CN113233503A - Method for improving purity of ammonium polyvanadate - Google Patents
Method for improving purity of ammonium polyvanadate Download PDFInfo
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- CN113233503A CN113233503A CN202110583421.1A CN202110583421A CN113233503A CN 113233503 A CN113233503 A CN 113233503A CN 202110583421 A CN202110583421 A CN 202110583421A CN 113233503 A CN113233503 A CN 113233503A
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- vanadium
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- polyvanadate
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 189
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 189
- 238000001556 precipitation Methods 0.000 claims abstract description 99
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 28
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 28
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 19
- 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 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 10
- 239000006228 supernatant Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
Abstract
The invention relates to the technical field of metallurgy, in particular to a method for improving the purity of ammonium polyvanadate, which comprises the following steps: firstly, preheating a vanadium-containing solution to 32-35 ℃, and then adjusting the pH value to 3.0-3.5; adding a vanadium precipitation agent and an ammonium polyvanadate seed crystal into the vanadium-containing solution, continuing heating to precipitate vanadium, and keeping the pH value of the solution constant at 1.5-2.5 in the vanadium precipitation process; step three, after the vanadium precipitation is finished, carrying out solid-liquid separation, and passing the solid through (NH)4)2SO4And washing the solution to obtain ammonium polyvanadate. The purification method is simple to operate, improves the purity of the ammonium vanadate product, can reduce the concentration of vanadium in the supernatant after vanadium precipitation, reduces the production cost, improves the vanadium yield, and has very important significance for purifying ammonium polyvanadate.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for improving the purity of ammonium polyvanadate.
Background
Vanadium is an associated element existing in vanadium titano-magnetite, the steel smelting industry changes the strength of steel by adding vanadium, and the dosage of vanadium in the steel industry is increasing year by year. Because of the variety of vanadium raw materials, mineral characteristics and large difference of vanadium content, the process and method for extracting vanadium from vanadium-containing materials are various, no matter which method is adopted to extract vanadium, leached vanadium solution can be obtained, and the vanadium solution can be separated from impurities only by further treatment, so that vanadium oxide with high purity can be obtained. The vanadium solution can be separated from impurities by adopting the processes of vanadium precipitation, calcination, solvent extraction, back extraction and the like. The vanadium precipitation method is divided into calcium salt precipitation, ferric salt precipitation, hydrolysis precipitation, ammonium salt precipitation and the like according to different precipitants, and the ammonium salt precipitation method is divided into a weakly alkaline ammonium salt precipitation method and a weakly acidic ammonium salt precipitation method according to different pH values of solutions during precipitation.
The traditional acidic ammonium salt vanadium precipitation process is to add a proper amount of ammonium salt into a purified vanadium solution, adjust the pH value to 2.0-3.0 by using inorganic acid, and precipitate vanadium at the temperature higher than 90 ℃. And after the vanadium is precipitated, filtering the precipitate, washing the precipitate with water, and drying and calcining the precipitate to obtain vanadium pentoxide. However, by adopting the traditional acid ammonium salt vanadium precipitation process, the concentration of sodium and vanadium in the solution after vanadium precipitation is high, the combination speed of sodium and vanadium is high, sodium polyvanadate is easy to generate, and the product purity is influenced.
In order to solve the existing problems, a new ammonium polyvanadate purification method is developed, so that the purity of an ammonium polyvanadate product is improved, the vanadium concentration of a supernatant after vanadium precipitation can be reduced, the production cost is reduced, the vanadium yield is improved, and the method has very important significance for purifying ammonium polyvanadate.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a method for improving the purity of ammonium polyvanadate, the purification method is simple to operate, the purity of the ammonium polyvanadate product is improved, the concentration of vanadium in the supernatant after vanadium precipitation can be reduced, the production cost is reduced, the vanadium yield is improved, and the defects in the prior art are overcome.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a method for improving the purity of ammonium polyvanadate, which comprises the following steps:
firstly, preheating a vanadium-containing solution to 32-35 ℃, and then adjusting the pH value to 3.0-3.5;
adding a vanadium precipitation agent and an ammonium polyvanadate seed crystal into the vanadium-containing solution, continuing heating to precipitate vanadium, and keeping the pH value of the solution constant at 1.5-2.5 in the vanadium precipitation process;
step three, after the vanadium precipitation is finished, carrying out solid-liquid separation, and passing the solid through (NH)4)2SO4And washing the solution to obtain ammonium polyvanadate.
