CN115947370B - Method for preparing refined vanadium oxychloride from vanadium-containing refined tailings - Google Patents
Method for preparing refined vanadium oxychloride from vanadium-containing refined tailings Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 91
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 18
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004886 process control Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 238000002386 leaching Methods 0.000 description 9
- 239000002893 slag Substances 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for preparing vanadium oxychloride from vanadium-containing refined tailings, which comprises the following steps: 1) Carrying out high-temperature treatment on the vanadium-containing refined tailings under inert gas, and keeping the temperature for a period of time to obtain pretreated refined tailings; 2) Cooling the pretreated refined tailings, and continuously introducing mixed gas of oxygen and chlorine to react; 3) Discharging the reacted mixed gas and performing low-temperature condensation to obtain condensed liquid, namely obtaining crude vanadium oxychloride; 4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride. The invention takes the common vanadium-containing refined tailings as the raw material, can realize the production of extracting vanadium by chlorination at low temperature, solves the problems of process control and impurity simultaneous chlorination caused by high-temperature chlorination, effectively reduces the energy consumption and the equipment requirement, and prepares the high-purity vanadium oxychloride.
Description
Technical Field
The invention belongs to the fields of metallurgy and chemical industry, and in particular relates to a method for preparing refined vanadium oxychloride by utilizing refined tailings containing vanadium.
Background
The refined tailings are solid waste generated in the process of producing titanium chloride white or titanium sponge by vanadium-containing titanium slag, wherein the vanadium content can reach 20%, and the refined tailings are vanadium resources with great utilization value. However, because vanadium, titanium and other impurities exist in the form of chloride/oxychloride, chlorine and hydrogen chloride pollutants are easy to generate, and the treatment difficulty is high. The prior treatment method mainly removes chlorine in the vanadium slag by oxidizing roasting, converts vanadium and titanium into oxides and then mixes the oxides with common vanadium slag for treatment. The method has the problems that the oxidation roasting temperature is high, a large amount of chlorine smoke dust generated in the roasting process is difficult to treat, the separation of vanadium and titanium in a roasting product is difficult, and the like.
Patent CN 104004920A discloses a method for extracting vanadium from titanium tetrachloride refined tailings, wherein the titanium tetrachloride refined tailings are subjected to high-temperature roasting and sulfuric acid leaching, and the vanadium leaching rate can reach more than 90%. But the energy consumption in the roasting stage is higher, the leached sulfuric acid consumption is high, the leaching solution is strong in acidity, and the subsequent treatment difficulty is high.
Patent CN 108996547a discloses a method for extracting vanadium from titanium tetrachloride refined tailings by ultrasonic assisted alkaline leaching, which adopts an alkaline leaching process, but needs to be carried out by introducing oxygen at the same time of ultrasonic assistance.
The patent CN 106929696A and the patent CN 107032400A respectively disclose a method for extracting vanadium from TiCl 4 refined tailings by ammonium leaching and alkaline leaching, wherein the method is characterized in that the TiCl 4 refined tailings are roasted and leached to obtain leaching liquid, and vanadium pentoxide is prepared by a purifying impurity-removing vanadium-precipitating process.
Vanadium oxychloride is an important chemical product, is used for manufacturing high-purity vanadium pentoxide powder, catalysts and the like, and is applied to various fields. The existing vanadium oxychloride production process mainly comprises the steps of chloridizing vanadium-containing minerals, wherein the vanadium-containing minerals comprise ammonium metavanadate, ammonium polyvanadate, vanadium pentoxide, vanadium slag, vanadium-containing refined tailings and the like, and the chloridizing agents comprise chlorine, ferric chloride and the like.
The literature on technology of extracting vanadium from high vanadium slag chlorination based on iron chloride proposes a comprehensive utilization process capable of simultaneously and efficiently recovering vanadium, iron and titanium, feCl 3 is used as a chlorinating agent, vanadium oxychloride is prepared at 900-1100K for 2h, and the vanadium extraction rate reaches 38%.
Patent CN110642294a discloses a method for preparing vanadium oxychloride by low-temperature chlorination of blast furnace slag, which comprises the steps of mixing blast furnace slag with a carbonaceous reducing agent, preheating, and then introducing chlorine gas for reaction to obtain a vanadium oxychloride mixture.
