CN113151684A - Method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid - Google Patents
Method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 160
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000001376 precipitating Effects 0.000 title claims abstract description 28
- 239000011734 sodium Substances 0.000 title claims abstract description 28
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 22
- 238000000746 purification Methods 0.000 title claims abstract description 18
- 238000002386 leaching Methods 0.000 title claims description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 34
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 77
- 150000003863 ammonium salts Chemical class 0.000 claims description 36
- 238000009835 boiling Methods 0.000 claims description 28
- 239000012266 salt solution Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 230000001502 supplementation Effects 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 4
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000001105 regulatory Effects 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 12
- NTGONJLAOZZDJO-UHFFFAOYSA-M disodium;hydroxide Chemical compound [OH-].[Na+].[Na+] NTGONJLAOZZDJO-UHFFFAOYSA-M 0.000 description 12
- 239000011651 chromium Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000003301 hydrolyzing Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N Sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- -1 vanadium-chromium Chemical compound 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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 discloses a method for precipitating vanadium from a sodium roasting water immersion purification solution by hydrochloric acid, belonging to the field of hydrometallurgy. The method for precipitating vanadium by using hydrochloric acid is characterized by adding hydrochloric acid into the purified liquor, regulating pH value of said solution, heating and continuously stirring to separate out precipitate, washing said precipitate, heating and melting so as to obtain the vanadium pentoxide product with vanadium pentoxide contents of 98.0%, 99.0% and 99.5%. The method has the advantages of simple process, less working procedures and high production efficiency. Under the same condition, the hydrochloric acid has higher vanadium precipitation rate than sulfuric acid, the obtained vanadium pentoxide is purer, and the problems of lower purity and vanadium precipitation rate of the vanadium product obtained by the existing sulfuric acid hydrolysis vanadium precipitation method are effectively solved.
Description
Technical Field
The invention belongs to the field of hydrometallurgy, and particularly relates to a method for precipitating vanadium from a sodium roasting water leaching purification solution by hydrochloric acid.
Background
At present, the vanadium precipitation method for sodium salt roasting water leaching purification solution mainly comprises the method of hydrolyzing ammonium salt and sulfuric acid to precipitate vanadium, and because the high ammonium concentration wastewater and ammonia waste gas generated by vanadium precipitation by ammonium salt pollute the environment and the treatment cost is high, the research on hydrolyzing vanadium precipitation is turned to.
At present, in the prior art for researching the vanadium precipitation by sulfuric acid hydrolysis, the problems of complex process, multiple working procedures, low production efficiency, poor practicability, and the need of technically modifying equipment, facilities and the like for precipitating vanadium from the original ammonium salt exist, such as: patent CN102897834A published in 1 month of 2013, relating to a method for precipitating vanadium and a method for preparing vanadium pentoxide; patent CN105256137A published in 6.2018 is a method for hydrolyzing and precipitating vanadium-containing solution.
And the literature, "vanadium-chromium solution hydrolysis vanadium precipitation test research" (Wuzhexiu, Jianglin vanadium-chromium solution hydrolysis vanadium precipitation test research [ J)]Vanadium-titanium iron 2020,41(05): 22-26) and literature "high-efficiency low-consumption green vanadium precipitation technology experimental research" (Lecidaceae, Tang Xian, high-efficiency low-consumption green vanadium precipitation technology experimental research [ J]Ferroalloy 2014,45(06):25-29.) shows that when the sulfuric acid hydrolysis vanadium precipitation method is adopted, vanadium precipitation is carried out at high sodium concentration (> 50g/L), and sodium vanadate is generated more, so that V is caused if sodium removal is incomplete2O5The purity is lower; at the same time because part of vanadium generates [ VO2SO4]-And the vanadium deposition rate is influenced by factors.
