CN115109948A - Method for extracting and separating tantalum and niobium and application thereof - Google Patents
Method for extracting and separating tantalum and niobium and application thereof Download PDFInfo
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- CN115109948A CN115109948A CN202210701595.8A CN202210701595A CN115109948A CN 115109948 A CN115109948 A CN 115109948A CN 202210701595 A CN202210701595 A CN 202210701595A CN 115109948 A CN115109948 A CN 115109948A
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 71
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 70
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 68
- 239000010955 niobium Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 48
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims abstract description 21
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000008346 aqueous phase Substances 0.000 claims description 19
- 239000008096 xylene Substances 0.000 claims description 19
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical group [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- -1 organic acid alkali metal salt Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 229960003975 potassium Drugs 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 239000003923 scrap metal Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 description 31
- 229910052593 corundum Inorganic materials 0.000 description 23
- 239000010431 corundum Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000012535 impurity Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000010814 metallic waste Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- VUWVDWMFBFJOCE-UHFFFAOYSA-N niobium(5+);oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Ta+5] VUWVDWMFBFJOCE-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- 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
- C22B34/24—Obtaining niobium or tantalum
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the field of hydrometallurgy, and provides a method for extracting and separating tantalum and niobium and application thereof, wherein the method comprises the following steps: sequentially carrying out oxidizing roasting, alkaline roasting and leaching on the material containing the metal tantalum niobium to obtain a leaching solution containing potassium hexatantalate and potassium hexaniobate; and extracting the leachate by adopting dimethylbenzene and methyl trioctyl ammonium chloride, and then performing back extraction on the organic phase by utilizing oxalic acid and nitric acid. The method has good leaching and separating effects on tantalum and niobium, the obtained tantalum and niobium leachate has high purity, the leaching rate reaches more than 99% under better conditions, the tantalum and niobium separation ratio after back extraction reaches 41.74, the fluoride-free process is realized in the tantalum and niobium extraction and separation processes, and the method has great significance for environmental protection and green production.
Description
Technical Field
The invention relates to the field of hydrometallurgy, in particular to a method for extracting and separating tantalum and niobium and application thereof.
Background
The tantalum and the niobium have similar properties, are commonly symbiotic in nature, have small distribution range in the crust, and have the characteristics of low reserves, uneven distribution, low grade and the like. Because of the advantages of high hardness, high melting point, good metal ductility and the like, the tantalum-niobium alloy is widely applied to the fields of aerospace industry, medical treatment, steel industry, superconducting materials, 3D printing and the like.
With the wide application of tantalum-niobium resources, the generated waste materials are increased day by day, and the regeneration of tantalum-niobium is very important because the geological resources of tantalum-niobium in the world are limited and tantalum-niobium is an important strategic rare metal.
Currently, known common metallurgical methods for tantalum and niobium mainly include an acid decomposition method, an alkali decomposition method and a chlorination method. The acid decomposition method is widely applied, but because hydrofluoric acid is used and reaction conditions need to be heated, volatilization of the hydrofluoric acid and generation of waste liquid are caused, a lot of environmental problems are inevitably generated, and the treatment cost is high, the Chinese invention patent application with the publication number of CN101955228A discloses a method, the generation of fluorine-containing waste liquid and waste residue is reduced by reducing the use concentration of the hydrofluoric acid in the extraction process, but although a certain amount of fluorine pollution is reduced in the extraction process, the fluorine pollution is not only generated in the extraction process, but also the leaching process is an important link for generating the fluorine-containing waste liquid and the waste residue, and the method can only reduce the fluorine pollution to a certain extent, and cannot essentially solve the problem of the fluorine pollution. The chlorination method refers to chloridizing and evaporating ores under the condition of a reducing agent, condensing and recovering, and rectifying and separating a mixture of tantalum pentachloride and niobium pentachloride prepared from condensate to obtain the niobium pentachloride, but the method has the defects of serious equipment corrosion and environmental pollution, poor operating conditions, high operating temperature and the like in the treatment process, so the method is rarely applied in the industry at present, and the boiling chlorination method improved by the Chinese patent with the publication number of CN 109182782A has high decomposition rate and is not limited by mineral components, but has larger corrosion to equipment, complex equipment and complex process operation. The alkali decomposition method has simple steps, realizes the leaching of tantalum and niobium under the fluorine-free condition, does not relate to the problems, and has good application prospect. The Chinese patent application with publication number CN 113151669A discloses a method, which comprises the steps of uniformly mixing potassium carbonate and a composite oxidant with a tantalum-niobium ore resource, then carrying out roasting treatment, and carrying out water leaching treatment on a roasted product to obtain a potassium polytantalate and potassium polyniobate solution with higher leaching rates, wherein the leaching rates reach more than 90 percent, but the method directly obtains tantalum-niobium oxides by adopting calcination after leaching without separating tantalum and niobium, and cannot meet the requirements of respectively recovering tantalum and niobium.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for extracting and separating tantalum and niobium and application thereof.
