CN115196677B - Method for refining vanadium pentoxide by vanadium liquid - Google Patents
Method for refining vanadium pentoxide by vanadium liquid Download PDFInfo
- Publication number
- CN115196677B CN115196677B CN202210945743.0A CN202210945743A CN115196677B CN 115196677 B CN115196677 B CN 115196677B CN 202210945743 A CN202210945743 A CN 202210945743A CN 115196677 B CN115196677 B CN 115196677B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- ammonium
- liquid
- solution
- refining
- 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.)
- Active
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 112
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000007788 liquid Substances 0.000 title claims abstract description 98
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000007670 refining Methods 0.000 title claims abstract description 19
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 56
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 54
- 239000012535 impurity Substances 0.000 claims abstract description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 40
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 29
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 29
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000004537 pulping Methods 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 230000001376 precipitating effect Effects 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 12
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims description 34
- 230000008025 crystallization Effects 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Abstract
The invention relates to a method for refining vanadium pentoxide by using vanadium liquid, wherein the vanadium liquid comprises sodium vanadium liquid or calcified vanadium liquid, and the method comprises the following steps: a. precipitating vanadium from the vanadium liquid by ammonium salt or hydrolyzing precipitated vanadium to obtain ammonium polyvanadate or red cake; b. pulping and dissolving ammonium polyvanadate or red cakes back by using ammonium bicarbonate and/or ammonium carbonate, and carrying out solid-liquid separation to obtain an ammonium metavanadate solution; c. cooling and crystallizing the ammonium metavanadate solution to obtain ammonium metavanadate crystals and a crystallized solution; d. adding ammonium bicarbonate and/or ammonium carbonate into the crystallized liquid, and returning to the step b; e. calcining the ammonium metavanadate crystal to obtain vanadium pentoxide. The raw liquid used in the invention is vanadium liquid, the range of the vanadium liquid is wide, and other impurities in the vanadium liquid are not limited. The method can realize high vanadium recovery rate and high-purity vanadium pentoxide, and has wide application range and low cost.
Description
Technical Field
The invention relates to the field of vanadium oxide preparation, in particular to a method for refining vanadium pentoxide by using vanadium liquid.
Background
Vanadium is a very rare metal element, is mainly applied to the steel industry to improve the strength, toughness and other performances of steel products, and has wide application in the fields of chemical industry, energy storage and medicine, and has high economic value. When vanadium is precipitated by utilizing the vanadium liquid, when the impurity in the vanadium liquid is higher, the obtained vanadium oxide can not meet the quality standard because of higher impurity. The traditional vanadium liquid impurity removal or vanadium oxide refining has the defects of high vanadium loss, difficult and complex working procedures.
Based on this, the prior art still remains to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for refining vanadium pentoxide by using vanadium liquid, which uses the vanadium liquid as a raw liquid, has wide vanadium liquid range, is free from limitation of other impurities in the vanadium liquid, precipitates vanadium or hydrolyzes the precipitated vanadium by using acid ammonium salt, precipitates ammonium polyvanadate or red cakes, uses ammonium bicarbonate/ammonium carbonate for pulping and dissolving back, separates solid impurities and ammonium metavanadate solution from solid and liquid, obtains ammonium metavanadate crystals by cooling and crystallizing the ammonium metavanadate solution, directly adds ammonium bicarbonate/ammonium carbonate into the liquid after crystallization for pulping or adds ammonium bicarbonate/ammonium carbonate into the liquid after crystallization for pulping after impurity removal. And calcining ammonium metavanadate to obtain vanadium pentoxide.
Specifically, the invention provides a method for refining vanadium pentoxide by using vanadium liquid, wherein the vanadium liquid comprises sodium vanadium liquid or calcified vanadium liquid, and the method comprises the following steps of:
a. precipitating vanadium from the vanadium liquid by ammonium salt or hydrolyzing precipitated vanadium to obtain ammonium polyvanadate or red cake;
b. pulping and dissolving ammonium polyvanadate or red cakes back by using ammonium bicarbonate and/or ammonium carbonate, and carrying out solid-liquid separation to obtain an ammonium metavanadate solution;
c. cooling and crystallizing the ammonium metavanadate solution to obtain ammonium metavanadate crystals and a crystallized solution;
d. adding ammonium bicarbonate and/or ammonium carbonate into the crystallized liquid, and returning to the step b;
e. calcining the ammonium metavanadate crystal obtained in the step c to obtain vanadium pentoxide.