In addition, in some methods, in order to remove sodium, the production cost is increased by adding sodium removal procedures, equipment and materials thereof, and meanwhile, vanadium loss is increased once in the sodium removal solution, so that the vanadium yield is reduced, namely the vanadium precipitation rate is reduced, such as: patent CN104694761A published in 6.2015, which is a method for extracting vanadium from vanadium liquid in a vanadium slag sodium salt roasting vanadium extraction process; patent CN111592042A published in 8.2020, which is a method for preparing high-purity vanadium pentoxide by vanadium liquid without ammonium precipitation; patent CN112030011A in 12.2020 discloses a method for producing vanadium pentoxide by one-step vanadium precipitation of vanadium-containing material by a full-wet method.
Therefore, compared with the prior art, the research on the vanadium precipitation rate is higher, and V is higher2O5The impurity content is lower, and a vanadium precipitation method with simple process steps is necessary.
Disclosure of Invention
The invention aims to solve the technical problem that the purity and vanadium precipitation rate of the vanadium product obtained by the existing sulfuric acid hydrolysis vanadium precipitation method are low.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for precipitating vanadium by using hydrochloric acid for the sodium salt roasting water leaching purification solution comprises the following steps:
a. under the stirring state, hydrochloric acid is used for adjusting the pH value of the purifying solution to 0.50-1.60, and the pH value is kept stable;
b. b, under the stirring state, putting the solution treated in the step a into a water bath kettle, heating the water bath kettle until the water is boiled, and keeping the boiling time to be more than or equal to 35 min;
c. b, filtering the liquid treated in the step b to obtain red vanadium precipitate, and washing the red vanadium precipitate by using an ammonium salt solution;
d. and c, heating the red vanadium washed in the step c to be molten, and cooling to obtain vanadium pentoxide.
In the step a, the purifying solution is obtained by leaching solution obtained by a sodium roasting water leaching process and removing impurities from calcium salt, aluminum salt or magnesium salt.
The concentration of vanadium in the purifying liquid is 10-70 g/L.
Further, the concentration of vanadium in the purifying liquid is 15-50 g/L.
In the step a, the concentration of the hydrochloric acid is 20-38%, and the hydrochloric acid can be diluted by 1-2 times when in use.
In the step a, the condition for keeping the pH value stable is that the pH value is changed to more than +/-0.05 within 10-30 s.
Further, the condition for keeping the pH value stable is that the pH value is not more than + -0.01 within 20 s.
In the steps a and b, the stirring speed is 300-400 r/min.
Further, in the above steps a and b, the stirring speed was 350 r/min.
And in the step b, timely supplementing the reduced evaporation amount of the vanadium precipitation solution with boiling water in the boiling process.
In the step c, the washing method comprises the following steps: according to the liquid-solid ratio of ammonium salt solution to precipitated red vanadium of 1.3-2.0mL to 1g, stirring to disperse red vanadium, filtering to dry, and repeating for 2-4 times.
Further, the above ammonium salt solution precipitated red vanadium 1.4-1.6 mL: 1 g.
In the step c, the concentration of the ammonium salt solution is 5-50g/L, and the ammonium salt is at least one of ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium acetate.
Further, the ammonium salt is ammonium chloride, and the concentration of the ammonium salt solution is 7-12 g/L.
The invention has the beneficial effects that: the invention adopts hydrochloric acid as a vanadium precipitation agent, and adjusts the pH value of the purifying solution to carry out hydrolysis and vanadium precipitation. High-purity poly-vanadic acid is obtained by depositing vanadium with hydrochloric acidSalt, washing the precipitate with low ammonium salt solution, heating to melt to obtain V2O5Products with the contents of 98.0%, 99.0% and 99.5% are obtained.
On the basis of equipment and facilities for precipitating vanadium from orthogenic ammonium salt, the method does not need additional production equipment and facilities besides replacing sulfuric acid with hydrochloric acid, and has the advantages of simple process, less working procedures and high production efficiency. Under the same condition, the hydrochloric acid has higher vanadium precipitation rate than sulfuric acid, and the obtained V2O5The method uses 1/10 of ammonium salt precipitated vanadium, which can increase the recycling times of the washing filtrate and greatly reduce the environmental pollution and the wastewater treatment cost.
Detailed Description
The technical solution of the present invention can be specifically implemented as follows.