Patent CN112142107A discloses a method for preparing high-purity vanadium oxychloride from vanadium-containing refined tailings, which comprises the steps of uniformly mixing the refined tailings with petroleum coke, carrying out chlorination reaction to obtain a crude vanadium oxychloride product, and carrying out hydrolysis and distillation on the crude vanadium oxychloride product to obtain the high-purity vanadium oxychloride.
Patent CN111410228a discloses a method for preparing high-purity vanadium oxychloride from ferrovanadium fine powder, wherein the ferrovanadium fine powder is subjected to chlorination reaction, chlorine is introduced, the temperature is raised to 300-600 ℃, nitrogen is regulated by introducing chlorine and oxygen for chlorination reaction, volatile matters are condensed to obtain a crude vanadium oxychloride product, and the crude vanadium oxychloride product is distilled and condensed to obtain the high-purity vanadium oxychloride.
Therefore, the current research shows that the titanium tetrachloride refining tailings have certain problems in vanadium extraction, mainly because most of vanadium and titanium in the vanadium removal slurry exist in the form of chloride, the separation of vanadium and titanium in the refining tailings is difficult, and the impurity content in the vanadium-containing leaching solution is high. The disclosed method for preparing high-purity vanadium oxychloride has the problem of higher chlorination temperature, so that the chlorination process is difficult to control, and a large amount of impurities are simultaneously chlorinated, so that the subsequent purification process is complex, or high-purity vanadium-containing raw materials are needed to reduce the impurities, but the extremely high production cost of the vanadium oxychloride is caused. These problems result in higher production costs of vanadium oxychloride, which affects the development of its application.
Accordingly, the prior art is in need of improvement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing refined vanadium oxychloride by using refined tailings containing vanadium, which takes common refined tailings containing vanadium as raw materials, can realize the production of chloridizing and extracting vanadium at low temperature, solves the problems of process control and impurity simultaneous chloridizing caused by high-temperature chloridizing, effectively reduces energy consumption and equipment requirements, and prepares the refined vanadium oxychloride.
In order to solve the technical problems, the invention adopts the following technical scheme:
according to aspects of the present invention, there is provided a method for preparing refined vanadium oxychloride from a vanadium-containing refined tailings, comprising the steps of:
1) Carrying out high-temperature treatment on the vanadium-containing refined tailings under inert gas, and keeping the temperature for a period of time to obtain pretreated refined tailings;
2) Cooling the pretreated refined tailings, and continuously introducing mixed gas of oxygen and chlorine to react;
3) Discharging the reacted mixed gas and performing low-temperature condensation to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
In one embodiment of the invention, in step 1), the inert gas is one or more of argon, helium and nitrogen.
In one embodiment of the invention, the vanadium-containing refined tailings consist of the following components in amounts ：C：9.8wt％;V：15.23wt％;Ti：14.44wt％;Cl：41.32wt％;Fe：0.20wt％;Si：0.026wt％;Ca：0.062wt％;Al：＜0.005wt％;S：0.02wt％;P：0.005wt％;Cr：＜0.005wt％.
In one embodiment of the invention, in step 1), the high temperature treatment is carried out at a temperature of 500-800℃and the incubation is carried out for a period of 30-120 minutes.
In one embodiment of the invention, in step 2), the pretreated refined tailings are cooled to 160-350 ℃.
In one embodiment of the invention, the reaction time is 30-90 minutes.
In one embodiment of the invention, the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
In one embodiment of the invention, in step 3), the cryocondensation temperature is from-20℃to 5 ℃.
In one embodiment of the invention, the vanadium yield is above 90% based on the total amount of vanadium in the vanadium-containing refined tailings.
In one embodiment of the invention, the obtained refined vanadium oxychloride has a Ti impurity content of 0.005% -0.02% and a Fe impurity content of 0.002% -0.005%.
By adopting the technical scheme, compared with the prior art, the invention has the following advantages:
(1) The invention adopts the inert gas pretreatment-ultralow temperature chlorination process of the vanadium-containing refined tailings, has low chlorination temperature, effectively reduces energy consumption and reduces equipment requirements;
(2) According to the invention, through ultralow-temperature vanadium selective chlorination, high-efficiency chloridizing extraction of vanadium and selective separation of vanadium and titanium are realized, and a high-purity vanadium oxychloride product is prepared.
Drawings
Fig. 1 shows a schematic flow chart of a method for preparing refined vanadium oxychloride from vanadium-containing refined tailings.