In an embodiment of the invention, in case the vanadium liquid comprises a sodium vanadium liquid, in step d: and stopping returning to the step b when the content of sodium element in the crystallized liquid is larger than a preset value.
In an embodiment of the invention, the predetermined value is 43g/L.
In an embodiment of the present invention, step d comprises: and (3) removing impurities from the post-crystallization liquid by using an impurity removing agent under the condition that the content of phosphorus in the post-crystallization liquid is 0.10g/L to 0.50 g/L.
In the embodiment of the invention, the impurity removing agent comprises one of calcium oxide, magnesium oxide and aluminum oxide, the adding amount of the impurity removing agent is controlled according to the ratio of the impurity removing agent metal ions to the phosphorus substances of 0.8-1.2, the impurity removing temperature is 40-90 ℃, and the impurity removing time is 15-60 min.
In an embodiment of the invention, the ammonium salt in step a comprises at least one of ammonium sulphate, ammonium carbonate, ammonium bicarbonate and ammonium nitrate, and the ammonium addition has a pH value of 2.4-4, an ammonium addition coefficient NH4 + The ratio of the amount of the substances of the/TV is 0.90-1.55, the pH of the precipitated vanadium is 1.4-2.0, the temperature of the precipitated vanadium is 90-99 ℃, and the time of the precipitated vanadium is 30-90 min; in the step a, under the condition of hydrolyzing and precipitating vanadium, the pH value of the precipitated vanadium is 1.4-2.4, the temperature of the precipitated vanadium is 90-99 ℃, and the time of precipitating vanadium is 60-90 min.
In the embodiment of the invention, the pulping liquid-solid ratio in the step b is 20-120:1, the pulping temperature is 60-99 ℃, and the ammonium addition amount NH4 is carried out + The ratio of the amount of the substances of the/TV is 1.0-1.5, the pH value of the solution is controlled to be 7.0-9.5 by adding ammonium bicarbonate and/or ammonium carbonate, and the pulping time is controlled to be 15-60 min.
In an embodiment of the present invention, step c comprises: one-time washing is carried out on ammonium metavanadate crystals, the washing water temperature is 10-40 ℃, and washing filtrate is mixed into a post-crystallization liquid:
clear water with the same volume as ammonium metavanadate crystals;
ammonia water in any proportion;
ammonium bicarbonate and/or ammonium carbonate solution in any ratio.
In the embodiment of the invention, in the step e, the calcination temperature of the ammonium metavanadate crystal is 500-550 ℃, the calcination time is 180-300 min, and the oxygen content in the calcination atmosphere in the calcination process is more than 15%.
In the embodiment of the invention, in the step c, the crystallization temperature of the ammonium metavanadate is 10-40 ℃ and the crystallization time is 120-300 min. The invention uses ammonium bicarbonate/ammonium carbonate to dissolve ammonium polyvanadate or red cake to convert ammonium polyvanadate into ammonium metavanadate solution, and weak alkaline crystallization ammonium metavanadate can obtain vanadium oxide with higher purity.
Drawings
FIG. 1 shows a schematic flow chart of a method for refining vanadium pentoxide from vanadium liquid;
FIG. 2 is a schematic flow chart of one embodiment of a method for refining vanadium pentoxide from vanadium liquid provided by the present invention; and
fig. 3 shows a schematic flow chart of another embodiment of the method for refining vanadium pentoxide from vanadium liquid.
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.