According to the method for improving the purity of the ammonium polyvanadate, the vanadium-containing solution is heated to 32-35 ℃, the pH value is adjusted to 3.0-3.5, the vanadium precipitation agent and the seed crystal are added, then the heating and the pH value adjustment are continued, and then the vanadium precipitation is carried out, so that the vanadium precipitation temperature and the pH value range can be controlled quickly and accurately, the steps are mutually synergistic, the vanadium precipitation time can be greatly shortened, the contact time of the ammonium polyvanadate and impurities in the solution is reduced, and the purity of the ammonium polyvanadate product is improved. Destroy the solution supersaturation through adding ammonium polyvanadate seed crystal during heavy vanadium, can shorten heavy vanadium time, reduce the contact time of ammonium polyvanadate and impurity, improve ammonium polyvanadate product purity, and can not produce harmful effects to product purity. By using (NH)4)2SO4On one hand, the solution washing solid can fully wash off impurities on the ammonium vanadate solid, reduce the contents of sodium, potassium and sulfur in the ammonium vanadate solid and improve the purity of the ammonium vanadate product, on the other hand, the solution washing solid is prepared byIn (NH)4)2SO4NH in solution4 +And the same ion effect of the ammonium polyvanadate can reduce the re-dissolution of the ammonium polyvanadate solid, does not influence the impurity removal effect, reduces the concentration of the vanadium in the supernatant after the vanadium precipitation, and improves the yield of the vanadium.
Preferably, in the first step, the concentration of vanadium in the vanadium-containing solution is 20-30 g/L in terms of vanadium pentoxide, and the sodium concentration is 10-30 g/L.
The preparation method is more suitable for low-concentration vanadium-containing solution.
Preferably, in the step one, the pH value is adjusted to 3.2-3.4.
Preferably, in the second step, the vanadium precipitation agent is a mixture of industrial ammonium sulfate and an ammonium sulfate solution recovered from vanadium precipitation wastewater, the ammonium addition coefficient is 0.8-1.0, and the molar ratio of the industrial ammonium sulfate to the ammonium sulfate recovered from the vanadium precipitation wastewater is 0-0.7: 1 to 0.3.
By utilizing the ammonium sulfate in the vanadium precipitation wastewater to precipitate vanadium, the production cost is reduced, and the resource waste is reduced.
Preferably, in the second step, the addition amount of the ammonium polyvanadate seed crystal is 1/250-1/220 of the mass of the theoretically generated ammonium polyvanadate.
And adding ammonium polyvanadate seed crystals when the low-concentration vanadium-containing solution is subjected to vanadium precipitation, wherein when the adding amount of the ammonium polyvanadate seed crystals is 1/250-1/220 of the final mass of the generated ammonium polyvanadate, the vanadium precipitation time can be shortened, and the vanadium precipitation rate of the acidic ammonium salt is further improved.
Preferably, in the second step, the heating temperature is 80-90 ℃.
Preferably, in the second step, the vanadium precipitation time is 20-30 min.
Preferably, step three, (NH)4)2SO4The mass concentration of the solution is 0.5-1.5%, and the temperature is 50-70 ℃.
The use temperature of the catalyst is 50-70 ℃, and the mass concentration of the catalyst is 0.5-1.5% (NH)4)2SO4The solution washing solid can fully wash off impurities on the ammonium vanadate solid, reduce the contents of sodium, potassium and sulfur in the ammonium vanadate solid, improve the product purity of the ammonium vanadate, and reduce the content of ammonium polyvanadateThe solid is re-dissolved, and the impurity removal effect is not influenced. In the obtained solid K2O+Na2The content of O is lower than 0.19 percent, the content of S is lower than 0.01 percent, the vanadium concentration of the supernatant after vanadium precipitation is lower than 0.17g/L, the vanadium concentration of the supernatant after vanadium precipitation is reduced, and the vanadium yield is improved.