The invention provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
sequentially carrying out oxidizing roasting, alkaline roasting and leaching on the material containing the metal tantalum niobium to obtain a leaching solution containing potassium hexatantalate and potassium hexaniobate;
and extracting the leachate by adopting dimethylbenzene and methyltrioctylammonium chloride, and then performing back extraction on the organic phase by utilizing oxalic acid and nitric acid.
The material containing the metal tantalum and niobium can be waste material containing the metal tantalum and niobium. Preferably, the wastes containing metal tantalum and niobium are subjected to impurity removal treatment before the oxidizing roasting. As the main impurities in the waste are calcium, iron and copper elements, the sulfuric acid and the hydrochloric acid can react with the impurities instead of the tantalum and niobium elements, thereby achieving the purpose of removing the impurities.
In some embodiments of the invention, the mixed acid used in the impurity removal process is hydrochloric acid and sulfuric acid, and the concentration is 1% -5%.
According to some embodiments of the present invention, the temperature of the oxidizing roasting is 300-.
The oxidizing roasting treatment is to convert tantalum and niobium elements in the raw materials into tantalum pentoxide and niobium pentoxide, break the large-size particles into small-size particles and increase the contact area with alkaline substances in the subsequent process. The research of the invention finds that the oxidizing roasting temperature is selected to be 500 ℃, which is beneficial to converting tantalum and niobium into tantalum pentoxide and niobium pentoxide, and the invention does not waste energy and saves resources.
According to some embodiments of the invention, during the alkaline calcination, the potassium hydroxide and the organic acid alkali metal salt are added in a mass ratio of 1-3:1, and the calcination temperature is 300-700 ℃, preferably 500-600 ℃. The roasting time is 1-3 hours.
Preferably, the organic acid alkali metal salt is potassium oxalate or potassium citrate, more preferably potassium oxalate. The total mass of the potassium hydroxide and the organic acid alkali metal salt is 2-6 times of that of the oxidation roasting product.
The addition of the organic acid alkali metal salt improves the alkaline roasting effect of potassium hydroxide, improves the leaching rate of tantalum and niobium, reduces the temperature of a reaction system, and saves the consumption of potassium hydroxide. When potassium hydroxide and potassium oxalate powder are used for alkaline roasting, the potassium hydroxide is used as a fluxing agent to reduce the melting points of tantalum pentoxide and niobium pentoxide, potassium oxalate can provide potassium ions, the reaction is further carried out in the forward direction, and gas generated by decomposition of potassium oxalate can play an activating role, so that the alkaline roasting efficiency is improved, and the effect of increasing the leaching rate is achieved.
When the alkaline roasting temperature is insufficient, the reaction time is insufficient or the ratio of alkali to material is low, the leaching rate is affected due to insufficient reaction, when the reaction temperature is too high and the reaction time is too long, the reaction product is changed from soluble to insoluble, the leaching rate is affected, and when the ratio of alkali to material is too high, the leaching rate cannot be further increased, and resources are wasted. Therefore, the roasting temperature, the reaction time and the alkali material ratio are selected to ensure that the best leaching effect is achieved. Namely, when the alkaline roasting temperature is 500-600 ℃, the roasting time is 1-3 hours, and the mass ratio of the potassium hydroxide to the potassium oxalate is 3:1, the effect is better.
According to some embodiments of the invention, the temperature of the leaching is 55-65 ℃, preferably 60 ℃ and the leaching time is 1 hour.