According to the present invention, there is provided a method for refining vanadium pentoxide from a vanadium liquid, as shown in fig. 1, the method may include the steps of:
a. precipitating vanadium from the vanadium liquid by ammonium salt or hydrolyzing precipitated vanadium to obtain ammonium polyvanadate or red cake;
b. pulping and dissolving ammonium polyvanadate or red cakes back by using ammonium bicarbonate and/or ammonium carbonate, and carrying out solid-liquid separation to obtain an ammonium metavanadate solution;
c. cooling and crystallizing the ammonium metavanadate solution to obtain ammonium metavanadate crystals and a crystallized solution;
d. adding ammonium bicarbonate and/or ammonium carbonate into the crystallized liquid, and returning to the step b;
e. calcining the ammonium metavanadate crystal obtained in the step c to obtain vanadium pentoxide.
The stock solution used in the invention is vanadium solution, including sodium vanadium solution or calcified vanadium solution, the vanadium content in the vanadium solution is 10-100 g/L, other impurities in the vanadium solution are not limited, and the vanadium solution is precipitated by acidic ammonium salt or hydrolyzed to precipitate vanadium, so that metal cation impurities in vanadium precipitation matters of the vanadium solution are less, and the vanadium content in the vanadium precipitation solution is less than 0.5g/L.
In the step a, after the pH value of the vanadium liquid is regulated, ammonium salt is used for precipitating vanadium or hydrolyzing and precipitating vanadium to obtain ammonium polyvanadate or red cakes.
In the embodiment of the invention, under the condition of adopting ammonium salt to precipitate vanadium, 400ml of vanadium liquid with the content of 35g/L of TV is measured by a weighing container such as a measuring cylinder, the pH value of the vanadium liquid is regulated to 2.4-4 by 1:1 sulfuric acid, and the ammonium addition coefficient NH4 is calculated + And adding ammonium salt into (total vanadium) =0.90-1.55 (the mass ratio of substances), regulating the pH of the precipitated vanadium to be 1.4-2.0 by using sulfuric acid with the ratio of 1:1, precipitating vanadium for 30-90 min at the temperature of 90-99 ℃, and carrying out solid-liquid separation to obtain ammonium polyvanadate. Under the condition of adopting the hydrolysis to precipitate vanadium, 400ml of vanadium liquid with the TV content of 35g/L is measured by a weighing container such as a measuring cylinder, the pH value of the vanadium liquid is regulated to be 1.4-2.4 by using sulfuric acid with the ratio of 1:1, the hydrolysis to precipitate vanadium is carried out at the vanadium precipitation temperature of 90-99 ℃, the vanadium precipitation time is 60-90 min, and the red cake is obtained by solid-liquid separation.
In the step b, ammonium polyvanadate or red cake is pulped and dissolved by ammonium bicarbonate and/or ammonium carbonate to obtain ammonium metavanadate solution. In the embodiment of the invention, the solid ratio of the sizing liquid is 20-120:1, the practical operation is that ammonium metavanadate can be completely dissolved, the pulping temperature is 60-99 ℃, and the ammonium adding amount is NH4 + Tv=1.0 to 1.5 (mass ratio), the pH of the solution is controlled to 7.0 to 9.5 by adding the ratio of ammonium bicarbonate and ammonium carbonate, and the beating time is controlled to 15 to 60 minutes. And then carrying out solid-liquid separation to obtain an ammonium metavanadate solution.
In step c, the ammonium metavanadate solution is cooled and crystallized at a proper temperature to obtain ammonium metavanadate crystals and a crystallized solution. In the embodiment of the invention, the crystallization temperature of ammonium metavanadate is 10-40 ℃ and the crystallization time is 120-300 min.
In the embodiment of the invention, in the step c, optionally, ammonium metavanadate crystals are washed once, the washing water volume is equivalent to that of the ammonium metavanadate crystals, the washing water can be clear water or ammonia water, ammonium bicarbonate and/or ammonium carbonate solution in any proportion, the washing water temperature is 10-40 ℃, and the washing filtrate is incorporated into the post-crystallization liquid. By this washing process, the impurity content of ammonium metavanadate can be reduced and the water balance of the post-crystallization liquor with the pulping of ammonium polyvanadate or red cake is maintained with recycling to step b.
