CN116022846A - Vanadium oxychloride preparation method based on vanadium-containing solution - Google Patents
Vanadium oxychloride preparation method based on vanadium-containing solution Download PDFInfo
- Publication number
- CN116022846A CN116022846A CN202211719335.XA CN202211719335A CN116022846A CN 116022846 A CN116022846 A CN 116022846A CN 202211719335 A CN202211719335 A CN 202211719335A CN 116022846 A CN116022846 A CN 116022846A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- containing solution
- oxychloride
- precipitate
- chlorinating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 165
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 165
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000002244 precipitate Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 70
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 46
- 239000011780 sodium chloride Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 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
- 229910052742 iron Inorganic materials 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a vanadium oxychloride preparation method based on a vanadium-containing solution. The technical proposal is as follows: and regulating the pH value of the vanadium-containing solution to 1.8-6.3 by using a precipitant, stirring for 80-100 min at the temperature of 95-100 ℃, and carrying out solid-liquid separation to obtain vanadium precipitate. Mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.2-1.9, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material. Placing the chlorinated rectifying raw material into a closed glass bottle, and carrying out chlorination reaction for 0.5-1 h under the conditions of protective atmosphere and 150-190 ℃ to prepare vanadium oxychloride gas based on vanadium-containing solution; condensing and collecting vanadium oxychloride gas based on the vanadium-containing solution to obtain vanadium oxychloride liquid based on the vanadium-containing solution. The method has the characteristics of low roasting temperature, low energy consumption, good separation effect of vanadium and impurities, and contribution to human health and environmental protection, and the vanadium oxychloride based on the vanadium-containing solution prepared by the method has high purity.
Description
Technical Field
The invention belongs to the technical field of vanadium oxychloride preparation. In particular to a method for preparing vanadium oxychloride based on a vanadium-containing solution.
Background
Vanadium oxychloride (VOCl) 3 ) Is an important chemical intermediate. Vanadium oxychloride is not only used as an organic solvent or catalyst, but also an important raw material for preparing high-purity vanadium pentoxide.
The patent technology of 'a preparation method of vanadium oxychloride' (CN 110937630A) comprises the steps of mixing and grinding a vanadium source and a chlorine source, then placing the mixture in a roasting furnace for roasting in a non-oxidizing atmosphere, and collecting distillate to obtain the vanadium oxychloride. The method takes one of ferric chloride, sodium chloride, magnesium chloride and calcium chloride as a chlorine source, and avoids chlorine as a chlorinating agent, but the roasting temperature reaches 800 ℃, and the energy consumption is high.
The patent technology of 'method for preparing vanadium oxychloride by low-temperature chlorination of blast furnace slag' (CN 110642294A) comprises the steps of mixing and preheating blast furnace slag and a carbonaceous reducing agent, and then introducing chlorine gas for reaction to obtain a mixed product containing vanadium oxychloride. The method can effectively extract vanadium in the blast furnace slag, but has poor separation effect of vanadium and impurities, and the content of vanadium oxychloride in the mixed product is only 1.2-1.5 wt% and the purity is lower.
In the technology of the patent (CN 111410228A) of the method for preparing high-purity vanadium oxychloride by utilizing ferrovanadium fine powder, the ferrovanadium fine powder is placed in a chlorination reactor, nitrogen is introduced, the temperature is raised to 300-600 ℃, chlorine and oxygen are introduced, and the total flow rate of the nitrogen, the chlorine and the oxygen is regulated to carry out chlorination reaction; in the reaction process, condensing volatile components in the reactor to obtain a vanadium oxychloride crude product, stopping introducing chlorine and oxygen after the chlorination reaction is finished, adjusting the flow rate of nitrogen again, stopping introducing nitrogen after the reactor is cooled to room temperature, distilling the vanadium oxychloride crude product, and condensing to obtain the high-purity vanadium oxychloride. Although the method realizes the preparation of high-purity vanadium oxychloride, the chlorine introduced in the reaction process is used as a chlorinating agent, so that the method has high corrosiveness and high toxicity and is not friendly to the environment.
In summary, in the existing method for preparing vanadium oxychloride, the technical defects of high roasting temperature, high energy consumption and unfriendly environment exist, and the purity of the prepared vanadium oxychloride is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to provide the vanadium oxychloride preparation method based on the vanadium-containing solution, which has the advantages of low roasting temperature, low energy consumption, good separation effect of vanadium and impurities and environmental friendliness.
