CN113186395A - Method for preparing vanadyl sulfate from vanadium-containing solution - Google Patents
Method for preparing vanadyl sulfate from vanadium-containing solution Download PDFInfo
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- CN113186395A CN113186395A CN202110393676.1A CN202110393676A CN113186395A CN 113186395 A CN113186395 A CN 113186395A CN 202110393676 A CN202110393676 A CN 202110393676A CN 113186395 A CN113186395 A CN 113186395A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 93
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 45
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 229940041260 vanadyl sulfate Drugs 0.000 title claims abstract description 25
- 229910000352 vanadyl sulfate Inorganic materials 0.000 title claims abstract description 25
- 239000012074 organic phase Substances 0.000 claims abstract description 56
- 238000000605 extraction Methods 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 21
- 239000011651 chromium Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 92
- 238000006722 reduction reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 239000008346 aqueous phase Substances 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 6
- 238000007127 saponification reaction Methods 0.000 claims description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229910004879 Na2S2O5 Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- -1 mono 2-ethylhexyl Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a method for preparing vanadyl sulfate from a vanadium-containing solution, which comprises the following steps: s1, reducing high-valence vanadium in the solution; s2, adjusting the content and acidity of vanadium in the solution; s3, extracting vanadium in the solution into an organic phase; s4, back-extracting vanadium from the vanadium-carrying organic phase by using sulfuric acid to obtain a vanadyl sulfate solution product; s5, carrying out back extraction of iron and chromium on the organic phase and washing with water, and recycling; the method for preparing vanadyl sulfate from the vanadium-containing solution provided by the invention is characterized in that vanadium is a variable-valence metal in the solution, and has different states with different pH, different potentials and different concentrations, so that the separation of vanadium and impurities in the extraction process is effectively solved, and the vanadyl sulfate product with high vanadium concentration and low impurity content is prepared in a short process.
Description
Technical Field
The invention relates to the technical field of preparation of vanadyl sulfate, in particular to a method for preparing vanadyl sulfate from a vanadium-containing solution.
Background
With the wide application of vanadium in the fields of flow batteries and alloys, the market demand of vanadium is gradually increasing. At present, a sodium roasting-hydrolysis vanadium precipitation-alkali dissolution-ammonium salt secondary vanadium precipitation process is a main method for extracting vanadium from a vanadium-containing raw material. However, most of the products of the process are ammonium metavanadate, vanadium pentoxide and other bulk chemical products, and the process flow is long, and if the fine chemical products are prepared, the process flow is further prolonged. Therefore, extraction of vanadium from a vanadium-containing solution is considered to be the best method for shortening the process flow, and in order to avoid the problem that iron in the vanadium-containing solution is prior to vanadium extraction, sodium hypophosphite is used to reduce ferric iron in the solution to divalent iron, so that vanadium is extracted preferentially, but the reducing agent sodium hypophosphite used in the method is easy to bring a large amount of phosphate radicals into a system, so that the phosphorus content in the product exceeds the standard. In addition, the method has the advantages of low vanadium content in the raw materials, high volume ratio of an organic phase to a water phase during extraction, low volume ratio of the organic phase to the water phase during back extraction, low production efficiency, no impurity separation procedure during production, and easily overproof impurities in products. Patent CN103937998A adopts a primary amine extraction system for extraction, the extraction agent has strong extraction effect on silicon in the solution, so the raw material solution must be desilicated, and the desilicated solution is extracted, therefore, the application range of the extraction system to vanadium-containing solution is small. In patent CN111172410A, a mixed solution of ammonia water and hydrogen peroxide is used as a stripping agent, the stripping solution is heated after stripping to obtain vanadium precipitate, and V is obtained by roasting2O5The product needs to be reduced and oxidized before extraction, and a large amount of waste salt is generated in the process.
In addition, although the current extraction process can shorten the process flow, most products are vanadium-containing solution, and the vanadium-containing solution can be subjected to vanadium precipitation and roasting to obtain bulk V2O5Products, e.g. V, to prepare downstream vanadyl sulfate products2O5The product is further treated, and compared with the traditional process, the process flow is not obviously shortened.