In step d, ammonium bicarbonate and/or ammonium carbonate is added to the post-crystallization liquid and returns to step b, so that the ammonium bicarbonate and/or ammonium carbonate comprising the post-crystallization liquid can start a new cycle of pulping and re-dissolving ammonium polyvanadate or red cakes. Since there is also a lot of vanadium and ammonium in the post-crystallization liquor, returning to step b, the recycling of the beating of ammonium polyvanadate or red cake with ammonium bicarbonate and/or ammonium carbonate comprising the post-crystallization liquor has at least the following advantages: 1. the vanadium loss can be reduced; 2. the utilization rate of ammonium is improved; 3. reducing the waste water.
In embodiments where the vanadium liquid comprises a sodium vanadium liquid, the return to step b is stopped when the content of sodium element in the post-crystallization liquid is greater than a predetermined value. Since too high a content of Na in the system will affect the purity of ammonium metavanadate, the solution having too high a content of Na will be discarded, and thus when it is detected that the content of Na exceeds a predetermined value, the cyclic beating of the solution can be stopped. In one embodiment of the invention, the predetermined value is 43g/L, i.e. the return to step b is stopped when the content of sodium element in the post-crystallization liquor is greater than 43g/L. It will be appreciated by those skilled in the art that the predetermined value may be formulated as desired and as industry standard.
In the embodiment of the invention, in the cyclic beating process, in the step d, in the case that the content of phosphorus in the liquid after crystallization is 0.10g/L to 0.50g/L, the impurity removal is required before returning to the step b. The impurity removing agent can comprise one of calcium oxide, magnesium oxide and aluminum oxide, the adding amount of the impurity removing agent is controlled according to the metal ion M/P=0.8-1.2 (the mass ratio of substances) of the impurity removing agent, the impurity removing temperature is 40-90 ℃, and the impurity removing time is 15-60 min.
In the step e, the ammonium metavanadate crystal is calcined for 180-300 min at the calcining temperature of 500-550 ℃, so that the oxygen content in the calcining atmosphere is required to be ensured to be more than 15% in the calcining process, and finally the high-purity vanadium pentoxide is obtained.
The above technical scheme of the present invention will be described in detail by specific examples.
Example 1
Referring to the flow chart shown in FIG. 2, 400ml of TV sodium with 35g/L content was measured with a cartridgeAdjusting the pH value of the vanadium solution to 2.4 by using 1:1 sulfuric acid, and adding ammonium coefficient NH4 + Tv=1.55 (mass ratio of substances) ammonium sulfate 18.11g was added, the pH of the precipitated vanadium was adjusted to 2.0 with 1:1 sulfuric acid, and at 95 ℃ the vanadium was precipitated for 40min, and solid-liquid separation was performed to obtain ammonium polyvanadate. Taking 20g of ammonium polyvanadate, pulping with 460ml of clear water according to a liquid-solid ratio of 23:1, wherein the pulping temperature is 90 ℃, and the ammonium adding amount is NH4 + 15.49g of ammonium bicarbonate is added to the solution of which the pH value is 7.54 and the pulping time is 30min, and the ammonium metavanadate solution and the solid impurities are obtained after solid-liquid separation. The ammonium metavanadate solution is cooled to crystallize ammonium metavanadate crystals (solids), the crystallization temperature is 20 ℃, the crystallization time is 120min, 20.41g of ammonium metavanadate solids after solid-liquid separation is washed once by 9ml of clean water with the same volume, the washing water temperature is 10 ℃, and the washing filtrate is incorporated into the liquid after crystallization. 463ml of the crystallized solution is returned to circulation to pulp ammonium polyvanadate (for example, 20g of ammonium polyvanadate can be additionally taken, ammonium polyvanadate is pulped by using ammonium bicarbonate containing the crystallized solution, and the like, circulation is performed), when the circulation times are 15 times, the concentration of P in the crystallized solution is 0.22g/L, caO is added according to Ca/P=0.8 (the mass ratio of substances) to remove impurities, the impurity removal temperature is 40 ℃, the impurity removal time is 30min, and the P in the impurity removal solution is 0.016g/L. Circulation was stopped when circulation was continued to 30 times, at which point the sodium concentration was 43.32g/L. Calcining ammonium metavanadate at 550 ℃ for 180min to ensure oxygen content in calcining atmosphere in calcining process>15%, and finally the purity of the obtained vanadium pentoxide is 99.93%.
