CN113213537B - Method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium - Google Patents
Method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium Download PDFInfo
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000011259 mixed solution Substances 0.000 title claims abstract description 44
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 239000011651 chromium Substances 0.000 title claims description 39
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052804 chromium Inorganic materials 0.000 title claims description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 41
- 239000011268 mixed slurry Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 21
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 12
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 abstract description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 abstract description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JHLSXUPXOUVLHN-UHFFFAOYSA-N [V+5].[Cr+6] Chemical compound [V+5].[Cr+6] JHLSXUPXOUVLHN-UHFFFAOYSA-N 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ROAYSRAUMPWBQX-UHFFFAOYSA-N ethanol;sulfuric acid Chemical compound CCO.OS(O)(=O)=O ROAYSRAUMPWBQX-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for separating and preparing vanadium trioxide from a vanadium (V) and chromium (VI) mixed solution. According to the method, clean gas hydrogen is utilized, the vanadium-chromium mixed solution can be directly subjected to reduction precipitation to obtain low-valence vanadium precipitate, the precipitate can be subjected to simple washing operation to obtain a qualified vanadium trioxide product, and compared with the prior art, the method omits the procedure of preparing an intermediate product ammonium vanadate or ammonium polyvanadate from complex ammonium salt precipitate, and then obtains a vanadium pentoxide product through calcination, so that the process is simplified; meanwhile, the generation of ammonia nitrogen wastewater is avoided; and the obtained vanadium trioxide product has higher added value than the vanadium pentoxide product.
Description
Technical Field
The invention belongs to the field of metal metallurgy, and particularly relates to a method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI).
Background
Vanadium and chromium are similar in properties and are usually added in vanadium titano-magnetite in a symbiotic manner, and chromium-containing vanadium slag obtained by smelting the vanadium titano-magnetite in a blast furnace-converter is a main raw material for producing vanadium pentoxide. The main process for extracting vanadium from chromium-containing vanadium slag is a sodium roasting-water leaching process. The chromium-containing vanadium slag is subjected to sodium salt roasting-water leaching process, and vanadium and chromium enter the solution respectively in the form of pentavalent V (V) and hexavalent Cr (VI). Because the chemical properties of the solutions of V (V) and Cr (VI) are similar, how to separate and prepare high-purity vanadium products from the solution containing Cr (VI) becomes a common problem in the industry.
At present, an ammonium salt vanadium precipitation method is generally adopted in industry to selectively precipitate vanadium from a V (V) and Cr (VI) mixed solution to realize primary separation of vanadium and chromium, but the method has poor applicability to a solution with high chromium content, chromium is easy to generate coprecipitation with vanadium, the quality of a final vanadium product is influenced, and if a qualified vanadium product is to be obtained, the vanadium product is required to be subjected to deep purification treatment, the process is complex, and a large amount of ammonia nitrogen wastewater is generated by ammonium salt vanadium precipitation, so that the treatment difficulty is high, and the cost is high. In order to solve the problems, various methods for separating and recovering vanadium and chromium from a vanadium-chromium-containing solution are developed at home and abroad, and mainly comprise a chemical precipitation method, a solvent extraction method, an ion exchange method and the like.
Chinese patent CN112442595A discloses a method for separating and extracting vanadium and chromium from a vanadium slag sodium salt roasting water extract, which comprises the steps of adding ammonium salt into the vanadium slag sodium salt roasting water extract, controlling the pH value of a solution system at 7.5-9.5, stirring for reaction, and then carrying out solid-liquid separation to obtain ammonium metavanadate crystals and a filtrate A; extracting the organic phase B and the filtrate A to obtain raffinate A1 and a loaded organic phase B1; carrying out back extraction on the loaded organic phase B1 by using a sodium hydroxide solution to obtain a back extraction solution A2; recycling raffinate A1; adding a vanadium precipitation agent into the back extraction solution A2, performing ball milling at room temperature, and filtering to obtain vanadium-containing filter residue C1 and chromium-containing filtrate A3; adding raffinate A1 into vanadium-containing filter residue C1, then carrying out ball milling, and filtering to obtain filter residue C2 and vanadium-containing filtrate A4; and calcining the filter residue C2, and then continuously using the filter residue C2 as a vanadium precipitation reagent, separating and recovering vanadium from the vanadium-containing filtrate A4 by adopting an ammonium salt vanadium precipitation method, and removing impurities from the chromium-containing filtrate A3, and then evaporating and crystallizing to obtain a sodium chromate product. The method can realize the separation and recovery of vanadium and chromium, but the process is complex, and the ammonium salt vanadium precipitation has the defects of high liquid ammonia nitrogen concentration after vanadium precipitation and high ammonia nitrogen recovery cost.
