CN108640153B - Method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy - Google Patents
Method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity niobium oxide by niobium-tantalum-iron alloy, which comprises the steps of roasting the niobium-tantalum-iron alloy, removing carbon, sulfur and phosphorus impurity elements in the niobium-tantalum-iron alloy, and simultaneously converting a metal simple substance in the niobium-tantalum-iron alloy into a metal oxide to avoid the reaction of the metal simple substance and acid to generate hydrogen; and then carrying out subsequent acid leaching and purification treatment, removing impurity elements such as antimony, copper and the like which are difficult to separate in the subsequent extraction process in the acid leaching solution by using a purifying agent, carrying out separation and purification by matching with the processes of extraction, acid pickling, niobium reverse extraction, tantalum extraction and the like to obtain a niobium-containing solution, finally precipitating niobium ions by ammonia water, and calcining to obtain the high-purity niobium oxide. The method provided by the invention can efficiently remove impurity elements in the niobium-tantalum-iron alloy, so that the antimony element is reduced to be less than 10ppm, the content of the copper element is reduced to be less than 3.0ppm, and a high-purity niobium oxide product with the purity of more than or equal to 99.95% is obtained.
Description
Technical Field
The invention belongs to the technical field of niobium oxide preparation, and particularly relates to a method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy.
Background
Compared with the ferrocolumbium alloy, the niobium-tantalum-iron alloy has much lower niobium content, the niobium content is 25-45%, the tantalum content is about 4%, and the balance is impurities such as iron, silicon, aluminum, carbon, sulfur, phosphorus and the like, so that the niobium-tantalum-iron alloy cannot be directly used as an iron alloy additive and needs to be subjected to impurity removal treatment. The conventional impurity removal method is to adopt wet smelting to carry out acid leaching on the niobium-tantalum-iron alloy, remove impurities capable of reacting with acid and then obtain niobium oxide. The method can control the generation rate of hydrogen and reduce the explosion risk, but because antimony, copper, carbon, sulfur, phosphorus and other impurity elements in the niobium-tantalum-iron alloy cannot be effectively removed in the extraction process, the purity and quality of the obtained niobium oxide are greatly influenced, and the actual requirements of the market cannot be met.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy, which can efficiently remove impurity elements in the niobium-tantalum-iron alloy so as to obtain high-purity niobium oxide with the purity of more than or equal to 99.95%.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for preparing high-purity niobium oxide by niobium-tantalum-iron alloy comprises the following steps:
(1) roasting niobium-tantalum-iron alloy powder in an oxygen-containing atmosphere to obtain a solid oxide;
(2) mixing the solid oxide obtained in the step (1) with hydrofluoric acid and sulfuric acid, and carrying out acid leaching to obtain acid leaching solution;
(3) diluting the acid leaching solution obtained in the step (2), mixing the obtained diluent with a purifying agent, performing a displacement reaction, and filtering to obtain a purified solution;
(4) sequentially extracting, acid-washing, niobium-removing and tantalum-extracting the purified liquid obtained in the step (3) to obtain a niobium-containing solution;
(5) neutralizing the niobium-containing solution obtained in the step (4) to be alkaline by using ammonia alkali to obtain niobium hydroxide;
(6) washing, drying and calcining the niobium hydroxide obtained in the step (5) in sequence to obtain high-purity niobium oxide; the purity of the high-purity niobium oxide is more than or equal to 99.95 percent.
Preferably, the niobium-tantalum-iron alloy powder obtained in the step (1) is mixed with an oxidation assistant and roasted; the oxidation assistant comprises NaNO2(ii) a The particle size of the niobium-tantalum-iron alloy powder is 250-400 meshes.
Preferably, the roasting temperature in the step (1) is 800-900 ℃, and the roasting time is 2-4 h.
Preferably, the mass concentration of the hydrofluoric acid in the step (2) is 53-55%; the mass concentration of the sulfuric acid is more than or equal to 96 percent;
the mass ratio of the solid oxide to the hydrofluoric acid to the sulfuric acid is 1 (1.2-1.5) to 0.8-1.2.
Preferably, the chemical composition of the purifying agent of the step (3) comprises: 40-60 wt.% Fe, 10-20 wt.% Al, 5-10 wt.% Zn and the balance Si.
Preferably, the purifying agent further comprises 5-10 wt.% of Mn and/or 5-10 wt.% of Mg.