Disclosure of Invention
The invention aims to provide a method for preparing vanadyl sulfate from a vanadium-containing solution so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing vanadyl sulfate from a vanadium-containing solution, comprising the following steps:
s1, mixing the reducing agent, acid and the vanadium-containing solution to reduce high-valence vanadium in the solution, carrying out solid-liquid separation after reduction, and removing insoluble impurities in the vanadium-containing solution to obtain a reduction solution;
s2, adjusting the vanadium concentration in the reducing solution in the S1 by using a pickling solution as a diluent, and adjusting the pH value of the reducing solution by using sodium hydroxide or acid as an acid-base regulator to obtain a water phase for extraction;
s3, extracting the aqueous phase for extraction obtained in the step S2 with a phosphoric acid extractant to obtain a vanadium-containing organic phase and raffinate;
s4, washing the vanadium-containing organic phase obtained in the step S3 with sulfuric acid solution to obtain pickling solution and an organic phase to be back-extracted, wherein the pickling solution is returned to the step S2 completely or partially according to the balance condition of process water and the vanadium content in the raw material solution;
s5, carrying out vanadium back extraction on the organic phase to be back extracted obtained in the S4 by using sulfuric acid to obtain a vanadyl sulfate solution product and a vanadium-free organic phase;
s6, carrying out back extraction on iron and chromium of the vanadium-free organic phase obtained in the step S5 by using hydrochloric acid to obtain an iron and chromium-containing solution and a blank organic phase, supplementing acid to the iron and chromium-containing solution for recycling, and entering a wastewater treatment process when the iron and chromium reach a certain concentration;
and S7, washing the blank organic phase obtained in the step S6 with water to obtain acid-containing waste liquid and a regenerated organic phase, treating the acid-containing waste liquid in a waste water treatment process, and returning the regenerated organic phase to the step S3 for recycling.
Preferably, the reducing agent in S1 may be Na2SO3、Na2S2O5、Na2S2O3One or more of; and the dosage of the raw agent is 0.8 to 2 times of the theoretical amount; the pH value of the reduction end point of the reduction reaction in the S1 is 0.5-3.5; the reduction temperature of the reduction reaction in the S1 is 15-120 ℃, and the reduction time is 5-120 min.
Preferably, the concentration of the vanadium is 8-16 g/L, the concentration of the chromium is 0.5-5 g/L, and the pH value is 3-3.5 after adjustment in S2.
Preferably, the phosphoric acid extraction system in S3 is an extraction system consisting of kerosene and one or more of di (2-ethylhexyl) phosphate (P204), 2-ethylhexyl phosphate mono 2-ethylhexyl (P507) or tributyl phosphate (TBP); the extraction system has a saponification rate of 0 to 80%.
Preferably, the acid washing process in S3 uses a sulfuric acid solution with pH of 0.4-1.5, the volume ratio of the organic phase to the aqueous phase is 1: 1-2: 1, the flow rate ratio of the organic phase to the aqueous phase is 1: 1-5: 1, and the number of stages is 2-8.
Preferably, the stripping agent used in the process of stripping iron and chromium in S4 is a sulfuric acid solution with a concentration of 4-6 mol/L, the volume ratio of the organic phase to the aqueous phase is 1: 1-3: 1, the flow rate ratio of the organic phase to the aqueous phase is 8: 1-12: 1, and the number of stages is 6-20.
Preferably, the detergent used in the step of washing residual acid in S7 is an aqueous solution, the volume ratio of the organic phase to the aqueous phase is 1: 1-8: 1, the flow rate ratio of the organic phase to the aqueous phase is 5: 1-20: 1, and the number of stages is 1-5.
Compared with the prior art, the invention has the beneficial effects that: the method for preparing vanadyl sulfate from the vanadium-containing solution optimizes the extraction process aiming at the situation that vanadium is a variable-valence metal in the solution, effectively solves the problem of separation of vanadium and impurities in the extraction process, and realizes the short-process preparation of vanadyl sulfate products with high vanadium concentration and low impurity content.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a method for preparing vanadyl sulfate from a vanadium-containing solution, comprising the following steps:
s1, mixing the reducing agent, acid and the vanadium-containing solution to reduce high-valence vanadium in the solution, carrying out solid-liquid separation after reduction, and removing insoluble impurities in the vanadium-containing solution to obtain a reduction solution;
s2, adjusting the vanadium concentration in the reducing solution in the S1 by using a pickling solution as a diluent, and adjusting the pH value of the reducing solution by using sodium hydroxide or acid as an acid-base regulator to obtain a water phase for extraction;
s3, extracting the aqueous phase for extraction obtained in the step S2 with a phosphoric acid extractant to obtain a vanadium-containing organic phase and raffinate;
s4, washing the vanadium-containing organic phase obtained in the step S3 with sulfuric acid solution to obtain pickling solution and an organic phase to be back-extracted, wherein the pickling solution is returned to the step S2 completely or partially according to the balance condition of process water and the vanadium content in the raw material solution;
s5, carrying out vanadium back extraction on the organic phase to be back extracted obtained in the S4 by using sulfuric acid to obtain a vanadyl sulfate solution product and a vanadium-free organic phase;
s6, carrying out back extraction on iron and chromium of the vanadium-free organic phase obtained in the step S5 by using hydrochloric acid to obtain an iron and chromium-containing solution and a blank organic phase, supplementing acid to the iron and chromium-containing solution for recycling, and entering a wastewater treatment process when the iron and chromium reach a certain concentration;
and S7, washing the blank organic phase obtained in the step S6 with water to obtain acid-containing waste liquid and a regenerated organic phase, treating the acid-containing waste liquid in a waste water treatment process, and returning the regenerated organic phase to the step S3 for recycling.