Example 2
Referring to the flow chart shown in FIG. 3, 1000ml of calcified vanadium liquid with TV content of 25g/L is measured by a measuring cylinder, the pH value of the vanadium precipitation of the vanadium liquid is regulated to 2.0 by using 1:1 sulfuric acid, the vanadium precipitation temperature is 90 ℃, the vanadium precipitation time is 60min, the hydrolysis vanadium precipitation is carried out, and the solid-liquid separation is finished after the vanadium precipitation, so that the red cake is obtained. Taking 20g of red cake, pulping with 600ml of crystallization liquid containing TV (all vanadium) 2.41g/L (for example, the crystallization liquid is from the previous round) according to a liquid-solid ratio of 30:1, wherein the pulping temperature is 80 ℃, and the ammonium adding amount is NH4 + And (3) adding 12.39g of ammonium bicarbonate and 1.88g of ammonium carbonate into the solution with the ratio of the mass per unit volume per tv=1.0, wherein the pH value of the solution is 8.01, the pulping time is 35min, and obtaining the ammonium metavanadate solution and solid impurities after solid-liquid separation. Ammonium metavanadate solution cooling crystallization ammonium metavanadate, crystallization temperatureThe temperature is 30 ℃, the crystallization time is 240min, 19.50g of ammonium metavanadate solid is obtained after solid-liquid separation, 8.5ml of ammonium bicarbonate with the same volume of 30g/L is used for washing once, the washing water temperature is 20 ℃, and the washing filtrate is merged into the liquid after crystallization. 601ml of the crystallized solution is returned to circularly pulp ammonium polyvanadate, when the circulation times are 10 times, the concentration of P in the crystallized solution is 0.16g/L, mgO is added according to the ratio of Mg/P=1.0 (the mass ratio of substances) to remove impurities, the impurity removal temperature is 60 ℃, the impurity removal time is 30min, the P in the impurity removal solution is 0.012g/L, and the impurity removal solution is returned to circularly pulp ammonium polyvanadate. In this embodiment, the ammonium polyvanadate may be recycled as many as desired for a predetermined number of times or even for an infinite number of cycles. Calcining ammonium metavanadate at 500 ℃ for 300min to ensure oxygen content in calcining atmosphere in calcining process>15%, and finally the purity of the obtained vanadium pentoxide is 99.95%.
Example 3
Referring to the flow chart shown in FIG. 2, 1000ml of sodium vanadium solution with the TV content of 60g/L is measured by a measuring cylinder, the pH value of the vanadium solution for precipitating vanadium is regulated to be 1.4 by using 1:1 sulfuric acid, the vanadium precipitating temperature is 96 ℃, the vanadium precipitating time is 90min, the hydrolysis vanadium precipitation is carried out, and the solid-liquid separation is finished after the vanadium precipitation, so that the red cake is obtained. Taking 20g of red cake, pulping 1550ml of crystallized liquid containing TV6.97g/L according to a liquid-solid ratio of 77.5:1, wherein the pulping temperature is 70 ℃, and the ammonium adding amount is NH4 + And (3) adding 18.59g of ammonium bicarbonate into the solution with the concentration of 1.2 (the mass ratio), wherein the pH value of the solution is 7.57, the pulping time is 15min, and the ammonium metavanadate solution and the solid impurities are obtained after solid-liquid separation. The ammonium metavanadate solution is cooled to crystallize ammonium metavanadate, the crystallization temperature is 40 ℃, the crystallization time is 300min, 21.21g of ammonium metavanadate solid is obtained after solid-liquid separation, 9ml of ammonia water with the same volume of 30% is used for washing once, the washing water temperature is 20 ℃, and the washing filtrate is merged into the liquid after crystallization. 1546ml of the crystallized liquid is returned to be circularly pulped to obtain ammonium polyvanadate, when the cycle times are 30 times, the concentration of P in the crystallized liquid is 0.33g/L, mgO is added according to the ratio of Mg/P=1.2 (the mass ratio of substances) to remove impurities, the impurity removal temperature is 40 ℃, the impurity removal time is 60min, the P in the impurity removal liquid is 0.011g/L, the circulation is stopped when the circulation is continuously carried out for 41 times, and the concentration of sodium is 43.77g/L. Calcining ammonium metavanadate at 500 ℃ for 300min to ensure oxygen content in calcining atmosphere in calcining process>15%, and finally, the purity of the obtained vanadium pentoxide is 99.96%.