According to some embodiments of the invention, the ratio of xylene to methyltrioctylammonium chloride is between 5 and 25 ml: 0.25-1.25 g.
According to some embodiments of the invention, the leachate is complexed with an organic acid prior to extraction; preferably, the organic acid is ascorbic acid, preferably 5% ascorbic acid, in an amount of 0.5 to 2 times the volume of the leachate.
In some embodiments of the invention, when the volume of the leachate is 2ml, the addition amount of the ascorbic acid is 0-4ml, the use amount of the xylene is 5-25ml, and the use amount of the methyltrioctylammonium chloride is 0.25-1.25 g. Preferably, 4ml of 5% ascorbic acid is added, the amount of xylene being 15ml and the amount of methyltrioctylammonium chloride being 0.75 g.
The research of the invention finds that the addition of the ascorbic acid increases the extraction effect of the extractant on the leachate, and in the extraction process, the methyl trioctyl ammonium chloride is used as the main extractant, the xylene is used as the secondary extractant, and the xylene is used as the diluent of the methyl trioctyl ammonium chloride, so that the good extraction effect can be exerted.
According to some embodiments of the invention, the stripping specifically comprises: adding oxalic acid and nitric acid into the extracted organic phase, mixing, standing for layering, back-extracting the niobium element into the water phase, taking the organic phase with the tantalum element, adding nitric acid into the organic phase, mixing, standing for layering, and back-extracting the tantalum element. Wherein, the concentration of oxalic acid is 0.1-15%, and the concentration of nitric acid is 0.1-10%.
Oxalic acid and nitric acid are matched for use, so that niobium is stripped out of an organic phase, tantalum is reserved in the organic phase, and then nitric acid is independently used for stripping the tantalum, so that the aim of separating tantalum and niobium is fulfilled. Preferably, the concentration of nitric acid is 8-10% when stripping tantalum. The subsequent use of high concentration nitric acid has better effect of stripping tantalum.
The method has good leaching and separating effects on tantalum and niobium, the obtained tantalum and niobium leachate has high purity, the leaching rate reaches over 99% under better conditions, the tantalum and niobium separation ratio after back extraction reaches 41.74, a fluoride-free process is realized in the tantalum and niobium extraction and separation processes, and the method has great significance for environmental protection and green production.
Drawings
FIG. 1 is a flow chart of the method for extracting and separating tantalum and niobium in example 1;
FIG. 2 is an XRD pattern of the powder after oxidative calcination in example 1;
FIG. 3 is an SEM photograph of tantalum-niobium containing scrap metal material of example 1;
FIG. 4 is an SEM image of the powder after oxidizing calcination in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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 experimental procedures used in the following examples are conventional unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
This example provides a method for extracting and separating tantalum and niobium, which is shown in fig. 1, and includes the following steps:
weighing 2g of tantalum-niobium-containing metal waste material by using 5% HCl + 5% H 2 SO 4 Acid washing is carried out for 1 hour at 65 ℃ in mixed acid with concentration, the impurity removal rate reaches more than 90 percent, filter residue is placed in a drying oven for drying treatment at 60 ℃ after impurity removal, dried waste is placed in a corundum crucible, the corundum crucible is placed in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, 1g of the waste after oxidizing roasting is weighed and placed in the corundum crucible after being cooled, 3g of potassium hydroxide and 1g of potassium oxalate are added, after uniform mixing, the waste is placed in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, 80ml of pure water is added into the corundum crucible after alkaline roasting and cooling, and a magnetic rotor is added into a water bath kettle for water bath leaching at 60 ℃ for 1 hour, so that leachate with the leaching rate of 99.9 percent of tantalum and 100 percent of niobium is obtained.
Taking 2ml of leachate, fully mixing with 4ml of 5% ascorbic acid, adding the leachate into a separating funnel after full reaction, taking 15ml of xylene, uniformly mixing with 0.75g of methyl trioctyl ammonium chloride to fully dissolve the methyl trioctyl ammonium chloride in the xylene, then adding the mixed organic phase into the separating funnel, fully vibrating, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 5ml of 15% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 10ml of 10% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, removing the lower-layer aqueous phase, and obtaining that the extraction rate of tantalum is 99.98%, the extraction rate of niobium is 99.75%, when niobium is back extracted, the extraction rate of niobium is 95.3%, and when tantalum is back extracted, the extraction rate is 86.1%.
