CN115109948B - Tantalum-niobium extraction and separation method and application thereof - Google Patents
Tantalum-niobium extraction and separation method and application thereof Download PDFInfo
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- CN115109948B CN115109948B CN202210701595.8A CN202210701595A CN115109948B CN 115109948 B CN115109948 B CN 115109948B CN 202210701595 A CN202210701595 A CN 202210701595A CN 115109948 B CN115109948 B CN 115109948B
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- 238000000605 extraction Methods 0.000 title claims abstract description 37
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000926 separation method Methods 0.000 title claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 61
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000002386 leaching Methods 0.000 claims abstract description 55
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 53
- 239000010955 niobium Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 42
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 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
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 15
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000008569 process Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 32
- 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 24
- 239000012071 phase Substances 0.000 claims description 21
- 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 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 12
- 239000011668 ascorbic acid Substances 0.000 claims description 12
- 239000003923 scrap metal Substances 0.000 claims description 10
- -1 organic acid alkali metal salt Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 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 20
- 229910052593 corundum Inorganic materials 0.000 description 19
- 239000010431 corundum Substances 0.000 description 19
- 239000012535 impurity Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000001354 calcination 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
- 238000001035 drying Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 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
- 239000003513 alkali Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 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
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 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
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 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 compound [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
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- 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 description 1
- 235000011082 potassium citrates Nutrition 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
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research 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
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
- 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 a material containing tantalum and niobium to obtain leaching liquid containing potassium hexatantalate and potassium hexaniobate; extracting the leaching solution by adopting dimethylbenzene and methyltrioctyl ammonium chloride, and then carrying out back extraction on an organic phase by utilizing oxalic acid and nitric acid. The method has good leaching and separating effects on tantalum and niobium, the purity of the obtained tantalum and niobium leaching solution is high, the leaching rate reaches more than 99% under the preferred condition, the tantalum and niobium separating ratio after back extraction reaches 41.74, the fluorine-free process is realized in the extraction and separating processes of tantalum and niobium, and the method has great significance on 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
Tantalum and niobium have similar properties, often form a symbiotic product in nature, have a small distribution range in the crust, and have the characteristics of low reserves, uneven distribution, low grade and the like. The tantalum-niobium has the advantages of high hardness, high melting point, good metal extensibility and the like, so that the tantalum-niobium 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 is also increasingly promoted, and due to the limited geological resources of tantalum-niobium in the world, tantalum-niobium is an important strategic rare metal, so that the regeneration of tantalum-niobium is very important.
Currently, known common metallurgical methods of tantalum and niobium mainly comprise an acid decomposition method, an alkali decomposition method and a chlorination method. The acid decomposition method is most 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 brought, a plurality of environmental problems are inevitably generated, the treatment cost is high, and the Chinese patent application with publication No. CN101955228A discloses a method for reducing the generation of fluorine-containing waste liquid and waste residue by reducing the use concentration of the hydrofluoric acid in the extraction process, but the method reduces a certain amount of fluorine pollution in the extraction process, but the fluorine pollution is not only generated in the extraction process, but also is an important link of the generation of fluorine-containing waste liquid and waste residue in the leaching process, and the method can only reduce the fluorine pollution to a certain extent and cannot essentially solve the fluorine pollution problem. The chlorination method is characterized in that ore is subjected to chlorination evaporation under the condition of reducing agent, condensation and recovery are carried out, and a mixture of tantalum pentachloride and niobium pentachloride prepared from condensate is subjected to rectification separation to obtain niobium pentachloride, but the method has the defects of serious equipment corrosion and environmental pollution, poor operation conditions, high operation temperature and the like in the treatment process, so that the method is rarely applied in the industry at present, and the improved boiling chlorination method disclosed in the patent of the invention of CN 109182782A is high in decomposition rate and free from limitation of mineral components, and has large corrosion to equipment, complex equipment and complex process operation. The alkaline decomposition method has simple steps, realizes tantalum-niobium leaching under the fluorine-free condition, does not involve the problems, and has good application prospect. The Chinese patent application with publication number of CN 113151669A discloses a method, which comprises the steps of uniformly mixing potassium carbonate and a composite oxidant with tantalum-niobium ore resources, roasting, and carrying out water leaching treatment on a roasting product to obtain potassium tantalate and potassium polycombate solution with higher leaching rate, wherein the leaching rate reaches more than 90 percent, but the method directly obtains tantalum-niobium oxide by roasting after leaching, does not separate tantalum and niobium, and cannot meet the requirement of separately recovering tantalum and niobium.