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 (8)
1. The method for refining vanadium pentoxide by using the vanadium liquid is characterized in that the vanadium liquid comprises sodium vanadium liquid or calcified vanadium liquid, the vanadium content in the vanadium liquid is 10-100 g/L, and the method comprises the following steps:
a. precipitating vanadium from the vanadium liquid by ammonium salt or hydrolyzing to obtain ammonium polyvanadate or red cake, wherein the pH value of ammonium is 2.4-4, and the ammonium coefficient NH is added under the condition of precipitating vanadium by ammonium salt 4 + The ratio of the amount of the substances of the/TV is 0.90-1.55, the pH of the precipitated vanadium is 1.4-2.0, the temperature of the precipitated vanadium is 90-99 ℃, and the time of the precipitated vanadium is 30-90 min; under the condition of hydrolyzing and precipitating vanadium, the pH value of the precipitated vanadium is 1.4-2.4, the temperature of the precipitated vanadium is 90-99 ℃, and the time of precipitating vanadium is 60-90 min;
b. pulping and dissolving ammonium polyvanadate or red cakes back by using ammonium bicarbonate and/or ammonium carbonate, and carrying out solid-liquid separation to obtain an ammonium metavanadate solution;
c. cooling and crystallizing the ammonium metavanadate solution to obtain ammonium metavanadate crystals and a crystallized solution;
d. adding ammonium bicarbonate and/or ammonium carbonate into the crystallized liquid, and returning to the step b;
e. calcining the ammonium metavanadate crystal obtained in the step c to obtain vanadium pentoxide,
wherein, in step d: stopping returning to the step b when the content of sodium element in the crystallized liquid is larger than a preset value; and (3) under the condition that the content of phosphorus in the crystallized liquid is 0.10 g/L-0.50 g/L, removing impurities from the crystallized liquid by using an impurity removing agent.
2. The method for refining vanadium pentoxide according to claim 1, wherein the predetermined value is 43g/L.
3. The method for refining vanadium pentoxide by using vanadium liquid according to claim 1, wherein the impurity removing agent comprises one of calcium oxide, magnesium oxide and aluminum oxide, the adding amount of the impurity removing agent is controlled according to the ratio of the impurity removing agent metal ions to the phosphorus substances of 0.8-1.2, the impurity removing temperature is 40-90 ℃, and the impurity removing time is 15-60 min.
4. The method for refining vanadium pentoxide from vanadium liquid according to claim 1, wherein the ammonium salt in step a comprises at least one of ammonium sulfate, ammonium carbonate, ammonium bicarbonate and ammonium nitrate.
5. The method for refining vanadium pentoxide by using vanadium liquid according to claim 1, wherein the pulping liquid-solid ratio in the step b is 20-120 mL/1 g, the pulping temperature is 60-99 ℃, and the ammonium amount NH is added 4 + The ratio of the amount of the substances of the/TV is 1.0-1.5, the pH value of the solution is controlled to be 7.0-9.5 by adding ammonium bicarbonate and/or ammonium carbonate, and the pulping time is controlled to be 15-60 min.