The method for precipitating vanadium by using hydrochloric acid for the sodium salt roasting water leaching purification solution comprises the following steps:
a. under the stirring state, hydrochloric acid is used for adjusting the pH value of the purifying solution to 0.50-1.60, and the pH value is kept stable;
b. b, under the stirring state, putting the solution treated in the step a into a water bath kettle, heating the water bath kettle until the water is boiled, and keeping the boiling time to be more than or equal to 35 min;
c. b, filtering the liquid treated in the step b to obtain red vanadium precipitate, and washing the red vanadium precipitate by using an ammonium salt solution;
d. and c, heating the red vanadium washed in the step c to be molten, and cooling to obtain vanadium pentoxide.
In the step a, the purifying solution is obtained by leaching solution obtained by a sodium roasting water leaching process and removing impurities from calcium salt, aluminum salt or magnesium salt. Among them, vanadium exists in pentavalent form, and usually contains impurities such as sodium, potassium, silicon, phosphorus, sulfur, calcium, magnesium, iron, aluminum, chromium, manganese, titanium, and the like.
In order to maximize the utilization of raw materials and achieve better experimental effects, it is preferable that the concentration of vanadium in the purified solution is 10-70 g/L. More preferably, the concentration of vanadium in the purified liquid is 15-50 g/L.
For better pH control, it is preferable that the hydrochloric acid concentration in the step a is 20-38%, and the hydrochloric acid can be diluted 1-2 times when used.
In order to reduce the influence of the solution pH value on the hydrolysis vanadium precipitation reaction, it is preferable that the pH value is kept stable in the step a under the condition that the pH value is not more than + -0.05 within 10-30 s. More preferably, the pH is maintained at a stable value within 20s under the condition that the pH value is not more than. + -. 0.01.
Since the hydrolysis precipitation of vanadium is a hydrolysis reaction process accompanied by heat and mass transfer, and the stirring speed is properly maintained, it is preferable that the stirring speed in the above steps a and b is 400 r/min. More preferably, the stirring speed is 350 r/min.
In order to reduce the change of the pH value and the temperature of the precipitated vanadium solution during the heating process, it is preferable that the evaporation reduction amount of the precipitated vanadium solution is timely supplemented with boiling water during the boiling process in the step b.
In order to remove impurities and achieve a product with higher purity, it is preferable that the washing method in the step c is: according to the liquid-solid ratio of ammonium salt solution to precipitated red vanadium of 1.3-2.0mL to 1g, stirring to disperse red vanadium, filtering to dry, and repeating for 2-4 times. More preferably, the ammonium salt solution precipitated red vanadium is 1.4-1.6 mL: 1 g.
In order to reduce the entry of impurities and achieve better impurity removal effect, it is preferable that in the step c, the concentration of the ammonium salt solution is 5 to 50g/L, and the ammonium salt is at least one of ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium acetate. More preferably, the ammonium salt is ammonium chloride and the concentration of the ammonium salt solution is 7-12 g/L.
The technical solution and effects of the present invention will be further described below by way of practical examples.
Examples
Example 1: taking 300mL of each of 2 parts of purified solution (wherein V is 24.58g/L, Na is 60.1g/L), respectively adjusting the pH value to 1.20 and 1.40 by hydrochloric acid (1+1) under stirring, wherein the pH value is not more than +/-0.01 within 20s, putting the purified solution into a room-temperature water bath kettle, stirring the vanadium precipitation solution at the speed of 350r/min, heating to boiling for 50min (supplementing the vanadium precipitation solution with boiling water in time during boiling for evaporation), taking out the solution, carrying out solid-liquid suction filtration separation, washing the precipitated red vanadium by using 10g/L of ammonium chloride solution, and obtaining the ammonium salt solution (mL): precipitating red vanadium (g) at a liquid-solid ratio of 1.5: 1, stirring to disperse the red vanadium, filtering to dry, repeating the steps for 3 times, heating the red vanadium in a muffle furnace to melt, taking out, pouring out, and cooling to obtain flaky vanadium pentoxide.