Chinese patent CN104556522A discloses a method for separating vanadium and chromium from a vanadium and chromium mixed solution, comprising the following steps: A. adjusting the pH value of the mixed solution to 3.0-4.0, and adsorbing vanadium and chromium in the mixed solution by an ion exchange resin adsorption method to obtain vanadium and chromium containing resin; B. eluting the vanadium-chromium-containing resin by using 3-4% sulfuric acid-ethanol solution to obtain vanadium-containing resin and chromium-containing solution; C. desorbing the vanadium-containing resin to obtain vanadium-containing desorption solution, and carrying out ammonium salt vanadium precipitation treatment on the vanadium-containing desorption solution to obtain vanadate; D. calcining vanadate to obtain vanadium pentoxide; E. the chromium-containing solution is adjusted in pH for neutralization, chromium precipitates as a hydrate Cr (OH)3·nH2Separating out the O form, and calcining to prepare the chromium sesquioxide. The process is beneficial to separation and recovery of vanadium and chromium resources, but the process uses ion exchange resin, has large one-time investment and harsh operating conditions, is easy to be poisoned to influence the exchange efficiency, and needs to be replaced in time, and simultaneously, the process adopts ammonium salt to precipitate vanadium to prepare vanadium products, so that the process also has the defects of high ammonia nitrogen content of vanadium precipitation wastewater and high treatment difficulty, and the obtained vanadium pentoxide product has low additional value.
Chinese patent CN103602819A adopts a reducing agent to reduce pentavalent vanadium and hexavalent chromium in a solution into tetravalent vanadium and trivalent chromium under a certain pH condition, then the tetravalent vanadium and trivalent chromium are coprecipitated, and finally vanadium and chromium are separated and recovered by adopting an alkali leaching and acid leaching way, wherein the reducing agent is one or more selected from sulfur dioxide, sodium sulfite, sodium thiosulfate, formaldehyde, formic acid and iron powder, and the adding amount of the reducing agent is 1-3 times of the theoretical total amount of the pentavalent vanadium and hexavalent chromium respectively reduced into tetravalent vanadium and trivalent chromium. The method has good separation effect, but has the problems of long flow path, large consumption of reducing agent and acid-base and easy introduction of new impurities.
At present, the problems of complex process, low added value of vanadium products and the like generally exist in the process of recovering vanadium from a vanadium-chromium solution, the final vanadium product is obtained by an ammonium salt vanadium precipitation process, a large amount of high-concentration ammonia nitrogen wastewater is generated by the process, the treatment difficulty is high, the cost is high, the environmental pollution risk is high, and the common problem that the clean production of the vanadium industry is restricted is caused.
Disclosure of Invention
Aiming at the technical defects of separating and recovering vanadium from a vanadium-chromium mixed solution in the prior art, the invention aims to provide a method for separating and recovering vanadium from a vanadium-chromium mixed solution, which has the advantages of simple process, environmental friendliness and high vanadium product added value.
In order to achieve the purpose, the invention provides a method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI), which comprises the following steps:
(1) adjusting the pH value of a mixed solution containing vanadium (V) and chromium (VI) to 4.0-7.0 by adopting an acid solution in a reaction kettle, wherein the concentration of vanadium is 10-60 g/L and the concentration of chromium is 1-45 g/L, and adding a catalyst into the mixed solution according to the ratio of the solid-to-liquid ratio of the catalyst to the mixed solution of 10 mg/L-40 mg/L to obtain a reaction solution;
(2) then, purging the reaction kettle containing the reaction liquid in the step (1) by using hydrogen, then introducing the hydrogen until the partial pressure of the hydrogen is 2 to 6MPa, stirring the reaction liquid at the reaction temperature of 250 to 300 ℃ for reaction for 1 to 6 hours to obtain mixed slurry, wherein the stirring speed is 500 to 2000 r/min;
(3) after the reaction in the step (2) is finished, carrying out solid-liquid separation on the mixed slurry to obtain a precipitate A and a filtrate A;
(4) washing the precipitate A in the step (3) by using dilute sulfuric acid: mixing dilute sulfuric acid and the precipitate A according to the liquid-solid ratio of 1-3 mL/g, and stirring in a reaction kettle at the vacuum or inert atmosphere at normal temperature for more than 20min to obtain mixed slurry B;
(5) and carrying out solid-liquid separation on the mixed slurry B to obtain a precipitate B and a filtrate B, and drying the precipitate B in vacuum or inert atmosphere to obtain vanadium trioxide.