Further, the reducing agent in the S1 may be one or more of Na2SO3, Na2S2O5, and Na2S2O 3; and the dosage of the raw agent is 0.8 to 2 times of the theoretical amount; the pH value of the reduction end point of the reduction reaction in the S1 is 0.5-3.5; the reduction temperature of the reduction reaction in the S1 is 15-120 ℃, and the reduction time is 5-120 min.
Further, the concentration of the vanadium is 8-16 g/L, the concentration of the chromium is 0.5-5 g/L, and the pH value is 3-3.5 after adjustment in S2.
Further, the phosphoric acid extraction system in S3 is an extraction system composed of kerosene and one or more of di (2-ethylhexyl) phosphate (P204), 2-ethylhexyl mono 2-ethylhexyl phosphate (P507) or tributyl phosphate (TBP); the extraction system has a saponification rate of 0 to 80%.
Further, the acid washing process in the S3 uses a sulfuric acid solution with the pH value of 0.4-1.5, the volume ratio of the organic phase to the water phase is 1: 1-2: 1, the flow rate ratio of the organic phase to the water phase is 1: 1-5: 1, and the number of stages is 2-8 stages.
Further, the stripping agent used in the process of stripping iron and chromium in S4 is a sulfuric acid solution with a concentration of 4-6 mol/L, the volume ratio of the organic phase to the aqueous phase is 1: 1-3: 1, the flow rate ratio of the organic phase to the aqueous phase is 8: 1-12: 1, and the number of stages is 6-20.
Furthermore, the detergent used in the step S7 of washing the residual acid is an aqueous solution, the volume ratio of the organic phase to the aqueous phase is 1: 1-8: 1, the flow rate ratio of the organic phase to the aqueous phase is 5: 1-20: 1, and the number of stages is 1-5.
Example 1
Taking 300ml of vanadium slag sodium salt roasting leachate, adding 120.6g of sodium sulfite into a beaker at 60 ℃, uniformly stirring, and adjusting the pH value of the solution to 2 by using sulfuric acid, wherein the concentration of vanadium is 33.24g/L and the content of chromium is 1.14 g/L; the reduction rate of vanadium is 99.89%; adding water to dilute the solution until the vanadium concentration is 15g/L, and adjusting the pH of the solution to 3.5 by using sodium hydroxide;
35% of P204, 15% of TBP and 50% of kerosene are used as an extractant, the saponification rate is 30%, the flow ratio is 1:1 compared with 1:1, extraction is 10-grade, and the vanadium concentration in raffinate is 0.05 g/L;
0.15mol/L of H is used2SO4The solution is used as a pickling agent, the flow ratio is 1:1 compared with 2:1, the pickling is 4-grade, the vanadium content in an organic phase after pickling is 15g/L, and the contents of impurities such as Na, K, Ca, Si and the like are lower than 2 ppm;
using 3mol/L of H2SO4The solution is used as a stripping agent, the flow ratio is 10:1 compared with 1:1, stripping is carried out by 10 grades, and the obtained stripping solution is used as a vanadyl sulfate product, wherein the content of vanadium is 105g/L, and the content of impurities such as Na, K, Ca, Si and the like is lower than 15 ppm.