The method for improving the purity of the ammonium polyvanadate is simple to operate, mild in reaction conditions, capable of reducing the concentration of vanadium in a supernatant after vanadium precipitation while improving the purity of an ammonium vanadate product, reducing the production cost, improving the vanadium yield and having very important significance for purifying the ammonium polyvanadate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a method for improving the purity of ammonium polyvanadate, which comprises the following steps:
(1) after the vanadium-containing solution is preheated to 35 ℃, sulfuric acid is used for adjusting the pH value to 3.0, the concentration of vanadium in the vanadium-containing solution is 30g/L calculated as vanadium pentoxide, and the sodium concentration is 17 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 88 ℃, precipitating vanadium for 25min, and keeping the pH of the solution constant at 2.5 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/250 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an industrial ammonium sulfate solution and an ammonium sulfate solution recovered from vanadium precipitation wastewater, the molar ratio of the industrial ammonium sulfate to the vanadium precipitation agent is 0.5:0.5, and the ammonium addition coefficient is 0.8.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and the solid is 0.5 percent (NH) at the temperature of 50 DEG C4)2SO4And washing the solution to obtain ammonium polyvanadate.
Example 2
The embodiment provides a method for improving the purity of ammonium polyvanadate, which comprises the following steps:
(1) after the vanadium-containing solution is preheated to 34 ℃, the pH value is adjusted to 3.2 by using sulfuric acid, the concentration of vanadium in the vanadium-containing solution is 25g/L calculated by vanadium pentoxide, and the sodium concentration is 20 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 84 ℃, precipitating vanadium for 30min, and keeping the pH value of the solution constant at 1.5 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/240 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an ammonium sulfate solution recovered from industrial ammonium sulfate and vanadium precipitation wastewater with the molar ratio of 0.7:0.3, and the ammonium addition coefficient is 0.9.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and the solid is 0.5 percent (NH) at the temperature of 60 DEG C4)2SO4And washing the solution to obtain ammonium polyvanadate.
Example 3
The embodiment provides a method for improving the purity of ammonium polyvanadate, which comprises the following steps:
(1) after the vanadium-containing solution is preheated to 33 ℃, the pH value is adjusted to 3.4 by using sulfuric acid, the concentration of vanadium in the vanadium-containing solution is 20g/L calculated by vanadium pentoxide, and the sodium concentration is 30 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 90 ℃, precipitating vanadium for 30min, and keeping the pH value of the solution constant at 1.9 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/220 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an industrial ammonium sulfate solution with the molar ratio of 0.3:0.7 and an ammonium sulfate solution recovered from vanadium precipitation wastewater, and the ammonium addition coefficient is 1.0.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and the solid is 1 percent (NH) at the temperature of 70 DEG C4)2SO4And washing the solution to obtain ammonium polyvanadate.
Example 4
The embodiment provides a method for improving the purity of ammonium polyvanadate, which comprises the following steps:
(1) after the vanadium-containing solution is preheated to 32 ℃, the pH value is adjusted to 3.5 by using sulfuric acid, the concentration of vanadium in the vanadium-containing solution is 22g/L calculated by vanadium pentoxide, and the sodium concentration is 10 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 80 ℃, precipitating vanadium for 30min, and keeping the pH of the solution constant at 2.1 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/230 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an ammonium sulfate solution recovered from industrial ammonium sulfate and vanadium precipitation wastewater with the molar ratio of 0:1, and the ammonium addition coefficient is 0.9.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and 1.2 percent (NH) of the solid at 65 ℃ is used4)2SO4And washing the solution to obtain ammonium polyvanadate.
Comparative example 1
The comparative example provides a method for improving the purity of ammonium polyvanadate without preheating, which is tested in the research process, and comprises the following steps:
the embodiment provides a method for improving the purity of ammonium polyvanadate, which comprises the following steps:
(1) regulating the pH value of the vanadium-containing solution at room temperature to 3.4 by using sulfuric acid, wherein the concentration of vanadium in the vanadium-containing solution is 20g/L in terms of vanadium pentoxide, and the concentration of sodium is 30 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 90 ℃, precipitating vanadium for 30min, and keeping the pH value of the solution constant at 1.9 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/220 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an industrial ammonium sulfate solution with the molar ratio of 0.3:0.7 and an ammonium sulfate solution recovered from vanadium precipitation wastewater, and the ammonium addition coefficient is 1.0.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and the solid is 1 percent (NH) at the temperature of 70 DEG C4)2SO4And washing the solution to obtain ammonium polyvanadate.