Disclosure of Invention
Aiming at the problems existing 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 a material containing tantalum and niobium to obtain leaching liquid containing potassium hexatantalate and potassium hexaniobate;
extracting the leaching solution by adopting dimethylbenzene and methyltrioctyl ammonium chloride, and then carrying out back extraction on an organic phase by utilizing oxalic acid and nitric acid.
The metal-containing tantalum-niobium material of the invention can be scrap material containing metal tantalum-niobium. Preferably, the scrap containing tantalum niobium is subjected to a impurity removal treatment prior to the oxidative calcination. Because the main impurities in the waste material are calcium, iron and copper elements, sulfuric acid and hydrochloric acid can react with the impurities instead of tantalum and niobium elements, and the aim of removing impurities is fulfilled.
In some embodiments of the invention, the mixed acid used in the impurity removal treatment is hydrochloric acid and sulfuric acid, and the concentration is 1% -5%.
According to some embodiments of the invention, the temperature of the oxidative calcination is 300-700 ℃, preferably 500-700 ℃, further preferably 500 ℃.
The oxidizing roasting treatment is to convert tantalum niobium element in the raw material 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 discovers that the selective oxidizing roasting temperature is 500 ℃, which is favorable for converting tantalum and niobium into tantalum pentoxide and niobium pentoxide, does not waste energy and saves resources.
According to some embodiments of the invention, the alkaline roasting process comprises adding potassium hydroxide and alkali metal salt of organic acid in a mass ratio of 1-3:1, and roasting at 300-700 ℃, preferably 500-600 ℃. The roasting time is 1-3 hours.
Preferably, the alkali metal salt of an organic acid 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 the mass of the oxidized 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 adopted 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, so that the reaction is further carried out forward, and the gas generated by decomposing the potassium oxalate can play a role in activation, thereby improving the alkaline roasting efficiency and achieving the effect of increasing the leaching rate.
When the alkaline roasting temperature is insufficient, the reaction time is insufficient or the alkali material ratio is low, insufficient reaction occurs to influence the leaching rate, when the reaction temperature is too high and the reaction time is too long, the reaction product is changed from soluble to insoluble to influence the leaching rate, and when the alkali material ratio is too high, the leaching rate cannot be further improved, and resources are wasted. Therefore, proper roasting temperature, reaction time and alkali ratio are selected to ensure the best leaching effect. Namely, when the alkaline roasting temperature is 500-600 ℃, the roasting time is 1-3 hours, and the mass ratio of potassium hydroxide to potassium oxalate is 3:1, the effect is better.
According to some embodiments of the invention, the leaching is carried out at a temperature of 55-65 ℃, preferably 60 ℃, for a leaching time of 1 hour.
According to some embodiments of the invention, the ratio of xylene to methyltrioctyl ammonium chloride is 5-25ml:0.25-1.25g.
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 0.5-2 times the volume of the leachate.
In some embodiments of the invention, when the volume of the leachate is 2ml, the ascorbic acid is added in an amount of 0-4ml, the xylene is used in an amount of 5-25ml, and the methyltrioctylammonium chloride is used in an amount of 0.25-1.25g. Preferably, 4ml of 5% ascorbic acid is added, the xylene amount is 15ml and the methyltrioctylammonium chloride amount is 0.75g.
According to the invention, the addition of the ascorbic acid increases the extraction effect of the extractant on the leaching solution, in the extraction process, the methyltrioctyl ammonium chloride is used as a main extractant, the xylene is used as a secondary extractant, and the presence of the xylene is used as a diluent of the methyltrioctyl ammonium chloride, so that the good extraction effect can be exerted.
According to some embodiments of the invention, the back extraction specifically comprises: adding oxalic acid and nitric acid into the extracted organic phase, mixing, standing for layering, back extracting niobium element into water phase, adding nitric acid into the organic phase for preserving tantalum element, mixing, standing for layering, and back extracting 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 element is reversely extracted from an organic phase, tantalum element is remained in the organic phase, and then nitric acid is independently used for reversely extracting tantalum element, so that the purpose of separating tantalum from niobium is achieved. Preferably, the nitric acid concentration is 8-10% when stripping tantalum. The concentration of nitric acid used later is high, and the effect of tantalum back extraction is better.