Example 2
Taking 300ml of vanadium slag sodium salt roasting leachate, adding 31g of sodium metabisulfite into the leachate at 60 ℃ after 300ml of the leachate with the vanadium concentration of 33.24g/L and the chromium content of 1.14g/L, and adjusting the pH value of the solution to 2.5 by using sulfuric acid after uniformly stirring; the reduction rate of vanadium is 99.89%; adding water to dilute the solution until the vanadium concentration is 12g/L, and adjusting the pH of the solution to 3.5 by using sodium hydroxide;
extracting by using 35% of P204, 10% of TBP and 55% of kerosene, wherein the saponification rate is 10%, the flow ratio is 1:1 compared with 1:1, the extraction is 10-grade, and the vanadium concentration in raffinate is 0.04 g/L;
0.15mol/L of H is used2SO4The solution is used as a pickling agent, the flow ratio is 1:1 compared with 2:1, the pickling is 6-grade, the vanadium content in an organic phase after pickling is 12g/L, and the contents of impurities such as Na, K, Ca, Si and the like are lower than 2 ppm;
using 3mol/L of H2SO4The solution is used as a stripping agent, the flow ratio is 10:1 compared with 1:1, stripping is carried out by 10 grades, and the obtained stripping solution is used as a vanadyl sulfate product, wherein the content of vanadium is 106.12g/L, and the content of impurities such as Na, K, Ca, Si and the like is lower than 13 ppm.
Example 3
Taking 300ml of leachate with vanadium concentration of 44.5g/L obtained by sodium salt roasting-water leaching of vanadium slag, putting the leachate into a beaker, adding 150.6g of sodium sulfite at 60 ℃, stirring uniformly, and adjusting the pH value of the solution to 2 by using sulfuric acid; the reduction rate of vanadium is 99.89%; adding water to dilute the solution until the vanadium concentration is 28g/L, and adjusting the pH of the solution to 3.5 by using sodium hydroxide;
40% of P204, 10% of TBP and 50% of kerosene are used as an extractant, the flow ratio is 0.5:1 compared with 1:1, the extraction is 8-grade, severe three phases are generated in the extraction process, and the phases cannot be separated.
Example 4
Taking 300ml of leachate with the vanadium concentration of 33.24g/L obtained by sodium salt roasting-water leaching of vanadium slag, putting the leachate into a beaker, adding 120.6g of sodium sulfite at the temperature of 60 ℃, stirring uniformly, and then adjusting the pH value of the solution to 2 by using sulfuric acid; the reduction rate of vanadium is 99.89%; adding water to dilute the solution until the vanadium concentration is 25g/L, and adjusting the pH of the solution to 3.5 by using sodium hydroxide;
extracting 8 grades by using 35% of P204, 15% of TBP and 50% of kerosene as an extracting agent in a flow ratio of 0.5:1 compared with 1:1, wherein the concentration of vanadium in raffinate is 3.25 g/L;
using 0.05mol/L H2SO4 solution as a pickling agent, wherein the ratio of the flow rate to the flow rate is 4:1, the pickling is 2-grade, and the vanadium content in the pickled organic phase is 16.3 g/L;
and (3) using a 3mol/L H2SO4 solution as a stripping agent, wherein the flow ratio is 6:1 compared with 1:1, the stripping is of 10 grades, and the obtained stripping solution is used as a vanadyl sulfate product, wherein the content of vanadium is 110g/L, the content of impurities Na is 115ppm, the content of K is 40ppm, the content of Ca is 27ppm, the content of Si and the like is 106.4ppm, the impurities seriously exceed the standard, and the product is unqualified.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A method for preparing vanadyl sulfate from a vanadium-containing solution is characterized by comprising the following steps:
s1, mixing the reducing agent, acid and the vanadium-containing solution to reduce high-valence vanadium in the solution, carrying out solid-liquid separation after reduction, and removing insoluble impurities in the vanadium-containing solution to obtain a reduction solution;
s2, adjusting the vanadium concentration in the reducing solution in the S1 by using a pickling solution as a diluent, and adjusting the pH value of the reducing solution by using sodium hydroxide or acid as an acid-base regulator to obtain a water phase for extraction;
s3, extracting the aqueous phase for extraction obtained in the step S2 with a phosphoric acid extractant to obtain a vanadium-containing organic phase and raffinate;
s4, washing the vanadium-containing organic phase obtained in the step S3 with sulfuric acid solution to obtain pickling solution and an organic phase to be back-extracted, wherein the pickling solution is returned to the step S2 completely or partially according to the balance condition of process water and the vanadium content in the raw material solution;
s5, carrying out vanadium back extraction on the organic phase to be back extracted obtained in the S4 by using sulfuric acid to obtain a vanadyl sulfate solution product and a vanadium-free organic phase;
s6, carrying out back extraction on iron and chromium of the vanadium-free organic phase obtained in the step S5 by using hydrochloric acid to obtain an iron and chromium-containing solution and a blank organic phase, supplementing acid to the iron and chromium-containing solution for recycling, and entering a wastewater treatment process when the iron and chromium reach a certain concentration;
and S7, washing the blank organic phase obtained in the step S6 with water to obtain acid-containing waste liquid and a regenerated organic phase, treating the acid-containing waste liquid in a waste water treatment process, and returning the regenerated organic phase to the step S3 for recycling.