Detailed Description
It should be understood that the embodiments of the invention shown in the exemplary embodiments are only illustrative. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art will readily appreciate that many modifications are possible without materially departing from the teachings of the subject matter of this disclosure. Accordingly, all such modifications are intended to be included within the scope of present invention. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and parameters of the exemplary embodiments without departing from the spirit of the present inventions.
As shown in fig. 1, a method for preparing refined vanadium oxychloride from vanadium-containing refined tailings comprises the following steps:
S101: carrying out high-temperature treatment on the vanadium-containing refined tailings under inert gas, and keeping the temperature for a period of time to obtain pretreated refined tailings;
S102: cooling the pretreated refined tailings, and continuously introducing mixed gas of oxygen and chlorine to react;
S103: discharging the reacted mixed gas and performing low-temperature condensation to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
S104: filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
The invention takes the common vanadium-containing refined tailings as the raw material, can realize the production of extracting vanadium by chlorination at low temperature, solves the problems of process control and impurity simultaneous chlorination caused by high-temperature chlorination, effectively reduces the energy consumption and the equipment requirement, and prepares the high-purity vanadium oxychloride.
In the above technical solution, in step S101, the inert gas is one or more of argon, helium, and nitrogen.
In the technical proposal, the vanadium-containing refined tailings consist of the following components with the content ：C：9.8wt％;V：15.23wt％;Ti：14.44wt％;Cl：41.32wt％;Fe：0.20wt％;Si：0.026wt％;Ca：0.062wt％;Al：＜0.005wt％;S：0.02wt％;P：0.005wt％;Cr：＜0.005wt％.
In the above technical scheme, in step S101, the temperature of the high-temperature treatment is 500-800 ℃, and the duration of the heat preservation is 30-120min.
In the above technical scheme, in step S102, the pretreated refined tailings are cooled to 160-350 ℃; the reaction time is 30-90min.
In the technical scheme, the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
In the above technical scheme, in step S103, the low-temperature condensation temperature is-20 ℃ to 5 ℃.
In the technical scheme, the vanadium yield is more than 90 percent according to the total vanadium in the refined tailings.
In the technical scheme, the content of Ti impurity in the obtained refined vanadium oxychloride is 0.005% -0.02%, and the content of Fe impurity is 0.002% -0.005%.
The above technical scheme of the present invention will be described in detail by specific examples.
The main component analysis of the vanadium-containing refined tailings adopted by the invention is shown in the following table 1:
TABLE 1 analysis of main component of vanadium-containing refined tailings wt%
Example 1
A method for preparing refined vanadium oxychloride from vanadium-containing refined tailings comprises the following steps:
(1) Heating the vanadium-containing refined tailings to 500 ℃ under argon, and preserving heat for 120min to obtain pretreated refined tailings;
(2) Cooling the pretreated refined tailings to 160 ℃, continuously introducing mixed gas of oxygen and chlorine according to the volume ratio of the oxygen to the chlorine of 10:1, and reacting for 30min;
(3) Discharging the reacted mixed gas, and performing low-temperature condensation at 5 ℃ to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
(4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
Through the above example 1, the vanadium yield reaches 95% based on the total vanadium content in the refined tailings, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are respectively 0.02% and 0.002%.
Example 2
A method for preparing refined vanadium oxychloride from vanadium-containing refined tailings comprises the following steps:
(1) Heating the vanadium-containing refined tailings to 800 ℃ under nitrogen, and preserving heat for 30min to obtain pretreated refined tailings;
(2) Cooling the pretreated refined tailings to 250 ℃, continuously introducing mixed gas of oxygen and chlorine according to the volume ratio of the oxygen to the chlorine of 1:1, and reacting for 90min;
(3) Discharging the reacted mixed gas, and performing low-temperature condensation at 0 ℃ to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
(4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
Through the above example 2, the vanadium yield reaches 90% based on the total vanadium content in the refined tailings, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are respectively 0.005% and 0.003%.
Example 3
A method for preparing refined vanadium oxychloride from vanadium-containing refined tailings comprises the following steps:
(1) Heating the vanadium-containing refined tailings to 650 ℃ under the mixed gas of argon and helium according to the volume ratio of 1:1, and preserving the heat for 60 minutes to obtain pretreated refined tailings;
(2) Cooling the pretreated refined tailings to 200 ℃, continuously introducing mixed gas of oxygen and chlorine according to the volume ratio of the oxygen to the chlorine of 5:1, and reacting for 60min;
(3) Discharging the mixed gas after the reaction, and performing low-temperature condensation at the temperature of minus 20 ℃ to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
(4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
Through the above example 3, the vanadium yield reaches 94% based on the total amount of vanadium in the refined tailings, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are respectively 0.01% and 0.005%.
