air drying, expansion drying, microwave drying, common drying machine are dried, dry be sent to molten salt furnace as raw material after reaching requirement, refinery coke is directly delivered to boiler house as fuel.
Thus, by adopting the method for preparing titanium dioxide of the embodiment of the present invention, can effectively prepare high-quality titanium dioxide product, simultaneously by titanium dioxide in chloride slag and refinery coke are recycled, can obviously improve raw material availability, thereby significantly reduce titanium dioxide production cost.
With reference to figure 2, according to the method for preparing titanium dioxide of the embodiment of the present invention, further comprise:
S900: thermal pretreatment
Before in resulting smart titanium tetrachloride and oxygen are supplied to oxidation reactor, in advance smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.According to embodiments of the invention, in advance smart titanium tetrachloride and oxygen are carried out the temperature of thermal pretreatment and be not particularly limited, according to a particular embodiment of the invention, can in advance smart titanium tetrachloride be preheated to and be not less than 350 degrees Celsius, by oxygen preheat to being not less than 1500 degrees Celsius.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, by smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, oxygen preheat, to being not less than 1500 degrees Celsius, can be reduced to the cost of preparing titanium dioxide significantly effectively.When excess Temperature, the needed cost of preheating can significantly increase, and when temperature is too low, in oxidation reactor, can consume too much energy.
In one embodiment of the invention, described the second gas-solid separating device is connected with described chlorination reactor, for obtained chlorine is back to described chlorination reactor, carries out chlorination reaction.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (6)
1. a method of preparing titanium dioxide, is characterized in that, comprising:
(1) titaniferous ore, reductive agent are supplied in chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore;
(2) the described chlorination reaction mixture obtaining in step (1) is carried out to the first gas solid separation processing, to obtain the gaseous mixture and the chlorination dust slag that contain titanium tetrachloride;
(3) the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid crude titanium tetrachloride;
(4) resulting described liquid crude titanium tetrachloride in step (3) is stored in titanium tetrachloride storing device;
(5) adopting mineral oil to remove vanadium to described liquid crude titanium tetrachloride processes, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the smart titanium tetrachloride that described process is refined, the content of vanadium is below 3ppm;
(6) the described smart titanium tetrachloride and the oxygen that in step (5), obtain are supplied in oxidation reactor, to there is oxidizing reaction in described oxidation reactor, to obtain the oxidation mixtures that contains titanium dioxide and chlorine;
(7) the described oxidation mixtures obtaining in step (6) is carried out to the second gas solid separation processing, to obtain respectively solid titanium dioxide and chlorine; And
(8) through the following steps described chlorination dust slag is processed:
(8-1) described chlorination dust slag is carried out to slurrying, press filtration, washing and filtration, to remove the soluble metal muriate in described chlorination dust slag, and obtain the solid slag that contains titanium dioxide and refinery coke;
(8-2) the described solid slag that contains titanium dioxide and refinery coke is carried out to carbon successively and roughly select and carbon choosing, to obtain respectively refinery coke and titanium dioxide titanium slag; And
(8-3) described titanium dioxide titanium slag is carried out to titanium gravity treatment, to obtain titanium dioxide solid.
2. method according to claim 1, is characterized in that, described chlorination reaction is to carry out at the temperature of 700～900 degrees Celsius.
3. method according to claim 1, is characterized in that, in step (3), further comprises:
By a part for described liquid crude titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture contact, to carry out the first cooling process; And
Utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid crude titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.
4. method according to claim 1, is characterized in that, in step (6), in the described smart titanium tetrachloride obtaining in step (5) and oxygen are supplied to oxidation reactor before, in advance described smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.
5. method according to claim 4, is characterized in that, in advance described smart titanium tetrachloride is preheated to and is not less than 350 degrees Celsius, in advance by described oxygen preheat to being not less than 1500 degrees Celsius.
6. method according to claim 1, is characterized in that, further comprises: the described chlorine obtaining in step (7) is back in step (1) and carries out chlorination reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030344A (en) * | 2014-05-22 | 2014-09-10 | 昆明有色冶金设计研究院股份公司 | Comprehensive treatment method for titanium tetrachloride dust collecting residue |
| CN109956498A (en) * | 2019-04-29 | 2019-07-02 | 渤海大学 | A kind of crude titanic chloride efficiently removes vanadium compounding organic matter and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
-
2013
- 2013-12-09 CN CN201310662644.2A patent/CN103693686B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
Non-Patent Citations (1)
| Title |
|---|
| 顾荣良: "四氯化钛的生产和市场研究", 《上海化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030344A (en) * | 2014-05-22 | 2014-09-10 | 昆明有色冶金设计研究院股份公司 | Comprehensive treatment method for titanium tetrachloride dust collecting residue |
| CN109956498A (en) * | 2019-04-29 | 2019-07-02 | 渤海大学 | A kind of crude titanic chloride efficiently removes vanadium compounding organic matter and preparation method thereof |
| CN109956498B (en) * | 2019-04-29 | 2021-08-03 | 渤海大学 | Compound organic matter for efficiently removing vanadium from crude titanium tetrachloride and preparation method thereof |
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Address after: 650100 Kunming, Xishan District, Yunnan Spring Road, No. 913 Patentee after: Yunnan metallurgy Xin Litai industry company limited Address before: 650100 Kunming, Xishan District, Yunnan Spring Road, No. 913 Patentee before: Yunnan Xinli Nonferrous Metal Co., Ltd. |