Preferably, the pH value of the reaction solution in the step (1) is adjusted to 5.0-6.0.
Preferably, the acid solution in the step (1) is a sulfuric acid solution, and the volume concentration of the sulfuric acid solution is 20-50%.
Preferably, the solid-to-liquid ratio of the catalyst to the vanadium-containing solution in the step (1) is 10-20 mg/L.
Preferably, the catalyst in step (1) is one or a mixture of palladium chloride, palladium metal powder and platinum metal powder.
Preferably, the hydrogen and the reaction solution in the step (2) are stirred in the reaction kettle under the following reaction conditions: the reaction temperature is 250-280 ℃, the hydrogen partial pressure is 2-4 MPa, and the stirring speed is 1000-1500 r/min.
Preferably, the time for washing the precipitate A with dilute sulfuric acid in the step (4) is 20-60 min, and the volume concentration of the dilute sulfuric acid is 10-20%.
Preferably, the liquid-solid ratio of the dilute sulfuric acid to the precipitate A in the step (4) is 1 to 2.5 mL/g.
Preferably, the inert atmosphere in step (4) is a nitrogen atmosphere or an argon atmosphere.
Preferably, the inert atmosphere in step (5) is a nitrogen atmosphere or an argon atmosphere.
The invention has the following positive effects:
the method utilizes clean gas hydrogen to directly carry out reduction precipitation on the vanadium-chromium mixed solution to obtain low-valence vanadium precipitate, and the precipitate can obtain a qualified vanadium trioxide product after simple washing operation; meanwhile, the generation of ammonia nitrogen wastewater is avoided; and the obtained vanadium trioxide product has higher added value than the vanadium pentoxide product. Therefore, the method has the advantages of simple process, environmental friendliness and high added value of vanadium products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram showing a method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) according to the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description herein is of preferred examples for the purpose of illustration only and is not intended to limit the scope of the present invention, so it will be understood that other equivalent implementations and modifications may be made without departing from the spirit and scope of the present invention.
In the method for separating and preparing vanadium trioxide from the vanadium (V) and chromium (VI) mixed solution, the solid-to-liquid ratio of the catalyst to the vanadium (V) and chromium (VI) mixed solution in the step (1) is 10mg/L to 40mg/L within the dosage range, so that the reaction rate can be effectively increased, the reaction activity of hydrogen is improved, and the recovery rate of vanadium is ensured; on the other hand, when the catalyst can not be effectively recovered, the influence of excessive addition of the catalyst on the purity of the final vanadium product and the process economy can be avoided. Further preferably, the solid-to-liquid ratio of the catalyst to the vanadium (V) and chromium (VI) containing mixed solution is 10-20 mg/L, within which the best recovery rate and the best economy according to the invention can be achieved.
Preferably, the catalyst in step (1) is one or a mixture of palladium chloride, palladium metal powder and platinum metal powder. The catalysts are all commercially available products, for example, palladium chloride powder can be obtained from the national formulary chemical agents ltd at a content (not less than 59.0% in terms of Pd), and platinum metal powder can be obtained from the national formulary chemical agents ltd at a content (not less than 99.0% in terms of Pt).
In the step (2), the hydrogen partial pressure is 2-6 MPa, preferably 2-4 MPa, the reaction temperature is 250-300 ℃, preferably 250-280 ℃, and the reaction liquid is stirred for reaction for 1-6 hours to obtain mixed slurry, wherein the stirring speed is 500-2000 r/min, preferably 1000-1500 r/min. Within the range, the reaction rate can be optimized, the reaction activity of hydrogen is improved, and the recovery rate of vanadium is ensured. For example, if the hydrogen partial pressure is less than 2MPa, the reaction time is too long, and if the hydrogen partial pressure is greater than 6MPa, although the reaction rate increases, the requirements for equipment safety also increase accordingly. For example, if the reaction temperature is lower than 250 ℃, the reaction rate may be too low, and if the reaction temperature is higher than 300 ℃, the energy consumption is high and the process economy is poor. For example, if the stirring speed is less than 500r/min, the separation effect of vanadium and chromium may not be sufficient, and if the stirring speed is more than 2000r/min, although the reaction efficiency is improved, the energy consumption is higher, and the requirement for the safety of the equipment is correspondingly improved.