The invention provides a method for extracting and separating tantalum and niobium and application thereof, the method has better leaching and separating effect of tantalum and niobium, the purity of the obtained tantalum and niobium leaching solution is higher, the leaching rate under better conditions is more than 99%, the separation ratio of tantalum and niobium after back extraction is up to 41.74, the fluorine-free process is realized in the process of extracting and separating tantalum and niobium, and the method has great significance for environmental protection and green production.
Drawings
FIG. 1 is a flow chart of a 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 image of tantalum-niobium-containing scrap metal of example 1;
fig. 4 is an SEM image of the powder after oxidative calcination in example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods used in the examples below are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples below are commercially available unless otherwise specified.
Example 1
The embodiment provides a method for extracting and separating tantalum and niobium, the flow chart of which is shown in fig. 1, and the steps are as follows:
2g of tantalum-niobium-containing scrap metal was weighed out using 5% HCl+5% H 2 SO 4 Pickling in mixed acid with concentration of 65 ℃ for 1 hour, wherein the impurity removal rate is over 90 percent, drying filter residues in an oven at 60 ℃ after impurity removal, placing dried waste in a corundum crucible, placing in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, weighing 1g of the oxidized roasting waste after cooling, placing in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, uniformly mixing, placing in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, adding 80ml of pure water into the corundum crucible after cooling after alkaline roasting, adding a magnetic rotor, leaching in a water bath at 60 ℃ for 1 hour, and obtaining leaching liquid with the leaching rate of tantalum of 99.9 percent and niobium of 100 percent.
Mixing 2ml of leaching solution with 4ml of 5% ascorbic acid fully, adding the mixture into a separating funnel after full reaction, mixing 15ml of dimethylbenzene with 0.75g of methyltrioctylammonium chloride uniformly, enabling methyltrioctylammonium chloride to be fully dissolved in the dimethylbenzene, adding the mixed organic phase into the separating funnel, fully oscillating, standing for solution layering, taking out a lower water phase, adding 5ml of 15% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, taking out the lower water phase, adding 10ml of 10% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, removing the lower water phase, and obtaining the tantalum extraction rate of 99.98%, the niobium extraction rate of 99.75%, the niobium extraction rate of 95.3% and the tantalum stripping rate of 86.1%.
FIG. 2 is an XRD pattern of the powder after oxidative calcination in example 1, showing that the scrap was converted from tantalum hydride, niobium hydride to tantalum oxide, niobium oxide at 500℃and all phases were converted to tantalum oxide and niobium oxide without the formation of other impurities, achieving optimal conditions.
Fig. 3 is an SEM image of the tantalum-niobium-containing scrap metal of example 1, which shows that the scrap microscopic morphology is dominated by large stripes.
Fig. 4 is an SEM image of the powder after oxidative calcination in example 1, which shows that the large-sized, bar-shaped particles are broken into small pieces after oxidative calcination, which is advantageous for the subsequent alkaline calcination.
Example 2
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
2g of tantalum-niobium-containing scrap metal was weighed out using 5% HCl+5% H 2 SO 4 Pickling in mixed acid with concentration of 65 ℃ for 1 hour, wherein the impurity removal rate is over 90 percent, drying filter residues in a baking oven at 60 ℃ after impurity removal, placing dried waste in a corundum crucible, placing in a muffle furnace for oxidizing roasting at 400 ℃ for 2 hours, weighing 1g of the oxidized roasting waste after cooling, placing in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, uniformly mixing, placing in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, adding 80ml of pure water into the corundum crucible after cooling after alkaline roasting, adding a magnetic rotor, leaching in a water bath at 60 ℃ for 1 hour, and obtaining leaching solution with leaching rate of tantalum of 86.8 percent and niobium of 93.9 percent.
Mixing 2ml of leaching solution with 1ml of 5% ascorbic acid fully, adding the mixture into a separating funnel after full reaction, mixing 10ml of dimethylbenzene with 0.5g of methyltrioctylammonium chloride uniformly, enabling methyltrioctylammonium chloride to be fully dissolved in the dimethylbenzene, adding the mixed organic phase into the separating funnel, fully oscillating, standing for solution layering, taking out a lower water phase, adding 5ml of 10% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, taking out the lower water phase, adding 10ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, removing the lower water phase, and obtaining tantalum extraction rate of 72.8%, niobium extraction rate of 65.7%, niobium extraction rate of 73.2% and tantalum stripping rate of 38.6%.