FIG. 2 is the XRD pattern of the powder after the oxidizing roasting in example 1, and it can be seen that the scrap completes the transformation from tantalum hydride, niobium hydride to tantalum oxide and niobium oxide at 500 deg.C, and the phase is completely transformed into tantalum oxide and niobium oxide, no other impurities are generated, and the optimal conditions are reached.
FIG. 3 is an SEM image of tantalum-niobium-containing metal scrap of example 1, showing that the microstructure of the scrap is much in the form of a large bar.
FIG. 4 is an SEM image of the powder of example 1 after oxidative roasting, and it can be seen that the large, strip-shaped particles after oxidative roasting are broken into small pieces, which is advantageous for the subsequent alkaline roasting.
Example 2
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
weighing 2g of tantalum-niobium-containing metal waste material by using 5% HCl + 5% H 2 SO 4 Acid washing is carried out in mixed acid with the concentration of 65 ℃ for 1 hour, the impurity removal rate reaches more than 90 percent, filter residue is placed in a drying oven for drying treatment at 60 ℃ after impurity removal, dried waste is placed in a corundum crucible, the corundum crucible is placed in a muffle furnace for oxidizing roasting at 400 ℃ for 2 hours, 1g of the waste after oxidizing roasting is weighed and placed in the corundum crucible after being cooled, 3g of potassium hydroxide and 1g of potassium oxalate are added, after uniform mixing, the waste is placed in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, 80ml of pure water is added into the corundum crucible after alkaline roasting is cooled, a magnetic rotor is added into a water bath kettle for water bath leaching at 60 ℃ for 1 hour, and leachate with the leaching rate of 86.8 percent of tantalum and 93.9 percent of niobium is obtained.
Taking 2ml of leachate, fully mixing with 1ml of 5% ascorbic acid, adding the leachate into a separating funnel after full reaction, taking 10ml of xylene, uniformly mixing with 0.5g of methyl trioctyl ammonium chloride to fully dissolve the methyl trioctyl ammonium chloride in the xylene, then adding the mixed organic phase into the separating funnel, fully vibrating, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 5ml of 10% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 10ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, removing the lower-layer aqueous phase, and obtaining that the extraction rate of tantalum is 72.8%, the extraction rate of niobium is 65.7%, when niobium is back extracted, the extraction rate of niobium is 73.2%, and when tantalum is back extracted, the extraction rate is 38.6%.
Example 3
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
weighing 2g of tantalum-niobium-containing metal waste material by using 5% HCl + 5% H 2 SO 4 Acid washing is carried out for 1 hour at 65 ℃ in mixed acid with concentration, the impurity removal rate reaches more than 90 percent, filter residue is placed in a drying oven for drying treatment at 60 ℃ after impurity removal, dried waste is placed in a corundum crucible, the corundum crucible is placed in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, 1g of the waste after oxidizing roasting is weighed and placed in the corundum crucible after being cooled, 3g of potassium hydroxide and 1g of potassium oxalate are added, after uniform mixing, the waste is placed in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, 80ml of pure water is added into the corundum crucible after alkaline roasting and cooling, and a magnetic rotor is added into a water bath kettle for water bath leaching at 60 ℃ for 1 hour, so that leachate with the leaching rate of 99.9 percent of tantalum and 100 percent of niobium is obtained.
Taking 2ml of leachate, fully mixing with 3ml of 5% ascorbic acid, adding the leachate into a separating funnel after full reaction, taking 10ml of xylene, uniformly mixing with 0.25g of methyl trioctyl ammonium chloride to fully dissolve the methyl trioctyl ammonium chloride in the xylene, then adding the mixed organic phase into the separating funnel, fully vibrating, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 5ml of 5% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 10ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, removing the lower-layer aqueous phase, and obtaining the tantalum extraction rate of 92.9%, the niobium extraction rate of 87.2%, when niobium is extracted, the niobium extraction rate of 89.9%, and when tantalum is extracted, the extraction rate of 42.1%.