6. The method for refining vanadium pentoxide according to claim 1, wherein step c comprises: one-time washing is carried out on ammonium metavanadate crystals, the washing water temperature is 10-40 ℃, and washing filtrate is mixed with the post-crystallization liquid:
clear water with the same volume as ammonium metavanadate crystals;
ammonia water in any proportion;
ammonium bicarbonate and/or ammonium carbonate solution in any ratio.
7. The method for refining vanadium pentoxide by using vanadium liquid according to claim 1, wherein in the step e, the calcination temperature of the ammonium metavanadate crystal is 500-550 ℃, the calcination time is 180-300 min, and the oxygen content in the calcination atmosphere in the calcination process is more than 15%.
8. The method for refining vanadium pentoxide by using vanadium liquid according to claim 1, wherein in the step c, the crystallization temperature of ammonium metavanadate is 10-40 ℃ and the crystallization time is 120-300 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210945743.0A CN115196677B (en) | 2022-08-08 | 2022-08-08 | Method for refining vanadium pentoxide by vanadium liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210945743.0A CN115196677B (en) | 2022-08-08 | 2022-08-08 | Method for refining vanadium pentoxide by vanadium liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115196677A CN115196677A (en) | 2022-10-18 |
| CN115196677B true CN115196677B (en) | 2023-11-28 |
Family
ID=83585552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210945743.0A Active CN115196677B (en) | 2022-08-08 | 2022-08-08 | Method for refining vanadium pentoxide by vanadium liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115196677B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412539A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Clean production process for vanadium oxide |
| CN103420416A (en) * | 2012-05-15 | 2013-12-04 | 攀钢集团攀枝花钢钒有限公司 | Ammonium metavanadate preparation method |
| CN103667710A (en) * | 2013-12-04 | 2014-03-26 | 四川省川威集团有限公司 | Technology for clean production of vanadium pentoxide employing high-calcium vanadium slag |
| WO2015161660A1 (en) * | 2014-04-21 | 2015-10-29 | 中国科学院过程工程研究所 | Method for preparing low-silicon vanadium pentoxide from solution containing vanadium, chromium and silicon |
| CN106241873A (en) * | 2016-08-26 | 2016-12-21 | 陕西华源矿业有限责任公司 | The preparation method of high-purity vanadium pentoxide |
| CN107500352A (en) * | 2017-08-26 | 2017-12-22 | 袁安会 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
| CN107540018A (en) * | 2017-08-01 | 2018-01-05 | 洛阳理工学院 | V in a kind of discarded SCR denitration2O5Extracting method |
| WO2018024083A1 (en) * | 2016-08-05 | 2018-02-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Method using highly concentrated vanadium solution for manufacturing ammonium polyvanadate |
| CN109502644A (en) * | 2019-01-02 | 2019-03-22 | 成都先进金属材料产业技术研究院有限公司 | The method that alkalinity prepares high purity vanadic anhydride containing vanadium leachate |
| CN113930629A (en) * | 2021-09-22 | 2022-01-14 | 河钢承德钒钛新材料有限公司 | Method for treating crystallization mother liquor of calcification vanadium precipitation process |
| CN114275815A (en) * | 2021-12-16 | 2022-04-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution |
-
2022
- 2022-08-08 CN CN202210945743.0A patent/CN115196677B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412539A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Clean production process for vanadium oxide |
| CN103420416A (en) * | 2012-05-15 | 2013-12-04 | 攀钢集团攀枝花钢钒有限公司 | Ammonium metavanadate preparation method |
| CN103667710A (en) * | 2013-12-04 | 2014-03-26 | 四川省川威集团有限公司 | Technology for clean production of vanadium pentoxide employing high-calcium vanadium slag |
| WO2015161660A1 (en) * | 2014-04-21 | 2015-10-29 | 中国科学院过程工程研究所 | Method for preparing low-silicon vanadium pentoxide from solution containing vanadium, chromium and silicon |