Comparative example 2
The comparative example provides a method for obtaining high ammonium polyvanadate purity without adjusting the pH value step by step, which is tested in the research process, and comprises the following steps:
(1) the vanadium-containing solution with the pH value of 8.5 is preheated to 33 ℃, the concentration of vanadium in the vanadium-containing solution is 20g/L calculated by vanadium pentoxide, and the concentration of sodium is 30 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 90 ℃, precipitating vanadium for 30min, and adjusting the pH value to be constant at 1.9 by using sulfuric acid in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/220 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an industrial ammonium sulfate solution with the molar ratio of 0.3:0.7 and an ammonium sulfate solution recovered from vanadium precipitation wastewater, and the ammonium addition coefficient is 1.0.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and the solid is 1 percent (NH) at the temperature of 70 DEG C4)2SO4And washing the solution to obtain ammonium polyvanadate.
Comparative example 3
The comparative example provides a method for improving the purity of ammonium polyvanadate without adding ammonium polyvanadate seed crystals, which is tested in the research process, and comprises the following steps:
(1) after the vanadium-containing solution is preheated to 33 ℃, the pH value is adjusted to 3.4 by using sulfuric acid, the concentration of vanadium in the vanadium-containing solution is 20g/L calculated by vanadium pentoxide, and the sodium concentration is 30 g/L.
(2) Adding a vanadium precipitation agent into the vanadium-containing solution, continuously heating to 90 ℃, precipitating vanadium for 30min, and keeping the pH value of the solution constant at 1.9 in the vanadium precipitation process. The vanadium precipitation agent is industrial ammonium sulfate with a molar ratio of 0.3:0.7 and an ammonium sulfate solution recovered from vanadium precipitation wastewater, and the ammonium addition coefficient is 1.0.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and the solid is 1 percent (NH) at the temperature of 70 DEG C4)2SO4And washing the solution to obtain ammonium vanadate.
Comparative example 4
This comparative example provides a method of increasing the purity of ammonium polyvanadate by washing the solids with tap water at 70 ℃ as tested in the study procedure, comprising the steps of:
(1) after the vanadium-containing solution is preheated to 33 ℃, the pH value is adjusted to 3.4 by using sulfuric acid, the concentration of vanadium in the vanadium-containing solution is 20g/L calculated by vanadium pentoxide, and the sodium concentration is 30 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 90 ℃, precipitating vanadium for 30min, and keeping the pH value of the solution constant at 1.9 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/220 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an industrial ammonium sulfate solution with the molar ratio of 0.3:0.7 and an ammonium sulfate solution recovered from vanadium precipitation wastewater, and the ammonium addition coefficient is 1.0.
(3) And after the vanadium precipitation is finished, carrying out solid-liquid separation, and washing the solid by using tap water at the temperature of 70 ℃ to obtain ammonium polyvanadate.
Comparative example 5
This comparative example provides a 1% use of (NH) at room temperature tested during the study4)2SO4A method for improving the purity of ammonium polyvanadate by washing solid with solution, comprising the following steps:
(1) after the vanadium-containing solution is preheated to 33 ℃, the pH value is adjusted to 3.4 by using sulfuric acid, the concentration of vanadium in the vanadium-containing solution is 20g/L calculated by vanadium pentoxide, and the sodium concentration is 30 g/L.
(2) Adding a vanadium precipitation agent and ammonium polyvanadate seed crystals into the vanadium-containing solution, continuously heating to 90 ℃, precipitating vanadium for 30min, and keeping the pH value of the solution constant at 1.9 in the vanadium precipitation process. The addition amount of the ammonium polyvanadate seed crystal is 1/220 of the mass of the theoretically generated ammonium polyvanadate, the vanadium precipitation agent is an industrial ammonium sulfate solution with the molar ratio of 0.3:0.7 and an ammonium sulfate solution recovered from vanadium precipitation wastewater, and the ammonium addition coefficient is 1.0.
(3) After the vanadium precipitation is finished, solid-liquid separation is carried out, and (NH) with the room temperature of 1 percent is used as solid4)2SO4And washing the solution to obtain ammonium polyvanadate.
Ammonium polyvanadate obtained by precipitation in examples 1-4 and comparative examples 1-5 is heated and calcined, and the contents of vanadium pentoxide and impurities of sodium, potassium and sulfur in the calcined product are detected, wherein the specific detection results are shown in table 1.
TABLE 1
According to the results shown in Table 1, the vanadium-containing solution is preheated by heating step by step, the vanadium-containing solution is heated to 32-35 ℃, the pH value is adjusted to 3.0-3.5, the vanadium precipitation agent and the seed crystal are added, the vanadium precipitation is carried out after the heating and the pH adjustment are continued, the vanadium precipitation temperature and the pH value range can be controlled quickly and accurately, the steps are mutually synergistic, the vanadium precipitation time can be greatly shortened, and the ammonium polyvanadate and impurities in the solution are reducedThe contact time of the ammonium polyvanadate is prolonged, and the purity of the ammonium polyvanadate product is improved. 0.5-1.5% by mass (NH) at 50-70 ℃4)2SO4Solution washed ammonium polyvanadate2O+Na2The content of O is less than 0.19 percent, and the content of S is less than 0.01 percent. The concentration of vanadium in the supernatant after vanadium precipitation is lower than 0.17g/L, so that the concentration of vanadium in the supernatant after vanadium precipitation is reduced, and the yield of vanadium is improved.
In conclusion, the method for improving the purity of the ammonium polyvanadate provided by the invention is simple to operate, the purity of the ammonium vanadate product is improved, the concentration of vanadium in a supernatant after vanadium precipitation can be reduced, the production cost is reduced, and the vanadium yield is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for improving the purity of ammonium polyvanadate is characterized by comprising the following steps:
firstly, preheating a vanadium-containing solution to 32-35 ℃, and then adjusting the pH value to 3.0-3.5;
adding a vanadium precipitation agent and an ammonium polyvanadate seed crystal into the vanadium-containing solution, continuing heating to precipitate vanadium, and keeping the pH value of the solution constant at 1.5-2.5 in the vanadium precipitation process;
step three, after the vanadium precipitation is finished, carrying out solid-liquid separation, and passing the solid through (NH)4)2SO4And washing the solution to obtain ammonium polyvanadate.
2. The method of claim 1, wherein the purity of ammonium polyvanadate is increased by: in the first step, the concentration of vanadium in the vanadium-containing solution is 20-30 g/L in terms of vanadium pentoxide, and the concentration of sodium is 10-30 g/L.
3. The method of claim 1, wherein the purity of ammonium polyvanadate is increased by: in the first step, the pH value is adjusted to 3.2-3.4.
4. The method of claim 1, wherein the purity of ammonium polyvanadate is increased by: in the second step, the vanadium precipitation agent is a mixture of industrial ammonium sulfate and an ammonium sulfate solution recovered from vanadium precipitation wastewater, the ammonium addition coefficient is 0.8-1.0, and the molar ratio of the industrial ammonium sulfate to the ammonium sulfate recovered from the vanadium precipitation wastewater is 0-0.7: 1 to 0.3.
5. The method of claim 1, wherein the purity of ammonium polyvanadate is increased by: in the second step, the addition amount of the ammonium polyvanadate seed crystal is 1/250-1/220 of the mass of the theoretically generated ammonium polyvanadate.
6. The method of claim 1, wherein the purity of ammonium polyvanadate is increased by: in the second step, the heating is carried out to 80-90 ℃.
7. The method of claim 6, wherein the purity of ammonium polyvanadate is increased by: in the second step, the vanadium precipitation time is 20-30 min.
8. The method of claim 1, wherein the purity of ammonium polyvanadate is increased by: in step three, the (NH)4)2SO4The mass concentration of the solution is 0.5-1.5%, and the temperature is 50-70 ℃.
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