Example 4
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
weighing 2g of tantalum-niobium-containing metal waste material by using 5% HCl + 5% H 2 SO 4 Acid washing is carried out in mixed acid with the concentration of 65 ℃ for 1 hour, the impurity removal rate reaches more than 90 percent, filter residues are placed in a drying oven for drying treatment at 60 ℃ after impurity removal, dried waste materials are placed in a corundum crucible and placed in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, 1g of the waste materials after oxidizing roasting are weighed and placed in the corundum crucible after cooling, 3g of potassium hydroxide and 1g of potassium oxalate are added, after uniform mixing, the waste materials are placed in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, 80ml of pure water is added into the corundum crucible after alkaline roasting, cooling is carried out, a magnetic rotor is added, and water bath leaching is carried out in a water bath kettle at 60 ℃ for 1 hour, so that a leaching solution with the leaching rate of 99.9 percent of tantalum and 100 percent of niobium is obtained.
Taking 2ml of leachate, fully mixing with 3ml of 5% ascorbic acid, adding the leachate into a separating funnel after full reaction, taking 15ml of xylene, uniformly mixing with 0.5g of methyl trioctyl ammonium chloride to fully dissolve the methyl trioctyl ammonium chloride in the xylene, then adding the mixed organic phase into the separating funnel, fully vibrating, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 5ml of 10% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 10ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix, standing until the solution is layered, removing the lower-layer aqueous phase, and obtaining the tantalum extraction rate of 95.4%, the niobium extraction rate of 91.9%, when niobium is reversely extracted, the niobium extraction rate of 89.5%, and when tantalum is reversely extracted, the extraction rate of 56.9%.
Example 5
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
weighing 2g of tantalum-niobium-containing metal waste material by using 5% HCl + 5% H 2 SO 4 Pickling in mixed acid of concentration at 65 ℃ for 1 hourAnd after impurity removal, placing filter residues in an oven for drying at 60 ℃, placing dried waste materials in a corundum crucible, placing the corundum crucible in a muffle furnace for oxidizing and roasting at 500 ℃ for 2 hours, after the waste materials after oxidizing and roasting are cooled, weighing 1g of the waste materials, placing the waste materials in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, uniformly mixing, placing the waste materials in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, after the alkaline roasting is cooled, adding 80ml of pure water into the corundum crucible, adding a magnetic rotor, and leaching in a water bath at 60 ℃ for 1 hour to obtain a leaching solution with the leaching rate of 99.9 percent of tantalum and 100 percent of niobium.
Taking 2ml of leachate, fully mixing the leachate with 3ml of 5% ascorbic acid, adding the leachate into a separating funnel after full reaction, taking 20ml of xylene, uniformly mixing the xylene with 1g of methyltrioctylammonium chloride to fully dissolve the methyltrioctylammonium chloride in the xylene, then adding a mixed organic phase into the separating funnel, fully vibrating, standing until the solution is layered, taking out a lower-layer aqueous phase, adding 5ml of 15% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix the solution, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 10ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix the solution, standing until the solution is layered, removing the lower-layer aqueous phase, and obtaining the tantalum extraction rate of 93.3%, the niobium extraction rate of 90.1%, when the niobium is extracted, the niobium extraction rate of 90.01%, and when the tantalum is extracted, the extraction rate of 57.4%.
Example 6
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
weighing 2g of tantalum-niobium-containing metal waste material by using 3% HCl + 3% H 2 SO 4 Pickling in mixed acid of concentration 65 ℃ for 1 hour, removing impurities to obtain calcium of about 48 percent and iron and copper of about 20 percent, drying the filter residue in a drying oven at 60 ℃ after removing impurities, placing the dried waste in a corundum crucible, placing the corundum crucible in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, weighing 1g of the waste after oxidizing roasting after cooling, placing the weighed waste in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, placing the waste in the muffle furnace for alkaline roasting at 350 ℃ for 1 hour after uniformly mixing, adding 80ml of pure water into the corundum crucible after alkaline roasting and cooling, and obtaining the productAdding a magnetic rotor, and leaching in a water bath at 60 ℃ for 1 hour to obtain a leaching solution with leaching rates of 58.6 percent of tantalum and 91.4 percent of niobium.