Through the inspection: 1. the vanadium deposition rate of pH1.20 is 99.53%, and V in the vanadium pentoxide2O5＝99.39％、Si＝0.045％、Fe＝0.01％、P＝0.003％、S＝0.006％。Na2O＝0.51％、K2O＝0.04％、Cr＝0.052％。
2. The vanadium deposition rate of pH1.40 is 99.70%, and V in vanadium pentoxide is2O5＝98.43％、Si＝0.120％、Fe＝0.03％、P＝0.007％、S＝0.009％。Na2O＝0.97％、K2O＝0.09％、Cr＝0.082％。
Example 2: taking 300mL of each of 2 parts of purified solution (wherein V is 29.47g/L, Na is 73.3g/L), respectively adjusting the pH value to 0.90 and 1.10 by hydrochloric acid (1+1) under stirring, wherein the pH value is not more than +/-0.01 within 20s, putting the purified solution into a room-temperature water bath kettle, stirring the vanadium precipitation solution at the speed of 350r/min, heating to boil for 40min (supplementing the vanadium precipitation solution with boiling water in time during boiling for evaporation), taking out the solution, carrying out solid-liquid suction filtration separation, washing the precipitated red vanadium by using 10g/L of ammonium chloride solution, and obtaining the ammonium salt solution (mL): precipitating red vanadium (g) at a liquid-solid ratio of 1.5: 1, stirring to disperse the red vanadium, filtering to dry, repeating the steps for 3 times, heating the red vanadium in a muffle furnace to melt, taking out, pouring out, and cooling to obtain flaky vanadium pentoxide.
Through the inspection: 1. the vanadium deposition rate of pH0.90 is 98.84%, and V in the vanadium pentoxide2O5＝99.55％、Na2O＝0.34％、K2O＝0.03％。
2. The vanadium deposition rate of pH1.10 is 99.63%, and V in the vanadium pentoxide is2O5＝98.87％、Na2O＝0.77％、K2O＝0.05％。
Example 3: taking 300mL of each of 2 parts of purified solution (wherein V is 51.99g/L, Na is 100.1g/L), respectively adjusting the pH value to 0.50 and 0.70 by hydrochloric acid (1+1) under stirring, wherein the pH value is not more than +/-0.01 within 20s, putting the purified solution into a room-temperature water bath kettle, stirring the vanadium precipitation solution at the speed of 400r/min, heating to boiling for 35min (supplementing the vanadium precipitation solution with boiling water in time during boiling for evaporation), taking out the solution, carrying out solid-liquid suction filtration separation, washing the precipitated red vanadium by using 10g/L of ammonium chloride solution, and obtaining the ammonium salt solution (mL): precipitating red vanadium (g) at a liquid-solid ratio of 2.0: 1, stirring to disperse the red vanadium, filtering to dry, repeating the steps for 4 times, heating the red vanadium in a muffle furnace to melt, taking out, pouring out and cooling to form flaky vanadium pentoxide.
Through the inspection: 1. the precipitation rate of vanadium with a pH value of 0.50 is 97.76%, and V in vanadium pentoxide is2O5＝99.61％、Na2O＝0.29％、K2O＝0.02％。
2. The precipitation rate of vanadium with pH of 0.70 is 99.48%, and V in vanadium pentoxide is2O5＝98.91％、Na2O＝0.72％、K2O＝0.05％。
Example 4: taking 300mL of each of 2 parts of purified solution (wherein V is 14.82g/L, Na is 31.85g/L), respectively adjusting the pH to 1.30 and 1.60 by hydrochloric acid (1+1) under stirring, wherein the pH value is not more than +/-0.01 within 20s, putting the purified solution into a room-temperature water bath kettle, stirring the vanadium precipitation solution at the speed of 350r/min, heating to boil for 60min (the boiling water is used for supplementing the evaporation reduction amount of the vanadium precipitation solution in time in the boiling process), taking out, carrying out solid-liquid suction filtration separation, washing the precipitated red vanadium by using 10g/L of ammonium chloride solution, and obtaining the ammonium salt solution (mL): precipitating red vanadium (g) at a liquid-solid ratio of 2.0: 1, stirring to disperse the red vanadium, filtering to dry, repeating the steps for 2 times, heating the red vanadium in a muffle furnace to melt, taking out, pouring out, and cooling to obtain flaky vanadium pentoxide.