2. The method for preparing vanadyl sulfate from vanadium-containing solution according to claim 1, wherein the reducing agent in S1 is Na2SO3、Na2S2O5、Na2S2O3One or more of; and the dosage of the raw agent is 0.8 to 2 times of the theoretical amount; the pH value of the reduction end point of the reduction reaction in the S1 is 0.5-3.5; the reduction temperature of the reduction reaction in the S1 is 15-120 ℃, and the reduction time is 5-120 min.
3. The method for preparing vanadyl sulfate from vanadium-containing solution as claimed in claim 1, wherein the concentration of vanadium is 8-16 g/L, the concentration of chromium is 0.5-5 g/L, and the pH value is 3-3.5 after adjustment in S2.
4. The method for preparing vanadyl sulfate from vanadium-containing solution according to claim 1, wherein the phosphoric acid extraction system in S3 is one or more of bis (2-ethylhexyl) phosphate (P204), mono 2-ethylhexyl 2-phosphate (P507) or tributyl phosphate (TBP) and kerosene; the extraction system has a saponification rate of 0 to 80%.
5. The method of claim 1, wherein the acid washing process in S3 uses a sulfuric acid solution with a pH of 0.4-1.5, the volume ratio of the organic phase to the aqueous phase is 1: 1-2: 1, the flow rate ratio of the organic phase to the aqueous phase is 1: 1-5: 1, and the number of stages is 2-8.
6. The method of claim 1, wherein the stripping agent used in the process of stripping iron and chromium in S4 is a sulfuric acid solution with a concentration of 4-6 mol/L, the volume ratio of the organic phase to the aqueous phase is 1: 1-3: 1, the flow rate ratio of the organic phase to the aqueous phase is 8: 1-12: 1, and the number of stages is 6-20.
7. The method for preparing vanadyl sulfate from vanadium-containing solution as claimed in claim 1, wherein the detergent used in the washing residual acid process of S7 is aqueous solution, the volume ratio of organic phase to aqueous phase is 1: 1-8: 1, the flow rate ratio of organic phase to aqueous phase is 5: 1-20: 1, and the number of stages is 1-5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015882A (en) * | 2021-10-29 | 2022-02-08 | 苏州博萃循环科技有限公司 | Method for recovering vanadium and nickel from POX carbon black |
| CN115404361A (en) * | 2022-09-02 | 2022-11-29 | 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 vanadyl sulfate solution from sodium salt roasting water extract of industrial vanadium slag |
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| CN101552346A (en) * | 2009-05-08 | 2009-10-07 | 昆明理工大学 | Method of preparing electrolyte of vanadium ion redox flow battery |
| CN106395899A (en) * | 2016-09-23 | 2017-02-15 | 中国科学院过程工程研究所 | Method for preparing vanadyl sulfate by use of vanadium-containing chloride solution |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101552346A (en) * | 2009-05-08 | 2009-10-07 | 昆明理工大学 | Method of preparing electrolyte of vanadium ion redox flow battery |
| CN106395899A (en) * | 2016-09-23 | 2017-02-15 | 中国科学院过程工程研究所 | Method for preparing vanadyl sulfate by use of vanadium-containing chloride solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015882A (en) * | 2021-10-29 | 2022-02-08 | 苏州博萃循环科技有限公司 | Method for recovering vanadium and nickel from POX carbon black |
| CN115404361A (en) * | 2022-09-02 | 2022-11-29 | 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 vanadyl sulfate solution from sodium salt roasting water extract of industrial vanadium slag |
| CN115404361B (en) * | 2022-09-02 | 2023-09-29 | 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 vanadyl sulfate solution from industrial vanadium slag sodium roasting water leaching solution |
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