Adding 2ml of leachate into a separating funnel, uniformly mixing 10ml of xylene with 0.25g of methyl trioctyl ammonium chloride to fully dissolve the methyl trioctyl ammonium chloride in the xylene, then adding a mixed organic phase into the separating funnel, fully vibrating, standing until the solution is layered, taking out a lower-layer aqueous phase, adding 5ml of 5% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix the oxalic acid and the nitric acid, standing until the solution is layered, taking out the lower-layer aqueous phase, adding 10ml of 5% nitric acid into the separating funnel, continuously vibrating to fully mix the nitric acid, standing until the solution is layered, removing the lower-layer aqueous phase, and obtaining the tantalum extraction rate of 55.8%, the niobium extraction rate of 59.4%, the niobium extraction rate of 32.8% when back extracting niobium, and the tantalum extraction rate of 7.3% when back extracting tantalum.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for extracting and separating tantalum and niobium is characterized by comprising the following steps:
sequentially carrying out oxidizing roasting, alkaline roasting and leaching on the material containing the metal tantalum niobium to obtain a leaching solution containing potassium hexatantalate and potassium hexaniobate;
and extracting the leachate by adopting dimethylbenzene and methyl trioctyl ammonium chloride, and then performing back extraction on the organic phase by utilizing oxalic acid and nitric acid.
2. The method for extracting and separating tantalum and niobium as claimed in claim 1, wherein the dosage ratio of xylene to methyltrioctylammonium chloride is 5-25 ml: 0.25-1.25 g.
3. The method for extracting and separating tantalum and niobium as claimed in claim 1, wherein the leachate is complexed with an organic acid before extraction;
preferably, the organic acid is ascorbic acid in an amount of 0.5 to 2 times the volume of the leachate.
4. The method for extracting and separating tantalum and niobium as claimed in claim 1, wherein the back extraction method comprises the following steps: adding oxalic acid and nitric acid into the extracted organic phase, mixing, standing for layering, back-extracting the niobium element into the aqueous phase, taking the organic phase with the tantalum element, adding nitric acid, mixing, standing for layering, and back-extracting the tantalum element.
5. The method for extracting and separating tantalum and niobium as claimed in claim 4, wherein the concentration of oxalic acid is 0.1-15%, and the concentration of nitric acid is 0.1-10%.
6. The method for extracting and separating tantalum and niobium as claimed in claim 1, wherein the temperature of the oxidizing roasting is 300-700 ℃, preferably 500-700 ℃.
7. The method for extracting and separating tantalum and niobium as claimed in claim 1, wherein the potassium hydroxide and the organic acid alkali metal salt are added in a mass ratio of 1-3:1 during the alkaline calcination, and the calcination temperature is 300-700 ℃, preferably 500-600 ℃.
8. The method for extracting and separating tantalum and niobium as claimed in claim 7, wherein the organic acid alkali metal salt is potassium oxalate or potassium citrate, and the total mass of the potassium hydroxide and the organic acid alkali metal salt is 2-6 times of the mass of the oxidation roasting product.
9. The method for extracting and separating tantalum and niobium as claimed in claim 1, wherein the temperature of leaching is 55-65 ℃.
10. Use of the method of any one of claims 1 to 9 for the recovery of tantalum niobium scrap metal.
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| CN1076731A (en) * | 1992-03-06 | 1993-09-29 | H.C施塔克公司 | The method of isolating tantalum and niobium |
| CN111286608A (en) * | 2020-03-11 | 2020-06-16 | 郑州大学 | Method for selectively separating tantalum and niobium step by step based on floating extraction |
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| CN113186399A (en) * | 2021-03-12 | 2021-07-30 | 北京工业大学 | Method for extracting tantalum and niobium |
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| CN1076731A (en) * | 1992-03-06 | 1993-09-29 | H.C施塔克公司 | The method of isolating tantalum and niobium |
| CN111286608A (en) * | 2020-03-11 | 2020-06-16 | 郑州大学 | Method for selectively separating tantalum and niobium step by step based on floating extraction |
| CN213652601U (en) * | 2020-12-03 | 2021-07-09 | 郑州大学 | Floating extraction system for extracting rare and noble metals |
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