Example 4
A method for preparing refined vanadium oxychloride from vanadium-containing refined tailings comprises the following steps:
(1) Heating the vanadium-containing refined tailings to 700 ℃ under the mixed gas of nitrogen and helium according to the volume ratio of 1:1, and preserving the heat for 100min to obtain pretreated refined tailings;
(2) Cooling the pretreated refined tailings to 350 ℃, continuously introducing mixed gas of oxygen and chlorine according to the volume ratio of the oxygen to the chlorine of 5:1, and reacting for 100min;
(3) Discharging the mixed gas after the reaction, and performing low-temperature condensation at the temperature of minus 10 ℃ to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
(4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
Through the above example 4, the vanadium yield reaches 92% based on the total amount of vanadium in the refined tailings, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are respectively 0.013% and 0.004%.
In a word, the invention adopts the inert gas pretreatment-ultralow temperature chlorination process of the vanadium-containing refined tailings, has low chlorination temperature, effectively reduces energy consumption and reduces equipment requirements; the invention also realizes the high-efficiency chloridizing extraction of vanadium and the selective separation of vanadium and titanium through the selective chloridizing of vanadium at ultralow temperature, and prepares the high-purity vanadium oxychloride product.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention; modifications and equivalent substitutions are intended to be included in the scope of the claims without departing from the spirit and scope of the present invention.
Claims (9)
1. The method for preparing the refined vanadium oxychloride by utilizing the refined tailings containing vanadium is characterized by comprising the following steps of:
1) Carrying out high-temperature treatment on vanadium-containing refined tailings under inert gas and/or nitrogen, and keeping the temperature for a period of time to obtain pretreated refined tailings;
2) Cooling the pretreated refined tailings to 160-350 ℃, and continuously introducing mixed gas of oxygen and chlorine for reaction;
3) Discharging the reacted mixed gas and performing low-temperature condensation to obtain condensed liquid, namely obtaining crude vanadium oxychloride;
4) Filtering the crude vanadium oxychloride to remove solid impurities, thereby obtaining the refined vanadium oxychloride.
2. The method for producing refined vanadium oxychloride from a refined tailings containing vanadium of claim 1 wherein in said step 1), said inert gas is one or more of argon and helium.
3. The method for preparing refined vanadium oxychloride from refined tailings containing vanadium as claimed in claim 1, wherein the refined tailings containing vanadium is composed of the following components in content ：C：9.8wt％;V：15.23wt％;Ti：14.44wt％;Cl：41.32wt％;Fe：0.20wt％;Si：0.026wt％;Ca：0.062wt％;Al：＜0.005wt％;S：0.02wt％;P：0.005wt％;Cr：＜0.005wt％.
4. The method for preparing refined vanadium oxychloride from refined tailings containing vanadium according to claim 1, wherein in the step 1), the high temperature treatment is carried out at 500-800 ℃ for 30-120min.
5. The method for preparing refined vanadium oxychloride from refined tailings containing vanadium according to claim 1, wherein in the step 2), the reaction time is 30-90min.
6. The method for preparing refined vanadium oxychloride from vanadium-containing refined tailings, according to claim 1, wherein the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
7. The method for preparing refined vanadium oxychloride from refined tailings containing vanadium of claim 1 wherein in the step 3), the temperature of low temperature condensation is-20 ℃ to 5 ℃.
8. The method for preparing refined vanadium oxychloride from the refined tailings containing vanadium according to claim 1, wherein the vanadium yield is more than 90 percent based on the total amount of vanadium in the refined tailings containing vanadium.
9. The method for preparing refined vanadium oxychloride from refined tailings containing vanadium according to claim 1, wherein the obtained refined vanadium oxychloride has a Ti impurity content of 0.005% -0.02% and a Fe impurity content of 0.002% -0.005%.
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| DE1936988C3 (en) * | 1969-07-21 | 1974-01-03 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of vanadium oxitrichloride |
| CN106048220A (en) * | 2010-05-19 | 2016-10-26 | Tng有限公司 | Method for the extraction and recovery of vanadium |
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