Example 3
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
2g of tantalum-niobium-containing scrap metal is weighed and 5 percent of the scrap metal is usedHCl+5％H 2 SO 4 Pickling in mixed acid with concentration of 65 ℃ for 1 hour, wherein the impurity removal rate is over 90 percent, drying filter residues in an oven at 60 ℃ after impurity removal, placing dried waste in a corundum crucible, placing in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, weighing 1g of the oxidized roasting waste after cooling, placing in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, uniformly mixing, placing in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, adding 80ml of pure water into the corundum crucible after cooling after alkaline roasting, adding a magnetic rotor, leaching in a water bath at 60 ℃ for 1 hour, and obtaining leaching liquid with the leaching rate of tantalum of 99.9 percent and niobium of 100 percent.
Mixing 2ml of leaching solution with 3ml of 5% ascorbic acid fully, adding the mixture into a separating funnel after full reaction, mixing 10ml of dimethylbenzene with 0.25g of methyltrioctylammonium chloride uniformly, enabling methyltrioctylammonium chloride to be fully dissolved in the dimethylbenzene, adding the mixed organic phase into the separating funnel, fully oscillating, standing for solution layering, taking out a lower water phase, adding 5ml of 5% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, taking out the lower water phase, adding 10ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, removing the lower water phase, and obtaining the tantalum extraction rate of 92.9%, the niobium extraction rate of 87.2%, the niobium extraction rate of 89.9% and the tantalum stripping rate of 42.1%.
Example 4
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
2g of tantalum-niobium-containing scrap metal was weighed out using 5% HCl+5% H 2 SO 4 Pickling in mixed acid with concentration of 65 ℃ for 1 hour, wherein the impurity removal rate is over 90 percent, drying filter residues in a baking oven at 60 ℃ after impurity removal, placing dried waste in a corundum crucible, placing in a muffle furnace, oxidizing and roasting at 500 ℃ for 2 hours, weighing 1g of oxidized and roasted waste after cooling, placing in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, mixing uniformly, placing in the muffle furnace, alkaline roasting at 500 ℃ for 2 hours, and treating after alkaline roastingAfter cooling, 80ml of pure water is added into a corundum crucible, and a magnetic rotor is added into the corundum crucible to leach for 1 hour in a water bath at 60 ℃ to obtain leaching solution with leaching rate of 99.9 percent of tantalum and 100 percent of niobium.
Mixing 2ml of leaching solution with 3ml of 5% ascorbic acid fully, adding the mixture into a separating funnel after full reaction, mixing 15ml of dimethylbenzene with 0.5g of methyltrioctylammonium chloride uniformly, enabling methyltrioctylammonium chloride to be fully dissolved in the dimethylbenzene, adding the mixed organic phase into the separating funnel, fully oscillating, standing for solution layering, taking out a lower water phase, adding 5ml of 10% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, taking out the lower water phase, adding 10ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, removing the lower water phase, and obtaining the tantalum extraction rate of 95.4%, the niobium extraction rate of 91.9%, the niobium extraction rate of 89.5% and the tantalum stripping rate of 56.9%.
Example 5
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
2g of tantalum-niobium-containing scrap metal was weighed out using 5% HCl+5% H 2 SO 4 Pickling in mixed acid with concentration of 65 ℃ for 1 hour, wherein the impurity removal rate is over 90 percent, drying filter residues in an oven at 60 ℃ after impurity removal, placing dried waste in a corundum crucible, placing in a muffle furnace for oxidizing roasting at 500 ℃ for 2 hours, weighing 1g of the oxidized roasting waste after cooling, placing in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, uniformly mixing, placing in the muffle furnace for alkaline roasting at 500 ℃ for 2 hours, adding 80ml of pure water into the corundum crucible after cooling after alkaline roasting, adding a magnetic rotor, leaching in a water bath at 60 ℃ for 1 hour, and obtaining leaching liquid with the leaching rate of tantalum of 99.9 percent and niobium of 100 percent.