In order to achieve the above purpose, the technical scheme adopted by the invention comprises the following specific steps:
step one, regulating the pH value of the vanadium-containing solution to 1.8-6.3 by using a precipitator, stirring for 80-100 min at the temperature of 95-100 ℃, and carrying out solid-liquid separation to obtain vanadium precipitate.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.2-1.9, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridized rectifying raw material.
And thirdly, placing the chlorinated rectifying raw material in a closed glass bottle, and carrying out chlorination reaction for 0.5-1 h under the conditions of protective atmosphere and 150-190 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 2.3-40 g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is-0.8-1.0.
The precipitant is one or more of sodium carbonate, sodium hydroxide, calcium carbonate and calcium hydroxide.
The chlorinating agent is anhydrous aluminum chloride or a mixture of the anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.05-0.45.
The protective atmosphere is one or more of nitrogen, helium and argon.
By adopting the method, compared with the prior art, the invention has the following positive effects:
(1) Low roasting temperature and low energy consumption. The invention adopts anhydrous aluminum chloride or the mixture of the anhydrous aluminum chloride and sodium chloride as the chlorinating agent, compared with the prior art that other chlorinating agents are adopted to bake the vanadium source, the gibbs free energy of the reaction is lower, and the gibbs free energy is easier to react with the vanadium source, so that the temperature required by baking is reduced, and the roasting temperature is low and the energy consumption is low.
(2) Is environment-friendly. The invention adopts anhydrous aluminum chloride or the mixture of the anhydrous aluminum chloride and sodium chloride as the chlorinating agent, avoids the harm of high-corrosiveness and high-toxicity chlorine gas to human bodies and environment, and is free from toxic and harmful substances, thereby being beneficial to human health and environmental protection.
(3) The separation effect of vanadium and impurities is good, and the purity of the prepared vanadium oxychloride is high. Compared with other chlorinating agents, the invention adopts anhydrous aluminum chloride or the mixture of the anhydrous aluminum chloride and sodium chloride as the chlorinating agent, the temperature required by the reaction of the anhydrous aluminum chloride and the vanadium source is lower, the temperature is 170 ℃, and the chlorides of impurity elements such as potassium, calcium, zinc, iron, magnesium and the like in the raw materials are not volatilized below 300 ℃. Therefore, when vanadium volatilizes in the form of vanadium oxychloride and is condensed to obtain vanadium oxychloride liquid in the chlorination process, other impurities cannot appear in the vanadium oxychloride product, so that the separation effect of vanadium and impurities is good.
(4) The vanadium oxychloride based on the vanadium-containing solution prepared by the invention is detected by: the purity is 99.902-99.988%.
Therefore, the method has the characteristics of low roasting temperature, low energy consumption, good separation effect of vanadium and impurities, and contribution to human health and environmental protection, and the vanadium oxychloride based on the vanadium-containing solution prepared by the method has high purity.
Detailed Description
The invention is further described in connection with the following detailed description, which is not intended to limit the scope of the invention.
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
step one, regulating the pH value of the vanadium-containing solution to 1.8-6.3 by using a precipitator, stirring for 80-100 min at the temperature of 95-100 ℃, and carrying out solid-liquid separation to obtain vanadium precipitate.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.2-1.9, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridized rectifying raw material.
And thirdly, placing the chlorinated rectifying raw material in a closed glass bottle, and carrying out chlorination reaction for 0.5-1 h under the conditions of protective atmosphere and 150-190 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 2.3-40 g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is-0.8-1.0.
The precipitant is one or more of sodium carbonate, sodium hydroxide, calcium carbonate and calcium hydroxide.
The chlorinating agent is anhydrous aluminum chloride or a mixture of the anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.05-0.45.
The protective atmosphere is one or more of nitrogen, helium and argon.
Example 1
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 5.5 by using a precipitating agent, stirring for 80 minutes at the temperature of 95 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.2, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chlorinated rectifying raw material in a closed glass bottle, and carrying out chlorination reaction for 0.5h under the conditions of protective atmosphere and 150 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 2.3g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is-0.8.