| WO2018024083A1 (en) * | 2016-08-05 | 2018-02-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Method using highly concentrated vanadium solution for manufacturing ammonium polyvanadate |
| CN106241873A (en) * | 2016-08-26 | 2016-12-21 | 陕西华源矿业有限责任公司 | The preparation method of high-purity vanadium pentoxide |
| CN107540018A (en) * | 2017-08-01 | 2018-01-05 | 洛阳理工学院 | V in a kind of discarded SCR denitration2O5Extracting method |
| CN107500352A (en) * | 2017-08-26 | 2017-12-22 | 袁安会 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
| CN109502644A (en) * | 2019-01-02 | 2019-03-22 | 成都先进金属材料产业技术研究院有限公司 | The method that alkalinity prepares high purity vanadic anhydride containing vanadium leachate |
| CN113930629A (en) * | 2021-09-22 | 2022-01-14 | 河钢承德钒钛新材料有限公司 | Method for treating crystallization mother liquor of calcification vanadium precipitation process |
| CN114275815A (en) * | 2021-12-16 | 2022-04-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution |
Non-Patent Citations (1)
| Title |
|---|
| 夏金童等.《常用建材化工日用品生产手册》.江西科学技术出版社,1994,(第1版),第317-318页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115196677A (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102127657A (en) | Comprehensive recovery method for extracting ferrovanadium from stone coal acid immersion liquid | |
| CN112320780A (en) | Method for recovering iron phosphate waste | |
| CN104357671A (en) | Method for separating and recovering vanadium and chromium from vanadium-chromium slag | |
| US3953580A (en) | Boric acid process | |
| CN108911237A (en) | The method of sodium vanadium extracting waste water resource utilization | |
| CN109928420B (en) | Production process of electronic grade ammonium ceric nitrate | |
| US3189407A (en) | Method of recovering lithium from lepidolite | |
| CN115196677B (en) | Method for refining vanadium pentoxide by vanadium liquid | |
| CN116715270A (en) | Method for removing impurity ions in sodium dichromate mother solution by hydration of chromium oxide | |
| CN116397112A (en) | Method for extracting vanadium from Bayer process seed precipitation mother liquor crystallization vanadium slag | |
| EP2172429A1 (en) | Method for the production of sodium sulphate and magnesium hydroxide | |
| WO2024055520A1 (en) | Method for preparing lithium hydroxide by recycling lithium sulfate feed liquid | |
| CN111592017A (en) | Method for preparing battery-grade lithium chloride by pressing and soaking spodumene | |
| CN110423893A (en) | The method that titanium tetrachloride purification tailings prepares vanadic sulfate | |
| CN113816393B (en) | Iron removal method for preparing high-purity boric acid | |
| US4933152A (en) | Continuous process for purifying molybdenum | |
| CN115286019A (en) | Method for producing high-purity lithium carbonate from spodumene | |
| CN114231732A (en) | Method for deeply extracting vanadium from vanadium-containing slurry | |
| CN112723413A (en) | Production method of nuclear-grade zirconium dioxide | |
| CN1078751A (en) | A kind of production method of cerium oxide | |
| CN116873977A (en) | Method for refining vanadium pentoxide by calcified acid leaching vanadium liquid | |
| RU2806940C1 (en) | Method for sulphuric acid processing of scandium-containing raw materials | |
| US1597216A (en) | Process of treating vanadium ores and solutions | |
| CN115448362B (en) | Method for separating and preparing zirconium salt from zirconium oxychloride mother solution and preparing zirconium oxide solid | |
| CN103395838A (en) | High-purity potassium metavanadate and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231213 Address after: Room 1006, 10th Floor, Unit 1, Building 17, No. 89 Hezuo Road, High tech Zone, Chengdu, Sichuan Province, 611730 Patentee after: PANGANG GROUP RESEARCH INSTITUTE Co.,Ltd. Patentee after: PANGANG GROUP VANADIUM TITANIUM & RESOURCES Co.,Ltd. Address before: No. 1006, Floor 10, Unit 1, Building 17, No. 89, Hezuo Road, High tech Zone, Chengdu, Sichuan 611731 Patentee before: PANGANG GROUP RESEARCH INSTITUTE Co.,Ltd. |