In addition, unless otherwise specified, the reagents and solvents disclosed below were purchased from the national pharmaceutical group chemical agents, ltd, and were chemically pure; and the concentrations of the vanadium and the chromium are measured by adopting an ICP-AES inductively coupled atomic emission spectrometer.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, as those skilled in the art will appreciate that various modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
A method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) comprises the following specific steps:
(1) adding 200mL of vanadium (V) and chromium (VI) mixed solution (the vanadium concentration is 15 g/L; the chromium concentration is 1.5g/L) into a reaction kettle, adjusting the pH value to 7.0 by adopting a sulfuric acid solution with the volume concentration of 40%, and adding palladium chloride powder into the mixed solution according to the solid-to-liquid ratio of 10mg/L of palladium chloride to the mixed solution to obtain a reaction solution;
(2) purging the reaction kettle containing the reaction liquid in the step (1) by using hydrogen, then introducing the hydrogen until the partial pressure of the hydrogen is 2MPa, stirring the reaction liquid at the reaction temperature of 250 ℃ for reaction for 2 hours to obtain mixed slurry, wherein the stirring speed is 800 r/min;
(3) carrying out solid-liquid separation on the mixed slurry to obtain a precipitate A and a filtrate A;
(4) washing the precipitate A by using dilute sulfuric acid with the volume concentration of 15 percent: mixing dilute sulfuric acid and the precipitate A according to the liquid-solid ratio of 1mL/g, transferring the solution into a reaction kettle, vacuumizing the reaction kettle, and stirring at normal temperature for 20min to obtain mixed slurry B;
(5) and carrying out solid-liquid separation on the mixed slurry B to obtain a precipitate B and a filtrate B, and drying the precipitate B in a vacuum drying oven to obtain 4.34g of vanadium trioxide with the purity of 99.2%.
Example 2
A method for separating and preparing vanadium trioxide from a vanadium (V) chromium (VI) mixed solution comprises the following specific steps:
(1) adding 400mL of vanadium (V) chromium (VI) mixed solution (the vanadium concentration is 30 g/L; the chromium concentration is 10g/L) into a reaction kettle, adjusting the pH value to 6.0 by adopting a sulfuric acid solution with the volume concentration of 50%, and adding palladium chloride powder into the mixed solution according to the solid-to-liquid ratio of 20mg/L of palladium chloride to the mixed solution to obtain a reaction solution;
(2) then, purging the reaction kettle containing the reaction liquid in the step (1) by using hydrogen, then introducing the hydrogen until the partial pressure of the hydrogen is 3MPa, stirring the reaction liquid at the reaction temperature of 260 ℃ for reaction for 4 hours to obtain mixed slurry, wherein the stirring speed is 1000 r/min;
(3) carrying out solid-liquid separation on the mixed slurry to obtain a precipitate A and a filtrate A;
(4) washing the precipitate A by using dilute sulfuric acid with the volume concentration of 10 percent: mixing dilute sulfuric acid and the precipitate A according to the liquid-solid ratio of 1.5mL/g, transferring the solution into a reaction kettle, vacuumizing the reaction kettle, and stirring at normal temperature for 40min to obtain mixed slurry B;
(5) and carrying out solid-liquid separation on the mixed slurry B to obtain a precipitate B and a filtrate B, and drying the precipitate B in a vacuum drying oven to obtain 17.35g of vanadium trioxide with the purity of 99.1%.