The precipitant is sodium hydroxide.
The chlorinating agent is anhydrous aluminum chloride.
The protective atmosphere is nitrogen.
The purity of vanadium oxychloride based on the vanadium-containing solution prepared in this example was 99.902%.
Example 2
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 5.9 by using a precipitating agent, stirring for 85min at the temperature of 95 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.4, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chlorinated rectifying raw material in a closed glass bottle, and carrying out chlorination reaction for 0.6h under the conditions of protective atmosphere and 160 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 2.32g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is-0.5.
The precipitant is calcium hydroxide.
The chlorinating agent is a mixture of anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.05.
The protective atmosphere is helium.
The purity of vanadium oxychloride based on the vanadium-containing solution prepared in this example was 99.927%.
Example 3
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 6.3 by using a precipitating agent, stirring for 90min at 96 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.5, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chloridizing and rectifying raw material into a closed glass bottle, and carrying out chloridizing reaction for 0.7h under the conditions of protective atmosphere and 180 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 2.32g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is-0.2.
The precipitant is sodium carbonate.
The chlorinating agent is a mixture of anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.2.
The protective atmosphere is argon.
The purity of vanadium oxychloride based on the vanadium-containing solution prepared in this example was 99.981%.
Example 4
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 2.1 by using a precipitating agent, stirring for 90min at 97 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.7, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chlorinated rectifying raw material in a closed glass bottle, and carrying out chlorination reaction for 0.8h under the conditions of protective atmosphere and 170 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 20.83g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is 0.2.
The precipitant is calcium carbonate.
The chlorinating agent is anhydrous aluminum chloride.
The protective atmosphere is a mixture of nitrogen and helium.
The vanadium oxychloride based solution prepared in this example had a degree of 99.915%.
Example 5
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 2.0 by using a precipitating agent, stirring for 95min at 98 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.8, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chloridizing and rectifying raw material into a closed glass bottle, and carrying out chloridizing reaction for 0.8h under the conditions of protective atmosphere and 180 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the vanadium ion concentration is 38.24g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is 0.5.
The precipitant is a mixture of sodium carbonate and sodium hydroxide.
The chlorinating agent is a mixture of anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.3.
The protective atmosphere is a mixture of nitrogen and argon.
The purity of vanadium oxychloride based on the vanadium-containing solution prepared in this example was 99.988%.
Example 6
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 1.8 by using a precipitating agent, stirring for 95min at 99 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.9, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chlorinated rectifying raw material in a closed glass bottle, and carrying out chlorination reaction for 0.9h under the conditions of protective atmosphere and 190 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the vanadium ion concentration is 38.24g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is 0.8.
The precipitant is a mixture of sodium hydroxide and calcium hydroxide.
The chlorinating agent is a mixture of anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.45.
The protective atmosphere is a mixture of nitrogen, helium and argon.
The purity of vanadium oxychloride based on the vanadium-containing solution prepared in this example was 99.973%.
Example 7
A method for preparing vanadium oxychloride based on vanadium-containing solution. The preparation method of the vanadium oxychloride comprises the following steps:
and step one, regulating the pH value of the vanadium-containing solution to 2 by using a precipitating agent, stirring for 100min at the temperature of 100 ℃, and carrying out solid-liquid separation to obtain vanadium precipitates.
And step two, mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.9, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain the chloridizing rectification raw material.
And thirdly, placing the chlorinated rectifying raw material into a closed glass bottle, and carrying out chlorination reaction for 1h under the conditions of protective atmosphere and 190 ℃ to obtain vanadium oxychloride gas based on the vanadium-containing solution.
And condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
The chemical components of the vanadium-containing solution are as follows: the concentration of vanadium ions is 40g/L, the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium, and the pH value of the vanadium-containing solution is 1.0.
The precipitant is a mixture of calcium carbonate and calcium hydroxide.
The chlorinating agent is a mixture of anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.45.
The protective atmosphere is a mixture of helium and argon.
The purity of vanadium oxychloride based on the vanadium-containing solution prepared in this example was 99.979%.