Preferably, the particle size of the purifying agent is 40-100 meshes.
Preferably, the dilution in step (3) is H+The concentration is 10.5-12.0 mol/L.
Preferably, the mass ratio of the purifying agent in the step (3) to the volume of the diluent is110～125kg/m3(ii) a The time of the replacement reaction is 0.5-2.0 h.
Preferably, the extractant for extraction in the step (4) comprises sec-octanol or methyl isobutyl ketone; the pickling agent for pickling is a sulfuric acid solution with the concentration of 3.2-3.7 mol/L; the niobium-resisting agent for resisting niobium is a sulfuric acid solution with the concentration of 1.4-1.8 mol/L.
The invention provides a method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy, which comprises the following steps: roasting niobium-tantalum-iron alloy powder in an oxygen-containing atmosphere to obtain a solid oxide; mixing the obtained solid oxide with hydrofluoric acid and sulfuric acid, and performing acid leaching to obtain acid leaching solution; diluting the obtained acid leaching solution, mixing with a purifying agent, performing a displacement reaction, and filtering to obtain a purified solution; extracting, acid washing, niobium removing and tantalum extracting are sequentially carried out on the purified liquid to obtain a niobium-containing solution; neutralizing the niobium-containing solution to be alkaline by using ammonia alkali to obtain niobium hydroxide; and finally, washing, drying and calcining the niobium hydroxide in sequence to obtain a high-purity niobium oxide product.
The niobium-tantalum-iron alloy is oxidized and roasted to remove carbon, sulfur and phosphorus impurity elements in the niobium-tantalum-iron alloy, and meanwhile, a metal simple substance in the niobium-tantalum-iron alloy is converted into a metal oxide, so that the situation that the metal simple substance reacts with acid to generate hydrogen is avoided; converting niobium and tantalum in the metal oxide into fluoroniobic acid and fluorotantalic acid by using hydrofluoric acid and sulfuric acid, and converting other metal oxides into metal ions; purifying, extracting, acid washing, niobium removing and tantalum extracting by using a purifying agent to obtain a niobium-containing solution, neutralizing and precipitating niobium ions by using ammonia water, and calcining to obtain the niobium oxide. The method provided by the invention can be used for efficiently removing impurity elements in the niobium-tantalum-iron alloy, so that the antimony element is reduced to be less than 10ppm, the content of the copper element is reduced to be less than 3.0ppm, and further, the niobium oxide with the purity of more than or equal to 99.95% is obtained.
Drawings
FIG. 1 is a process flow chart of preparing high purity niobium oxide from the niobium-tantalum-iron alloy provided by the invention.
Detailed Description
The invention provides a method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy, which comprises the following steps:
(1) roasting niobium-tantalum-iron alloy powder in an oxygen-containing atmosphere to obtain a solid oxide;
(2) mixing the solid oxide in the step (1) with hydrofluoric acid and sulfuric acid, and performing acid leaching to obtain acid leaching solution;
(3) diluting the acid leaching solution in the step (2), mixing the obtained diluent with a purifying agent, performing a displacement reaction, and filtering to obtain a purified solution;
(4) sequentially extracting, acid-washing, niobium-removing and tantalum-extracting the purified liquid obtained in the step (3) to obtain a niobium-containing solution;
(5) neutralizing the niobium-containing solution obtained in the step (4) to be alkaline by using ammonia alkali to obtain niobium hydroxide;
(6) washing, drying and calcining the niobium hydroxide obtained in the step (5) in sequence to obtain high-purity niobium oxide; the purity of the high-purity niobium oxide is more than or equal to 99.95 percent.
In the invention, the niobium-tantalum-iron alloy powder is roasted in an oxygen-containing atmosphere to obtain a solid oxide. In the present invention, the chemical composition of the niobium-tantalum-iron alloy powder preferably includes, by mass: 3.4-3.6% of tantalum, 38-40% of niobium, 0.05-0.07% of tungsten, 1.6-1.9% of aluminum, 1.3-1.8% of copper, 7-20% of silicon, 0.10-0.15% of antimony, 2.12-2.20% of sulfur, 2.0-2.4% of phosphorus, 1.0-1.2% of carbon and the balance of iron. The grain size of the niobium-tantalum-iron alloy powder is preferably 250-400 meshes, and more preferably 300-350 meshes; the niobium-tantalum-iron alloy powder is preferably obtained by crushing and sieving. The invention has no special requirements on the crushing and sieving modes of the niobium-tantalum-iron alloy, and the raw material powder with the particle size range can be obtained.
The niobium-tantalum-iron alloy powder is preferably mixed with an oxidation assistant and roasted to improve the oxidation effect of the niobium-tantalum-iron alloy powder. In the present invention, the oxidation aid preferably comprises NaNO2(ii) a The amount of the oxidation promoter is preferably 5-10% of the niobium-tantalum-iron alloy powder, more preferably 6-10%, and most preferably 6-9%. The invention has no special requirement on the mixing mode of the niobium-tantalum-iron alloy powder and the oxidation auxiliary agent, and adopts the technical fieldIn a manner well known to the skilled person.
In the invention, the roasting temperature is preferably 800-900 ℃, more preferably 820-880 ℃, and further preferably 830-860 ℃; the roasting time is preferably 2-4 hours, and more preferably 2.5-3.5 hours. The present invention does not require any particular embodiment of the firing, and firing methods known to those skilled in the art may be used.
According to the invention, metal components in the niobium-tantalum-iron alloy are made into metal oxides by roasting, so that a large amount of hydrogen is prevented from being generated in the subsequent acid leaching process, the safety of the acid leaching reaction is improved, and the aim of improving the efficiency of the acid leaching reaction is fulfilled; meanwhile, C, S and P impurity elements in the niobium-tantalum-iron alloy can be removed by roasting. The roasting can reduce the impurity elements in the niobium-tantalum-iron alloy to 0.50-0.53 wt.% of sulfur, 0.30-0.32 wt.% of phosphorus and 0.05-0.07 wt.% of carbon.
After the solid oxide is obtained, the solid oxide is mixed with hydrofluoric acid and sulfuric acid for acid leaching to obtain acid leaching solution. In the invention, the mass ratio of the solid oxide, the hydrofluoric acid and the sulfuric acid is preferably 1 (1.2-1.5) to 0.8-1.2, and more preferably 1 (1.3-1.4) to 0.9-1.0; the mass concentration of the hydrofluoric acid is preferably 52-57%, and more preferably 53-55%; the mass concentration of the sulfuric acid is preferably not less than 96%, and more preferably 97-98%. In the present invention, the mixing manner of the solid oxide, the hydrofluoric acid and the sulfuric acid preferably includes adding the hydrofluoric acid, the sulfuric acid and the solid oxide in this order.
In the invention, the acid leaching process is an exothermic reaction, and the temperature of a reaction system in the acid leaching process is preferably 60-80 ℃; the acid leaching time is preferably 14-18 h, and more preferably 15-16 h. In the invention, the acid leaching is preferably carried out under the conditions, so that the leaching rate of tantalum and niobium can be improved.
In the invention, in the acid leaching process, silicon dioxide in the solid oxide reacts with hydrofluoric acid to generate fluosilicic acid (H)2SiF6) (ii) a Niobium pentoxide and tantalum pentoxide in the solid oxide react with hydrofluoric acid respectively to generate fluoroniobate (H)2NbF7) And fluorotantalic acid (H)2TaF7) (ii) a The remaining metal oxide components of the solid oxide can react with an acid to produce the corresponding metal ions.
In the present invention, the chemical composition of the acid leachate preferably comprises the following ions: h+:16.0～16.5mol/L、NbF7 5+:184.0～186.1g/L、TaF7 5+:18.5～19.5g/L、Cu2+1.9-2.1 g/L and Sb5+:0.10～0.52g/L。
After the acid leaching solution is obtained, the invention dilutes the acid leaching solution to adjust the acidity, mixes the obtained dilution solution with a purifying agent, performs a displacement reaction, and filters to obtain the purifying solution. The invention dilutes the acid leaching solution, reduces the concentration of each component in the acid leaching solution, and leads the subsequent displacement reaction to be carried out at a proper speed. In the present invention, H is contained in the diluent+The concentration of (B) is preferably 10.5 to 12.0mol/L, and more preferably 11.0 to 11.8 mol/L. The present invention preferably dilutes the acid leachate with water, preferably deionized water. The invention has no special requirement on the dosage of the water so as to obtain the diluent with the hydrogen ion concentration range. The present invention has no special requirement on the dilution method of the acid leachate, and the dilution method known to those skilled in the art can be adopted.
After the diluent is obtained, the diluent is mixed with a purifying agent for a displacement reaction, and the purifying solution is obtained after filtration. In the present invention, the chemical composition of the scavenger preferably comprises 40 to 60 wt.% Fe, 10 to 20 wt.% Al, 5 to 10 wt.% Zn, and the balance Si.
The chemical composition of the purifying agent comprises 40-60 wt.% of Fe, preferably 45-55 wt.%, and more preferably 48-52 wt.%; the chemical composition of the purifying agent further comprises 10-20 wt.% of Al, preferably 12-18 wt.%, more preferably 14-15 wt.%; the chemical composition of the purifying agent comprises 5-10 wt.% Zn, preferably 6-9 wt.%, more preferably 7-8 wt.%.
According to the invention, metals such as Fe, Al and Zn are used for replacing metal ions with low chemical activity in the diluent, so that the inactive metal ions are converted into metal simple substances to be precipitated from the solution, and the purpose of separating the inactive metal elements is achieved.
In the invention, the purifying agent preferably further comprises 5-10 wt.% of Mn and/or 5-10 wt.% of Mg, and the content of Mn is more preferably 6-9 wt.%; the content of Mg is more preferably 6-9 wt.%.
In the present invention, the scavenger further comprises Si. The invention has no special requirement on the content of Si, and the sum of the contents of all elements in the chemical composition of the purifying agent can reach 100%.
In the invention, the particle size of the purifying agent is preferably 40-100 meshes, more preferably 50-90 meshes, and even more preferably 60-80 meshes. The invention preferably limits the grain diameter of the purifying agent in the range, can promote the reaction of the purifying agent and impurity components in the solution to be purified, and improves the impurity removal efficiency.
In the present invention, the method for preparing the scavenger preferably comprises: smelting the raw materials according to the chemical composition of the purifying agent to obtain an alloy melt; and sequentially carrying out water quenching, crushing and sieving on the alloy melt to obtain the purifying agent. The present invention does not require a particular source for the starting materials, and may employ commercially available products well known to those skilled in the art. The invention has no special requirements on the smelting mode of the raw materials, and the mode known by the technical personnel in the field can be adopted. The present invention does not require any particular embodiment of the water quenching, crushing and sieving, and can be practiced in a manner well known to those skilled in the art.
In the invention, the mass ratio of the purifying agent to the volume of the diluent is preferably 110-125 kg/m3May be 115kg/m3、119kg/m3、120kg/m3、121kg/m3、122kg/m3、123kg/m3、124kg/m3Or 125kg/m3. The mixing mode of the diluent and the purifying agent is not particularly required in the invention, and the mode known by the technicians in the field can be adopted. After the diluent is mixed with the purifying agent, the purifying agent adsorbs copper ions and antimony ions in the diluent on the surface of the purifying agent through a displacement reaction, and the copper ions and the antimony ions are removed through subsequent filtration.
In the present invention, the time for the substitution reaction is preferably 0.5 to 2 hours, and more preferably 1.5 to 2 hours. After the replacement reaction is finished, the invention immediately filters the materials after the replacement reaction to separate the solid impurities of the copper simple substance and the antimony simple substance generated by the reaction, thereby avoiding the re-dissolution of the copper simple substance and the antimony simple substance and obtaining the purified liquid. In the present invention, Cu in the purification solution2+The content is less than 0.1g/L, and the Sb is5+And Sb3+Independently < 0.002 g/L.
After the purified liquid is obtained, the invention sequentially performs extraction, acid washing, niobium removing and tantalum extraction on the purified liquid to obtain the niobium-containing solution. Before extraction, the concentration of hydrofluoric acid and sulfuric acid in the purification solution is preferably adjusted to make the concentration of hydrofluoric acid reach 6.3-6.6 mol/L; the concentration of the sulfuric acid reaches 3.3-3.7 mol/L. The concentration of hydrofluoric acid and sulfuric acid is preferably adjusted to the range, so that the extraction rate of impurities such as tungsten ions, iron ions and the like can be reduced on the basis of ensuring the extraction rate of fluoroniobate and fluorotantalate, and a better separation and purification effect can be achieved.
In the present invention, the extraction preferably comprises:
mixing the purified solution with an extracting agent, oscillating, standing and layering to obtain an organic phase and a water phase;
and separating the organic phase from the water phase to obtain an organic phase.
In the present invention, the extractant for extraction preferably includes sec-octanol or methyl isobutyl ketone (MIBK); further preferably sec-octanol; the volume ratio of the extracting agent to the purifying liquid is preferably 1.0-1.5: 1, and more preferably 1.2-1.4: 1. The invention has no special requirement on the mixing mode of the purifying liquid and the extracting agent, and the mixing mode which is well known by the technical personnel in the field can be adopted.
After mixing, the mixed solution obtained after mixing is oscillated and stood so that the fluoroniobate and the fluorotantalic acid fully enter an organic phase. The invention has no special requirement on the oscillation mode, and can fully mix the extracting agent and the purifying liquid. The invention has no special requirement on the standing time, and can fully layer the mixed solution.
After obtaining the organic phase and the aqueous phase, the present invention preferably separates the organic phase and the aqueous phase to obtain the organic phase. The present invention does not require any particular means for separation, and may be practiced in a manner well known to those skilled in the art.
After the organic phase is obtained, the invention carries out acid washing on the organic phase to remove impurity elements such as tungsten, silicon, iron and the like in the organic phase, and obtains the tantalum-niobium-containing solution. In the invention, the washing liquid for acid washing preferably comprises a sulfuric acid washing liquid, and the concentration of the sulfuric acid washing liquid is preferably 3.2-3.7 mol/L, and more preferably 3.4-3.5 mol/L; the sulfuric acid wash is preferably formulated with 98% CP pure sulfuric acid. In the present invention, the volume ratio of the organic phase to the sulfuric acid washing liquid is preferably 3 to 3.3:1, and more preferably 3: 1. In the present invention, the pickling method is preferably 10-stage counter-current washing. The present invention does not require any particular embodiment of the acid wash, and can be practiced as is well known to those skilled in the art.
After acid washing, the invention carries out niobium-reversing tantalum extraction on the material after acid washing to obtain high-purity niobium liquid. The anti-niobium tantalum extraction method comprises an anti-niobium section and a tantalum extraction section, wherein the anti-niobium agent for the anti-niobium section preferably comprises a sulfuric acid solution, and the concentration of the sulfuric acid solution is preferably 1.4-1.8 mol/L, and is further preferably 1.5-1.6 mol/L; the purity of the sulfuric acid solution is preferably A.R. grade; the anti-niobium section is preferably grade 10 anti-niobium. The preferable grade 14 tantalum extraction section is the tantalum extraction section, the flow ratio of the organic tantalum extraction agent to the anti-niobium agent is 1-1.2: 1. the specific implementation of the anti-niobium tantalum extraction can be realized by adopting a mode well known by the technical personnel in the field.
After obtaining the niobium-containing solution, the present invention neutralizes the niobium-containing solution to alkaline with ammonia base. In the invention, the pH value of the alkaline niobium-containing solution is preferably 8.5-9.5. In the present invention, the ammonia base preferably includes ammonia gas, liquid ammonia, or aqueous ammonia; when the ammonia base is ammonia water, the invention has no special requirement on the concentration of the ammonia water. The specific amount of the ammonia base is not particularly required in the invention, so that the pH value of the niobium-containing solution can be neutralized to the range. According to the invention, the solution containing niobium is neutralized to be alkaline by using ammonia alkali, so that on one hand, niobium ions in the solution can be fully precipitated, and on the other hand, the ammonia alkali is volatile gas and is easy to remove, and the introduction of new impurities can be avoided.
After obtaining the niobium hydroxide, the niobium hydroxide is sequentially washed, dried and calcined to obtain the niobium oxide. In the present invention, it is preferable to wash niobium hydroxide with high purity water to remove fluorine ions adsorbed on the surface of niobium hydroxide.
After washing, the invention dries the material obtained after washing. The invention has no special requirements on the drying temperature and time to remove the moisture in the niobium hydroxide; after drying, the invention preferably crushes and screens the dried material to obtain niobium hydroxide particles with smaller particle size, thereby improving the subsequent calcining efficiency and reducing the energy consumption. In the present invention, the manner of said crushing is well known to the person skilled in the art; the mesh number of the screen mesh for sieving is preferably 60-100 meshes, more preferably 60-80 meshes, and undersize is used as a target object.
After drying, the invention calcines the dried material to obtain the niobium oxide. In the invention, the calcination temperature is preferably 850-1000 ℃, and more preferably 900-950 ℃; the calcination time is preferably 5 to 7 hours, and more preferably 5.5 to 6.5 hours.
In the invention, Ta element is less than 10ppm, Sb element is less than 10ppm, Cu element is less than 3.0ppm in the niobium oxide, and the niobium oxide meets the high-purity niobium pentoxide nonferrous metal industry standard FNb2O5-035 and above standards.
In the invention, after the lifting, a tantalum-containing solution is also obtained. The invention preferably produces the potassium fluotantalate by tantalum in the tantalum-containing solution so as to improve the recovery rate of the tantalum. The method for producing the potassium fluotantalate has no special requirements and can be well known by the technical personnel in the field.
For further illustration of the present invention, the method for preparing high purity niobium oxide from an alloy of niobium, tantalum and iron provided by the present invention is described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Niobium-tantalum-iron alloy powders having the compositions shown in table 1 were used.
TABLE 1 chemical composition of NbTaFeFe alloy
| Element(s) | Ta | Nb | W | Si | Al | Cu | Fe | Sb | S | P | C |
| Mass content | 3.51 | 39.62 | 0.06 | 18.3 | 1.7 | 1.5 | 28.4 | 0.12 | 2.17 | 2.2 | 1.09 |
Crushing and grinding the niobium-tantalum-iron alloy to 300 meshes, and roasting at 850 ℃ for 3 hours to obtain a solid oxide; detecting and analyzing main impurity components in the solid oxide: copper: 1.35%, antimony: 0.1%, sulfur: 0.52%, phosphorus: 0.31%, carbon: 0.06 percent;
carrying out acid leaching on the solid oxide by using hydrofluoric acid and sulfuric acid according to the mass ratio of 1:1.4:0.9, and reacting for 16 hours, wherein the mass concentration of the hydrofluoric acid is 55%, the mass concentration of the sulfuric acid is 98%, and acid leaching liquid is obtained, and the chemical components are as follows: nb2O5:185.6g/L，Ta2O5:19.5g/L，Cu2+:2.1g/L，Sb5+:0.52g/L，∑H+16.4 mol/l. Nb in leaching slag2O5：0.15％，Ta2O5<0.1 percent and the leaching rates of tantalum and niobium are all more than 99 percent.
Diluting the acidity of the acid leachate to ∑ H+11.8mol/L, 120kg/m3Adding a purifying agent in an amount of the above components, stirring for 2h and filtering to obtain a purified solution, wherein the purified solution is Cu<0.1g/L，Sb<0.002g/L。
Adjusting the acid of the purified liquid to 6.5mol/L hydrofluoric acid and 3.5mol/L sulfuric acid by using hydrofluoric acid and sulfuric acid, and extracting by using octanol as an extracting agent, wherein the volume ratio of an organic phase to water is 1.2:1, so as to obtain an organic phase containing tantalum and niobium.
Preparing a pickling agent with the volume ratio of the tantalum-niobium-containing organic phase to the pickling agent being 3:1 by using 98% C.P pure sulfuric acid, and carrying out 10-stage countercurrent washing to obtain an acid-washed organic phase; A.R pure sulfuric acid is used for preparing 1.6mol/L sulfuric acid solution as an anti-niobium agent, and the niobium-containing solution is obtained through 10-grade anti-niobium and 14-grade tantalum extraction.
Neutralizing the niobium-containing solution with ammonia gas until the pH value is 9 to obtain niobium hydroxide precipitate, washing with high-purity water, performing solid-liquid separation, drying, crushing, sieving with a 60-mesh sieve, and purifying the obtained productCalcining for 6 hours at 830 ℃ to obtain the high-purity niobium oxide product. Detection shows that the product impurity tantalum in the high-purity niobium oxide: 2.0ppm, 5.6ppm of Sb and 3.0ppm of Cu, and other impurities can all meet the non-ferrous metal industry standard FNb2O5The requirement of 04 mark, the specific element components are shown in Table 3.
Example 2
The TaNb-Fe alloy powder was processed in the same manner as in example 1, except that the chemical composition of the cleaning agent (shown in Table 2) was changed, the particle size of the TaNb-Fe alloy powder was 280 mesh, the oxidizing roasting temperature was 870 ℃, and 6.5% NaNO was added during the oxidizing roasting2The extraction agent is MIBK, the mixture is calcined at 850 ℃ for 5 hours, and other specific contents are shown in tables 2-3. The purity of the high-purity niobium oxide obtained in the embodiment is detected to meet the non-ferrous metal industry standard FNb2O5-04 grade requirement.
Example 3
A cleaning agent was prepared and used as in example 1, except that the chemical composition of the cleaning agent (shown in Table 2), the particle size of the tantalum-niobium-iron alloy powder was 300 mesh, the oxidizing roasting temperature was 900 ℃ and 8.5% NaNO was added during the oxidizing roasting2The used extracting agent is sec-octanol, and the secondary octanol is calcined at 880 ℃ for 5 hours, and other specific contents are shown in tables 2-3. The purity of the high-purity niobium oxide obtained in the embodiment is detected to meet the non-ferrous metal industry standard FNb2O5-04 grade requirement.
TABLE 2 chemical composition of purifiers of examples 1 to 3 (in mass%)
| Examples | Fe | Al | Zn | Mn | Mg | Si |
| 1 | 40 | 11 | 10 | —— | —— | Balance of |
| 2 | 60 | 13 | 5 | 5 | 7 | Balance of |
| 3 | 52 | 20 | 7 | 8 | 10 | Balance of |
TABLE 3 EXAMPLES 1-3 high purity niobium oxide chemistries
| Element content | FNb2O5-04 | FNb2O5-035 | Example 1 | Example 2 | Example 3 |
| Ta | 10.0 | 20.0 | 2 | 2 | 3 |
| Al | 3.0 | 5.0 | 2.0 | 1.0 | 0.5 |
| As | 5.0 | 10.0 | 1.0 | 0.5 | 0.5 |
| B | 1.0 | - | ＜1 | ＜1 | ＜1 |
| Bi | 2.0 | 3.0 | ＜0.5 | ＜0.5 | ＜0.5 |
| Ca | 5.0 | - | 1.0 | 1.0 | 1.0 |
| Co | 1.0 | - | ＜0.1 | ＜0.1 | ＜0.1 |
| Cr | 3.0 | 5.0 | 0.5 | 0.5 | 0.5 |
| Cu | 3.0 | 5.0 | 3.0 | 1.0 | 0.5 |
| F | 75.0 | 100 | 50 | 18 | 23 |
| Fe | 5.0 | 10.0 | 4.0 | 2.1 | 0.9 |
| K | 5.0 | - | ＜2 | ＜2 | ＜2 |
| Mg | 2.0 | - | ＜0.5 | ＜0.5 | ＜0.5 |
| Mn | 2.0 | 5.0 | 0.2 | 0.2 | 0.2 |
| Mo | 2.0 | 8.0 | ＜0.1 | ＜0.1 | ＜0.1 |
| Na | 5.0 | - | 3.0 | 0.5 | 0.5 |
| Ni | 3.0 | 10.0 | ＜0.5 | ＜0.5 | ＜0.5 |
| Sb | 3.0 | 10.0 | 5.6 | 1.6 | 1.5 |
| Si | 10.0 | - | 10 | 6.8 | 8.2 |
| Sn | 1.0 | 5.0 | 2.0 | 0.5 | 0.5 |
| Ti | 1.0 | 5.0 | 0.8 | 0.5 | 0.5 |
| V | 1.0 | - | ＜0.1 | ＜0.1 | ＜0.1 |
| W | 3.0 | 5.0 | ＜0.5 | ＜0.5 | ＜0.5 |
| Zr | 1.0 | - | ＜0.1 | ＜0.1 | ＜0.1 |
| LOI | 500 | 620 | 480 |
As is clear from Table 3, the high purity niobium oxide obtained in examples 1 to 3 had a low content of each impurity elementIs up to and even better than FNb2O5-04 and FNb2O5035, the method provided by the invention can fully remove antimony and copper elements in the tantalum-niobium-iron alloy, and the obtained niobium oxide has high purity and meets the market demand for high-purity niobium oxide.
From the above embodiments, the method for preparing high-purity niobium oxide from niobium-tantalum-iron alloy provided by the invention solves the defects and shortcomings in the existing niobium-tantalum-iron alloy treatment technology by the methods of oxidizing roasting, purifying and removing impurities, extracting niobium, precipitating and calcining: the niobium-tantalum-iron alloy is converted into an oxide form from a metal state through oxidizing roasting, hydrogen is not generated in the subsequent acid leaching process, and the safety accident risk caused by improper operation is reduced; the oxidizing roasting can also volatilize and remove impurities such as carbon, sulfur, phosphorus and the like in the niobium-tantalum-iron alloy, so that the problem of modifying and poisoning of an extracting agent caused by long-term use is avoided; the purifying agent is used for purifying the acid leaching solution, so that impurity elements such as antimony, copper and the like which are difficult to separate in the extraction process are removed, and the niobium oxide with the purity of more than or equal to 99.95 percent is obtained.
Besides the advantages, the method for preparing the high-purity niobium oxide from the niobium-tantalum-iron alloy also has high efficiency. The traditional process without oxidizing roasting is safe production, in order to control the reaction speed to be too high so as to generate a large amount of hydrogen, uncrushed raw materials or raw material granularity controlled to be 1-5 mm are required to be used, the feeding speed is 50-200 kg/h, and the leaching rate of tantalum and niobium is only 91-93%; according to the scheme of the invention, the feeding speed reaches 1500-3000 kg/h, the leaching rate of tantalum and niobium reaches more than 98.5%, and the production rate is obviously improved.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (9)
1. A method for preparing high-purity niobium oxide by niobium-tantalum-iron alloy comprises the following steps:
(1) roasting niobium-tantalum-iron alloy powder in an oxygen-containing atmosphere to obtain a solid oxide;
(2) mixing the solid oxide obtained in the step (1) with hydrofluoric acid and sulfuric acid, and carrying out acid leaching to obtain acid leaching solution;
(3) diluting the acid leaching solution obtained in the step (2), mixing the obtained diluent with a purifying agent, performing a displacement reaction, and filtering to obtain a purified solution;
(4) sequentially extracting, acid-washing, niobium-removing and tantalum-extracting the purified liquid obtained in the step (3) to obtain a niobium-containing solution;
(5) neutralizing the niobium-containing solution obtained in the step (4) to be alkaline by using ammonia alkali to obtain niobium hydroxide;
(6) washing, drying and calcining the niobium hydroxide obtained in the step (5) in sequence to obtain high-purity niobium oxide; the purity of the high-purity niobium oxide is more than or equal to 99.95 percent;
the chemical composition of the purifying agent in the step (3) comprises: 40-60 wt.% Fe, 10-20 wt.% Al, 5-10 wt.% Zn and the balance Si.
2. The method according to claim 1, wherein the niobium-tantalum-iron alloy powder of step (1) is mixed with an oxidation aid and calcined; the oxidation assistant comprises NaNO2(ii) a The particle size of the niobium-tantalum-iron alloy powder is 250-400 meshes.
3. The method of claim 1, wherein the roasting temperature in the step (1) is 800-900 ℃ and the roasting time is 2-4 h.
4. The method according to claim 1, wherein the mass concentration of the hydrofluoric acid in the step (2) is 53-55%; the mass concentration of the sulfuric acid is more than or equal to 96 percent;
the mass ratio of the solid oxide to the hydrofluoric acid to the sulfuric acid is 1 (1.2-1.5) to 0.8-1.2.
5. The method of claim 1, wherein the scavenger further comprises 5 to 10 wt.% Mn and/or 5 to 10 wt.% Mg.
6. The method according to claim 1 or 5, wherein the scavenger has a particle size of 40 to 100 mesh.
7. The method of claim 1, wherein the H of the diluent in step (3)+The concentration is 10.5-12.0 mol/L.
8. The method as claimed in claim 1 or 7, wherein the mass-to-volume ratio of the scavenger of step (3) to the diluent is 110 to 125kg/m3(ii) a The time of the replacement reaction is 0.5-2.0 h.
9. The process according to claim 1, wherein the extractant for extraction in the step (4) comprises sec-octanol or methyl isobutyl ketone; the pickling agent for pickling is a sulfuric acid solution with the concentration of 3.2-3.7 mol/L; the niobium-resisting agent for resisting niobium is a sulfuric acid solution with the concentration of 1.4-1.8 mol/L.
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| CN111485122B (en) * | 2020-04-20 | 2022-05-17 | 北京工业大学 | Method for recycling niobium from waste NbTaZr alloy |
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| CN111719055A (en) * | 2020-07-15 | 2020-09-29 | 江西拓泓新材料有限公司 | Method for decomposing and leaching tantalum and niobium from sodium-reduced tantalum-niobium metal waste |
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