Example 3
A method for separating and preparing vanadium trioxide from a vanadium (V) chromium (VI) mixed solution comprises the following specific steps:
(1) adding 500mL of vanadium (V) and chromium (VI) mixed solution (the vanadium concentration is 60 g/L; the chromium concentration is 45g/L) into a reaction kettle, adjusting the pH value to 5.0 by adopting a sulfuric acid solution with the volume concentration of 50%, and adding palladium chloride powder into the mixed solution according to the solid-to-liquid ratio of 40mg/L of palladium chloride to the mixed solution to obtain a reaction solution;
(2) then, purging the reaction kettle containing the reaction liquid in the step (1) by using hydrogen, then introducing the hydrogen until the partial pressure of the hydrogen is 4MPa, stirring the reaction liquid at the reaction temperature of 270 ℃ for reacting for 6 hours to obtain mixed slurry, wherein the stirring speed is 1500 r/min;
(3) carrying out solid-liquid separation on the mixed slurry to obtain a precipitate A and a filtrate A;
(4) washing the precipitate A by using dilute sulfuric acid with the volume concentration of 10 percent: mixing dilute sulfuric acid and the precipitate A according to the liquid-solid ratio of 3mL/g, transferring the solution into a reaction kettle, vacuumizing the reaction kettle, and stirring at normal temperature for 60min to obtain mixed slurry B;
(5) and carrying out solid-liquid separation on the mixed slurry B to obtain a precipitate B and a filtrate B, and drying the precipitate B in a vacuum drying oven to obtain 43.36g of vanadium trioxide with the purity of 98.8%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) comprises the following steps:
(1) adjusting the pH value of a mixed solution containing vanadium (V) and chromium (VI) to 4.0-7.0 by adopting an acid solution in a reaction kettle, wherein the concentration of vanadium is 10-60 g/L and the concentration of chromium is 1-45 g/L, and adding a catalyst into the mixed solution according to the ratio of the solid-to-liquid ratio of the catalyst to the mixed solution of 10 mg/L-40 mg/L to obtain a reaction solution;
(2) then, purging the reaction kettle containing the reaction liquid in the step (1) by using hydrogen, then introducing the hydrogen until the hydrogen partial pressure is 2-6 MPa, stirring the reaction liquid at the reaction temperature of 250-300 ℃ for reacting for 1-6 hours to obtain mixed slurry, wherein the stirring speed is 500-2000 r/min;
(3) after the reaction in the step (2) is finished, carrying out solid-liquid separation on the mixed slurry to obtain a precipitate A and a filtrate A;
(4) washing the precipitate A in the step (3) by using dilute sulfuric acid: mixing dilute sulfuric acid and the precipitate A according to the liquid-solid ratio of 1-3 mL/g, and stirring in a reaction kettle at the vacuum or inert atmosphere at normal temperature for more than 20min to obtain mixed slurry B;
(5) carrying out solid-liquid separation on the mixed slurry B to obtain a precipitate B and a filtrate B, and drying the precipitate B in vacuum or inert atmosphere to obtain vanadium trioxide;
wherein, the catalyst in the step (1) is one or a mixture of more of palladium chloride, palladium metal powder and platinum metal powder.
2. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) according to claim 1, wherein the pH value of the reaction solution in the step (1) is adjusted to 5.0-6.0.
3. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) according to claim 1, wherein the acid solution in the step (1) is a sulfuric acid solution with a volume concentration of 20-50%.
4. The method for separating and preparing vanadium trioxide from a vanadium (V) and chromium (VI) mixed solution according to claim 1, wherein the solid-to-liquid ratio of the catalyst to the vanadium-containing solution in the step (1) is 10-20 mg/L.
5. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) according to claim 1, wherein the hydrogen and the reaction solution in the step (2) are stirred in a reaction kettle under the following reaction conditions: the reaction temperature is 250-280 ℃, the hydrogen partial pressure is 2-4 MPa, and the stirring speed is 1000-1500 r/min.
6. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) according to claim 1, wherein the washing operation time of the precipitate A with dilute sulfuric acid in the step (4) is 20-60 min, and the volume concentration of the dilute sulfuric acid is 10-20%.
7. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) as claimed in claim 1, wherein the liquid-solid ratio of dilute sulfuric acid to precipitate A in step (4) is 1-2.5 mL/g.
8. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) as claimed in claim 1, wherein the inert atmosphere in the step (4) is a nitrogen atmosphere or an argon atmosphere.
9. The method for separating and preparing vanadium trioxide from a mixed solution of vanadium (V) and chromium (VI) as claimed in claim 1, wherein the inert atmosphere in the step (5) is a nitrogen atmosphere or an argon atmosphere.
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