Compared with the prior art, the specific embodiment has the following positive effects:
1. low roasting temperature and low energy consumption. In the specific embodiment, anhydrous aluminum chloride or a mixture of the anhydrous aluminum chloride and sodium chloride is used as a chlorinating agent, compared with other chlorinating agents adopted to bake a vanadium source in the prior art, the gibbs free energy of the reaction is lower, and the gibbs free energy is easier to react with the vanadium source, so that the temperature required for baking is reduced, and the baking temperature of the specific embodiment is low and the energy consumption is low.
2. Is environment-friendly. The specific embodiment adopts anhydrous aluminum chloride or a mixture of the anhydrous aluminum chloride and sodium chloride as a chlorinating agent, so that the harm of high-corrosiveness and high-toxicity chlorine to human bodies and the environment is avoided, and the specific embodiment has no toxic and harmful substances and is beneficial to human health and environmental protection.
3. The separation effect of vanadium and impurities is good, and the purity of the prepared vanadium oxychloride is high. In the specific embodiment, anhydrous aluminum chloride or a mixture of the anhydrous aluminum chloride and sodium chloride is adopted as a chlorinating agent, compared with other chlorinating agents, the required temperature for the reaction of the anhydrous aluminum chloride and a vanadium source is lower, the temperature is 170 ℃, and chlorides of impurity elements such as potassium, calcium, zinc, iron, magnesium and the like in the raw materials are not volatilized below 300 ℃. Therefore, when vanadium volatilizes in the form of vanadium oxychloride and condenses to obtain vanadium oxychloride liquid in the chlorination process, other impurities cannot appear in the vanadium oxychloride product, so that the separation effect of the vanadium and the impurities in the specific embodiment is good.
4. Vanadium oxychloride prepared in this embodiment based on the vanadium-containing solution is detected: the purity is 99.902-99.988%.
Therefore, the specific embodiment has the characteristics of low roasting temperature, low energy consumption, good separation effect of vanadium and impurities, and contribution to human health and environmental protection, and the vanadium oxychloride based on the vanadium-containing solution prepared by the method has high purity.
Claims (5)
1. The preparation method of the vanadium oxychloride based on the vanadium-containing solution is characterized by comprising the following steps of:
step one, regulating the pH value of the vanadium-containing solution to 1.8-6.3 by using a precipitator, stirring for 80-100 min at 95-100 ℃, and carrying out solid-liquid separation to obtain vanadium precipitate;
mixing the vanadium precipitate and the chlorinating agent according to the mass ratio of the vanadium precipitate to the chlorinating agent of 1:1.2-1.9, and grinding the mixture until the particle size is less than 0.074mm and is more than or equal to 80wt percent to obtain a chloridizing rectification raw material;
step three, placing the chloridized and rectified raw material into a closed glass bottle, and carrying out chloridizing reaction for 0.5-1 h under the conditions of protective atmosphere and 150-190 ℃ to obtain vanadium oxychloride gas based on vanadium-containing solution;
and condensing and collecting the vanadium oxychloride gas based on the vanadium-containing solution to prepare the vanadium oxychloride liquid based on the vanadium-containing solution.
2. The method for preparing vanadium oxychloride based on a vanadium-containing solution according to claim 1, wherein the chemical composition of the vanadium-containing solution is: the concentration of vanadium ions is 2.3-40 g/L, and the vanadium ions of the vanadium-containing solution exist in the form of pentavalent vanadium; the pH value of the vanadium-containing solution is-0.8-1.0.
3. The method for preparing vanadium oxychloride based on a vanadium-containing solution according to claim 1, wherein the precipitant is one or more of sodium carbonate, sodium hydroxide, calcium carbonate and calcium hydroxide.
4. The method for preparing vanadium oxychloride based on vanadium-containing solution according to claim 1, wherein the chlorinating agent is anhydrous aluminum chloride or a mixture of anhydrous aluminum chloride and sodium chloride; the mass ratio of the anhydrous aluminum chloride to the sodium chloride in the mixture is 1:0.05-0.45.