Mixing 2ml of leaching solution with 3ml of 5% ascorbic acid fully, adding the mixture into a separating funnel after full reaction, mixing 20ml of dimethylbenzene with 1g of methyltrioctylammonium chloride uniformly, enabling methyltrioctylammonium chloride to be fully dissolved in the dimethylbenzene, adding the mixed organic phase into the separating funnel, fully oscillating, standing for solution layering, taking out a lower water phase, adding 5ml of 15% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, taking out the lower water phase, adding 10ml of 5% nitric acid into the separating funnel, continuously oscillating for full mixing, standing for solution layering, removing the lower water phase, and obtaining the tantalum extraction rate of 93.3%, the niobium extraction rate of 90.1%, the niobium extraction rate of 90.01% and the tantalum stripping rate of 57.4%.
Example 6
The embodiment provides a method for extracting and separating tantalum and niobium, which comprises the following steps:
2g of tantalum-niobium-containing scrap metal was weighed out using 3% HCl+3% H 2 SO 4 Pickling in mixed acid with concentration of 65 ℃ for 1 hour, removing impurities to about 48% of calcium, 20% of iron and copper, drying filter residues in a baking oven at 60 ℃ after removing impurities, placing dried waste in a corundum crucible, oxidizing and roasting in a muffle furnace at 500 ℃ for 2 hours, weighing 1g of oxidized and roasted waste, placing in the corundum crucible, adding 3g of potassium hydroxide and 1g of potassium oxalate, mixing uniformly, placing in the muffle furnace for alkaline roasting at 350 ℃ for 1 hour, adding 80ml of pure water into the corundum crucible after cooling after alkaline roasting, adding a magnetic rotor, leaching in a water bath at 60 ℃ for 1 hour, and obtaining leaching liquid with leaching rate of tantalum of 58.6% and niobium of 91.4%.
Adding 2ml of leaching solution into a separating funnel, uniformly mixing 10ml of dimethylbenzene and 0.25g of methyltrioctylammonium chloride to enable methyltrioctylammonium chloride to be fully dissolved in the dimethylbenzene, then adding the mixed organic phase into the separating funnel, fully oscillating, standing, taking out a lower water phase after layering of the solution, adding 5ml of 5% oxalic acid and 5ml of 5% nitric acid into the separating funnel, continuously oscillating to enable the solution to be fully mixed, standing, taking out the lower water phase after layering of the solution, adding 10ml of 5% nitric acid into the separating funnel, continuously oscillating to enable the solution to be fully mixed, standing, removing the lower water phase after layering of the solution, obtaining a tantalum extraction rate of 55.8%, a niobium extraction rate of 59.4%, and a niobium extraction rate of 32.8% when back extracting tantalum.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (6)
1. A method for extracting and separating tantalum and niobium, which is characterized by comprising the following steps:
sequentially carrying out oxidizing roasting, alkaline roasting and water leaching on a material containing tantalum and niobium to obtain leaching liquid containing potassium hexatantalate and potassium hexaniobate; the temperature of the oxidizing roasting is 500-700 ℃; in the alkaline roasting process, adding potassium hydroxide and organic acid alkali metal salt in a mass ratio of 1-3:1, wherein the roasting temperature is 500-600 ℃, the organic acid alkali metal salt is potassium oxalate, and the total mass of the potassium hydroxide and the organic acid alkali metal salt is 2-6 times of the mass of an oxidized roasting product;
complexing the leaching solution with ascorbic acid, extracting by adopting dimethylbenzene and methyltrioctyl ammonium chloride, and then carrying out back extraction on an organic phase by using oxalic acid and nitric acid; the back extraction specifically comprises the following steps: adding oxalic acid and nitric acid into the extracted organic phase, mixing, standing for layering, back extracting niobium element into water phase, adding nitric acid into the organic phase for preserving tantalum element, mixing, standing for layering, and back extracting tantalum element.
2. The method for extracting and separating tantalum and niobium according to claim 1, wherein the dosage ratio of xylene to methyltrioctyl ammonium chloride is 5-25ml:0.25-1.25g.
3. The method for extracting and separating tantalum and niobium according to claim 1, wherein the volume amount of the ascorbic acid is 0.5-2 times of the volume of the leaching solution.
4. The method for extracting and separating tantalum and niobium according to claim 1, wherein the concentration of oxalic acid is 0.1-15% and the concentration of nitric acid is 0.1-10%.
5. The method of tantalum-niobium extraction and separation according to claim 1, wherein the leaching temperature is 55-65 ℃.
6. Use of the method of any one of claims 1-5 for recovering 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 |
| CN213652601U (en) * | 2020-12-03 | 2021-07-09 | 郑州大学 | Floating extraction system for extracting rare and noble metals |
| 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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