Through the inspection: 1. the vanadium deposition rate of the vanadium pentoxide is 98.52 percent, and V is contained in the vanadium pentoxide2O5＝99.62％、Na2O＝0.37％、K2O＝0.02％。
2. The vanadium deposition rate of the vanadium pentoxide is 99.03 percent, and V is contained in the vanadium pentoxide2O5＝98.72％、Na2O＝0.86％、K2O＝0.04％。
Example 5: taking 300mL of each of 2 parts of purified solution (wherein V is 27.31g/L, Na is 54.6g/L, and Cr is 20.22g/L), respectively adjusting the pH value to 1.20 and 1.40 by hydrochloric acid (1+1) under stirring, wherein the pH value is not more than +/-0.01 within 20s, putting the purified solution into a room-temperature water bath kettle, stirring the vanadium precipitation solution at the speed of 350r/min, heating to boiling, then 50min (the evaporation reduction amount of the vanadium precipitation solution is timely compensated by boiling water in the boiling process), taking out, carrying out suction filtration and separation, washing the precipitated vanadium with 10g/L of ammonium chloride solution, and obtaining the ammonium salt solution (mL): precipitating red vanadium (g) at a liquid-solid ratio of 2.0: 1, stirring to disperse the red vanadium, filtering to dry, repeating the steps for 3 times, heating the red vanadium in a muffle furnace to melt, taking out, pouring out, and cooling to obtain flaky vanadium pentoxide.
Through the inspection: 1. the vanadium deposition rate of pH1.20 is 99.30%, and V in the vanadium pentoxide2O5＝99.35％、Na2O＝0.43％、K2O＝0.03％、Cr＝0.083％。
2. The vanadium deposition rate of the vanadium pentoxide is 99.51 percent, and V is contained in the vanadium pentoxide2O5＝98.22％、Na2O＝1.36％、K2O＝0.07％、Cr＝0.121％。
Comparative example: taking 300mL of each of 2 parts of purified solution (wherein V is 24.58g/L, Na is 60.1g/L), respectively adjusting the pH value to 1.20 and 1.40 by using sulfuric acid (1+1) under stirring, wherein the pH value is not more than +/-0.01 within 20s, putting the purified solution into a room-temperature water bath kettle, stirring the vanadium precipitation solution at the speed of 350r/min, heating to boiling for 50min (supplementing the vanadium precipitation solution with boiling water in time during boiling for evaporation), taking out the solution, carrying out solid-liquid suction filtration separation, washing the precipitated red vanadium by using 10g/L of ammonium chloride solution, and obtaining the ammonium salt solution (mL): precipitating red vanadium (g) at a liquid-solid ratio of 1.5: 1, stirring to disperse the red vanadium, filtering to dry, repeating the steps for 3 times, heating the red vanadium in a muffle furnace to melt, taking out, pouring out, and cooling to obtain flaky vanadium pentoxide.
Through the inspection: 1. the vanadium deposition rate of pH1.20 is 98.07%, and V in the vanadium pentoxide is2O5＝98.57％、Si＝0.164％、Fe＝0.02％、P＝0.004％、S＝0.026％。Na2O＝0.76％、K2O＝0.05％、Cr＝0.109％。
2. The vanadium deposition rate of the vanadium pentoxide is 99.22 percent, and V is contained in the vanadium pentoxide2O5＝97.87％、Si＝0.246％、Fe＝0.04％、P＝0.008％、S＝0.039％。Na2O＝1.22％、K2O＝0.09％、Cr＝0.122％。
The above implementationIn the examples, 2 portions of different pH values of the same purification solution were used for vanadium precipitation, only to compare the vanadium precipitation rate with the V obtained2O5The difference of product purity does not require 2 times of vanadium precipitation for the same purifying liquid.
In the above embodiment, the vanadium deposition rate is determined by the percentage of the difference between the total vanadium amount in the purifying solution for vanadium deposition and the vanadium amount in the vanadium deposition supernatant solution in the total vanadium amount.
As can be seen from the above, the vanadium precipitation rate of the embodiment of the method of the invention is 97.76-99.70%, and the V of the obtained vanadium flake2O5The content is 98.22-99.62%. As can be seen from the comparison between example 1 and the comparative example, the hydrochloric acid has a higher vanadium deposition rate and a higher vanadium pentoxide purity than sulfuric acid under the same experimental conditions. The method of the invention is based on equipment and facilities for precipitating vanadium from ortho-acidic ammonium salt, and does not need additional equipment and facilities except for replacing sulfuric acid with hydrochloric acid. Simple process, less working procedures and high production efficiency. The method of the invention uses hydrochloric acid to precipitate vanadium, uses solution with low ammonium salt concentration to wash and precipitate red vanadium, uses 1/10 of ammonium salt to precipitate vanadium, can increase the recycling times of the washing filtrate, and can greatly reduce environmental pollution and wastewater treatment cost.
Claims (10)
1. The method for precipitating vanadium by using hydrochloric acid for the sodium salt roasting water leaching purification solution is characterized by comprising the following steps of:
a. under the stirring state, hydrochloric acid is used for adjusting the pH value of the purifying solution to 0.50-1.60, and the pH value is kept stable;
b. b, under the stirring state, putting the solution treated in the step a into a water bath kettle, heating the water bath kettle until the water is boiled, and keeping the boiling time to be more than or equal to 35 min;
c. b, filtering the liquid treated in the step b to obtain red vanadium precipitate, and washing the red vanadium precipitate by using an ammonium salt solution;
d. and c, heating the red vanadium washed in the step c to be molten, and cooling to obtain vanadium pentoxide.
2. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: in the step a, the purifying solution is obtained by leaching solution obtained by a sodium roasting water leaching process and removing impurities from calcium salt, aluminum salt or magnesium salt.
3. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: in the step a, the concentration of vanadium in the purifying liquid is 10-70 g/L.
4. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: in the step a, the condition of keeping the pH value stable is that the pH value is changed to more than +/-0.05 within 10-30 s.
5. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: in the steps a and b, the stirring speed is 300-400 r/min.
6. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: and in the step b, in the boiling process, timely supplementing the reduced amount of the vanadium precipitation solution by using boiling water.
7. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: in the step c, the washing method comprises the following steps: according to the liquid-solid ratio of ammonium salt solution to precipitated red vanadium of 1.3-2.0mL to 1g, stirring to disperse red vanadium, filtering to dry, and repeating for 2-4 times.
8. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 7, characterized in that: ammonium salt solution precipitated red vanadium 1.4-1.6 mL: 1 g.
9. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 1, characterized in that: in the step c, the concentration of the ammonium salt solution is 5-50g/L, and the ammonium salt is at least one of ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium acetate.
10. The method for precipitating vanadium from sodium roasting water leaching purification solution by hydrochloric acid as claimed in claim 9, characterized in that: the ammonium salt is ammonium chloride, and the concentration of the ammonium salt solution is 7-12 g/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1221243A (en) * | 1984-02-01 | 1987-05-05 | Thomas H. Etsell | Vanadium recovery from ash from oil sands |
| CN102167400A (en) * | 2011-03-18 | 2011-08-31 | 中南大学 | Method for preparing vanadium pentoxide from vanadium-containing solution |
| CN102336437A (en) * | 2011-09-06 | 2012-02-01 | 中南大学 | Process for producing vanadium pentoxide by vanadium-contained solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1221243A (en) * | 1984-02-01 | 1987-05-05 | Thomas H. Etsell | Vanadium recovery from ash from oil sands |
| CN102167400A (en) * | 2011-03-18 | 2011-08-31 | 中南大学 | Method for preparing vanadium pentoxide from vanadium-containing solution |
| CN102336437A (en) * | 2011-09-06 | 2012-02-01 | 中南大学 | Process for producing vanadium pentoxide by vanadium-contained solution |
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