5. The method for preparing vanadium oxychloride based on a vanadium-containing solution according to claim 1, wherein the protective atmosphere is one or more of nitrogen, helium and argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211719335.XA CN116022846A (en) | 2022-12-30 | 2022-12-30 | Vanadium oxychloride preparation method based on vanadium-containing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211719335.XA CN116022846A (en) | 2022-12-30 | 2022-12-30 | Vanadium oxychloride preparation method based on vanadium-containing solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116022846A true CN116022846A (en) | 2023-04-28 |
Family
ID=86071885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211719335.XA Pending CN116022846A (en) | 2022-12-30 | 2022-12-30 | Vanadium oxychloride preparation method based on vanadium-containing solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116022846A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830077A (en) * | 2017-01-17 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of method of vanadic anhydride purification |
| CN106946290A (en) * | 2016-01-07 | 2017-07-14 | 中国科学院过程工程研究所 | A kind of method of vanadic anhydride purification |
| CN110937630A (en) * | 2019-12-20 | 2020-03-31 | 大连博融新材料有限公司 | Preparation method of vanadium oxytrichloride |
| CN114408971A (en) * | 2022-02-28 | 2022-04-29 | 武汉科技大学 | Method for cleanly and efficiently preparing 99-grade vanadium pentoxide |
-
2022
- 2022-12-30 CN CN202211719335.XA patent/CN116022846A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946290A (en) * | 2016-01-07 | 2017-07-14 | 中国科学院过程工程研究所 | A kind of method of vanadic anhydride purification |
| CN106830077A (en) * | 2017-01-17 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of method of vanadic anhydride purification |
| CN110937630A (en) * | 2019-12-20 | 2020-03-31 | 大连博融新材料有限公司 | Preparation method of vanadium oxytrichloride |
| CN114408971A (en) * | 2022-02-28 | 2022-04-29 | 武汉科技大学 | Method for cleanly and efficiently preparing 99-grade vanadium pentoxide |
Non-Patent Citations (1)
| Title |
|---|
| 姜单单: "氯化铝低温氯化法五氧化二钒提纯工艺研究", 15 January 2018 (2018-01-15), pages 13 - 64 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Leaching of niobium and tantalum from a low-grade ore using a KOH roast–water leach system | |
| CN112074617B (en) | Smelting method of bastnaesite and application of carbon powder | |
| US11938527B2 (en) | Process for the purification of waste materials or industrial by-products comprising chlorine | |
| CN112430740B (en) | Method for strengthening vanadium-chromium separation by cooperatively roasting vanadium slag through calcium salt and manganese salt | |
| CN111926196B (en) | Method for recovering zinc from smelting waste residues | |
| CN114836635B (en) | Method for preparing high-purity metal arsenic by nonferrous smelting arsenic-containing solid waste short process | |
| CN113862464B (en) | Method for recovering copper and scattered metal in black copper sludge | |
| CN109868370B (en) | Method for recovering valuable metals in vanadium-chromium slag | |
| CN108677025A (en) | The method that titanium-containing blast furnace slag carries titanium | |
| CN109809494B (en) | Arsenic fixation method for preparing scorodite by stabilizing arsenic alkali residue | |
| CN116022846A (en) | Vanadium oxychloride preparation method based on vanadium-containing solution | |
| CN101787432A (en) | Method for preparing acid-soluble titanium slag from high-titanium slag | |
| CN115947370A (en) | Method for preparing refined vanadium oxytrichloride from vanadium-containing refined tailings | |
| CN1099424A (en) | Method for treating blast furnace slag with diluted chlorhydric acid | |
| CN109881015B (en) | Method for treating arsenic sulfide slag and co-producing elemental arsenic | |
| CN111172401A (en) | Method for treating high-arsenic white smoke | |
| US20240110259A1 (en) | Method for co-producing blister copper by enriching germanium and indium from a copper sulfide ore | |
| CN105800675B (en) | A kind of preparation method of stannous fluoride | |
| CN112080648B (en) | Method for treating indium-containing high-iron zinc sulfide concentrate | |
| CN115536055B (en) | Method for preparing germanium dioxide from zinc hydrometallurgy inorganic germanium slag | |
| CN110436519B (en) | Method for preparing vanadium trioxide from vanadium slag in short process | |
| CN116200592A (en) | Method for separating iron, vanadium and titanium in vanadium titano-magnetite | |
| JPS59156901A (en) | Improvement of process for recovering metallic oxide | |
| CN110643825A (en) | Method for extracting vanadium from blast furnace slag by boiling chlorination | |
| CN115821060A (en) | Method for extracting lithium from lepidolite through composite salt method sectional roasting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |