CN114540642A - Method for recovering valuable metal from tantalum raffinate - Google Patents

Method for recovering valuable metal from tantalum raffinate Download PDF

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CN114540642A
CN114540642A CN202210191023.XA CN202210191023A CN114540642A CN 114540642 A CN114540642 A CN 114540642A CN 202210191023 A CN202210191023 A CN 202210191023A CN 114540642 A CN114540642 A CN 114540642A
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raffinate
titanium
tantalum
chromium
organic phase
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王杰
行卫东
朱刘
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First Rare Materials Co Ltd
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First Rare Materials Co Ltd
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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
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • 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
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention provides a method for recovering valuable metals from tantalum raffinate, which comprises the following steps: mixing tantalum raffinate with an extracting agent 1, and selectively extracting titanium from the tantalum raffinate to obtain a titanium-loaded organic phase and titanium raffinate; step two, introducing chlorine into the titanium raffinate, mixing the titanium raffinate with an extracting agent 2, and selectively extracting chromium from the titanium raffinate to obtain a chromium-loaded organic phase and a chromium raffinate; step three, mixing the titanium-loaded organic phase with a stripping agent 1, performing stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the step one for recycling; step four, mixing the loaded organic phase of the chromium obtained in the step two with a stripping agent 2, performing stripping to obtain chromium-rich slag, and returning the organic phase to the step two for recycling after the organic phase is regenerated; and fifthly, carrying out defluorination treatment on the chromium raffinate. According to the method, after the valuable metals such as titanium and chromium in the tantalum raffinate are selectively extracted, the stripping solution with high purity is obtained through stripping.

Description

Method for recovering valuable metal from tantalum raffinate
Technical Field
The invention relates to the field of recycling of valuable metals in waste acid, in particular to a method for recycling valuable metals from tantalum raffinate.
Background
More than 99% of metal tantalum in the tantalum-chromium-titanium alloy cutting material is recovered by adopting a hydrofluoric acid-sulfuric acid leaching-extraction separation process, and a large amount of valuable metal chromium and titanium are left in raffinate to be recovered and reused. Other valuable metals in the liquid after the tantalum separation and recovery are recovered, so that the method is not only beneficial to reducing the recovery cost of the tantalum chromium titanium target material waste and improving the economic benefit, but also has great strategic significance on the aspect of protecting the environment.
At present, in the tantalum recovery industry, a step precipitation method is mainly adopted for treating wastewater, and the method generally adds a precipitator into tantalum raffinate to obtain potassium fluotitanate precipitate and chromium-containing solution, and then adds alkali to control pH to obtain chromium hydroxide precipitate. The fractional precipitation process precipitates titanium and chromium ions in the acid waste liquid, is simple to operate, has low equipment requirement and low treatment cost, but consumes a large amount of precipitator in the precipitation process, has long treatment time, and causes resource waste when a small amount of tantalum in the raffinate is difficult to recycle.
Due to the wide application of tantalum alloy, the demand of tantalum alloy is increasing, the secondary tantalum resource is increased, and a large amount of tantalum raffinate containing valuable metals is generated in the recovery process of tantalum alloy waste. Therefore, it is necessary to develop a method for recovering valuable metals in tantalum raffinate.
Disclosure of Invention
In view of the problems in the prior art, the present disclosure is directed to a method for recovering valuable metals from a tantalum raffinate.
In order to achieve the above objects, the present disclosure provides a method for recovering valuable metals from tantalum raffinate, comprising the steps of: mixing tantalum raffinate with an extracting agent 1 according to a certain ratio, and selectively extracting titanium from the tantalum raffinate to obtain a titanium loaded organic phase and titanium raffinate; step two, introducing chlorine into the titanium raffinate for 1-3 hours, mixing the titanium raffinate with an extracting agent 2 according to a certain ratio, and selectively extracting chromium from the titanium raffinate to obtain a chromium-loaded organic phase and a chromium raffinate; step three, mixing the loaded organic phase of the titanium obtained in the step one with a stripping agent 1 according to a certain ratio, performing stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the step one for recycling; step four, mixing the chromium-loaded organic phase obtained in the step two with a stripping agent 2 according to a certain ratio, performing stripping to obtain chromium-rich slag, and returning the regenerated organic phase to the step two for recycling; and fifthly, carrying out defluorination treatment on the chromium raffinate.
In some embodiments, the tantalum raffinateThe concentration of medium tantalum is 0.1g/L-1g/L, the concentration of titanium is 1g/L-10g/L, the concentration of chromium is 1g/L-10g/L, H2SO4The content is 150-200 g/L, and the HF content is 10-50 g/L.
In some embodiments, the extractant 1 comprises an extraction titanium extractant, a modifier, and a diluent.
In some embodiments, the extractive titanium extractant is at least one of a primary amine or a secondary amine-based extractant.
In some embodiments, the modifier is sec-octanol or isoamyl alcohol.
In some embodiments, the diluent is sulfonated kerosene.
In some embodiments, the composition of extractant 1 is, in volume fraction: 10 to 20 percent of primary amine or secondary amine extractant, 3 to 5 percent of sec-octanol or isoamylol and 75 to 87 percent of sulfonated kerosene.
In some embodiments, the primary or secondary amine-based extractant is N1923At least one of Alamine 21F81, Primene JMT or N-dodecylamine.
In some embodiments, in the step one, the ratio is 1-3: 1, the oscillation time at normal temperature is 10-30 min, and the number of extraction stages is five.
In some embodiments, the extractant 2 comprises a pyridine ionic liquid extractant and n-pentanol.
In some embodiments, the pyridine ionic liquid extractant comprises N-octyl pyridinium chloride ([ OPy ] C1) ionic liquid.
In some embodiments, the composition of extractant 2 is 5-10% by volume of N-octyl pyridinium chloride ([ OPy ] C1) ionic liquid, and the proportion of N-pentanol is 95-90%.
In some embodiments, in the second step, the ratio is 1-3: 1, the oscillation time at room temperature is 10-30 min, and the number of extraction stages is five.
In some embodiments, in the third step, the stripping agent 1 is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 2-5 mol/L; the molecular mass ratio of the hydrogen peroxide dosage to the titanium content in the loaded organic phase is 2-4, the ratio is 1-5: 1, the normal-temperature oscillation time is 10-30 min, and the back extraction stage number is five.
In some embodiments, in the fourth step, the stripping agent 2 is an ammonium chloride solution with a concentration of 2-5 mol/L and a stripping ratio of 1-5: 1; the normal temperature oscillation time is 10-30 min, and the back extraction stage number is five.
The beneficial effects of this disclosure are as follows:
the method disclosed by the invention has the advantages that after the titanium and chromium valuable metals in the tantalum raffinate are selectively extracted, the stripping solution with higher purity is obtained through stripping, the product with high purity can be further prepared, the operation is simple, various intermediate products can be obtained, the economic benefit is high, in addition, the titanium and chromium separated liquid can be used for preparing the ammonium fluoride product with higher purity through simple treatment, the ammonium fluoride product can return to the tantalum stripping stage in the early stage, the ammonium fluoride can be repeatedly utilized, the resource regeneration and cyclic utilization can be realized, and the economic and social benefits are better.
Detailed Description
The method for recovering valuable metals from a tantalum raffinate according to the present disclosure is described in detail below.
The application discloses a method for recovering valuable metals from tantalum raffinate, which comprises the following steps: mixing tantalum raffinate with an extracting agent 1 according to a certain ratio, and selectively extracting titanium from the tantalum raffinate to obtain a titanium-loaded organic phase and titanium raffinate; step two, introducing chlorine into the titanium raffinate for 1-3 hours, mixing the titanium raffinate with an extracting agent 2 according to a certain ratio, and selectively extracting chromium from the titanium raffinate to obtain a chromium-loaded organic phase and a chromium raffinate; step three, mixing the loaded organic phase of the titanium obtained in the step one with a stripping agent 1 according to a certain ratio, performing stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the step one for recycling; step four, mixing the chromium-loaded organic phase obtained in the step two with a stripping agent 2 according to a certain ratio, performing stripping to obtain chromium-rich slag, and returning the regenerated organic phase to the step two for recycling; and fifthly, carrying out defluorination treatment on the chromium raffinate.
The metal-enriched liquid disclosed by the disclosure can be recovered through different processes, for example, titanium dioxide can be obtained by hydrolyzing, washing and calcining the titanium-enriched liquid, and the liquid can also be directly returned to the titanium dioxide process; the chromium-rich slag can be further recycled to prepare chromium metal.
In the second step, chlorine is introduced to lead Cr in the solution to3+Oxidation to Cr6+。
In some embodiments, the tantalum raffinate has a tantalum concentration of 0.1g/L to 1g/L, a titanium concentration of 1g/L to 10g/L, a chromium concentration of 1g/L to 10g/L, and H2SO4The content is 150-200 g/L, and the HF content is 10-50 g/L.
In some embodiments, the extractant 1 comprises an extraction titanium extractant, a modifier, and a diluent; the extraction titanium extractant is at least one of primary amine extractant or secondary amine extractant; the modifier is sec-octanol or isoamylol; the diluent is sulfonated kerosene.
The primary and secondary amine extractants are effective extractants for extracting titanium; the primary and secondary amine extractants have polymerization in non-polar diluent, so polar modifier, i.e. secondary octanol and isoamyl alcohol, is added.
In some embodiments, the composition of extractant 1 is, in volume fraction: 10 to 20 percent of primary amine or secondary amine extractant, 3 to 5 percent of sec-octanol or isoamylol and 75 to 87 percent of sulfonated kerosene.
In some embodiments, the primary or secondary amine-based extractant is N19234-ethyloctylamine, Primene JMT or N-dodecylamine.
In some embodiments, in the step one, the ratio is 1-3: 1, the oscillation time at normal temperature is 10-30 min, and the number of extraction stages is five. The extraction rate of titanium increases with increasing phase ratio, and the magnitude of the increase in extraction rate becomes smaller and smaller with increasing phase ratio. Within the above range, the extraction rate is relatively high.
In some embodiments, the extractant 2 is a pyridine ionic liquid extractant, which is a pyridine ionic liquid-to-Cr extractant6+Has better extraction selectivity. The pyridine ionic liquid extractant comprises N-octyl pyridinium chloride ([ OPy)]Cl) ionic liquid.
In some embodiments, the extractant 2 is formulated with a volume fraction of 5% to 10% N-octyl pyridinium chloride ([ OPy ] Cl) ionic liquid, and a proportion of 90% to 95% N-pentanol.
In some embodiments, in the second step, the ratio is 1-3: 1, the oscillation time at room temperature is 10-30 min, and the number of extraction stages is five.
In some embodiments, in the third step, the stripping agent 1 is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of sulfuric acid is 2-5 mol/L, the molecular mass ratio of the amount of hydrogen peroxide to the titanium content in the loaded organic phase is 2-4, the ratio is 1-5: 1, the normal temperature oscillation time is 10-30 min, and the number of stripping stages is five.
H2O2-H2SO4The complex stripping with the mixed solution as the stripping agent has better stripping effect, and can effectively strip Ti in the loaded organic phase. The complex stripping is carried out by reacting titanium with H under acidic condition2O2Red peroxy complexes are formed, thereby changing the existing form of titanium and obtaining stripping of titanium.
The back extraction rate of titanium is increased along with the increase of the consumption of hydrogen peroxide, and when the ratio of the back extraction rate of titanium is larger than 4, the back extraction rate of titanium is not increased any more, so that the selection is 2-4 times.
In some embodiments, the stripping agent 2 is an ammonium chloride solution with a concentration of 2-5 mol/L, and the stripping phase ratio is 1-5: 1; the normal temperature oscillation time is 10-30 min, and the back extraction stage number is five.
N-octyl pyridinium chloride salt ([ OPy)]Cl) ionic liquid has large polarity and strong ion binding capacity, and can effectively extract hexavalent chromium. The Cr in the loaded organic phase can be stripped by using ammonium chloride solution2O7 2-Back extraction to obtain chromium-rich slag (NH)4)2Cr2O7。
In the fifth step, the chromium raffinate is subjected to defluorination treatment, ammonium fluoride products with higher purity can be prepared through simple treatment, and the ammonium fluoride products can return to the early tantalum back-extraction stage for recycling, so that the resources are recycled.
[ test ]
Example 1
Step one, the tantalum concentration in the tantalum raffinate0.1g/L, 10g/L titanium and 10g/L, H chromium2SO4The content of the tantalum raffinate is 150g/L, the content of HF is 10g/L, the tantalum raffinate and an extracting agent 1 (10% of N1923-3% of secondary octanol-87% of sulfonated kerosene) are mixed according to the ratio of 1: 1, the titanium is extracted by three-stage countercurrent for 10min at normal temperature, the titanium is selectively extracted from the tantalum raffinate, and a titanium loaded organic phase and titanium raffinate are obtained;
step two, introducing chlorine gas into the titanium raffinate for 1h, and adding Cr in the solution3+Oxidation to Cr6+Then with extractant 2 (5% N-octyl pyridine chloride salt ([ OPy))]C1) Ionic liquid-95% n-pentanol) as compared to 1: 1, mixing, oscillating for 10min at normal temperature, and selectively extracting chromium from the titanium raffinate to obtain a chromium-loaded organic phase and chromium raffinate;
thirdly, the loaded organic phase of the titanium obtained in the first step and a stripping agent 1(2mol/L sulfuric acid solution + 10% hydrogen peroxide) are vibrated for 10min at normal temperature, the stripping stage number is five, the phase ratio is 1: 1, a titanium-rich solution is obtained by stripping, and the organic phase is recycled in the first step after regeneration;
step four, comparing the supported organic phase of the chromium obtained in the step two with a stripping agent 2(2mol/L ammonium chloride solution) in a ratio of 1: 1, oscillating for 10min at normal temperature, performing five-stage stripping on the chromium, performing stripping to obtain chromium-rich slag, and returning the regenerated organic phase to the step two for recycling.
As a result:
the extraction rate of titanium is more than or equal to 99 percent, the back extraction rate is more than or equal to 97 percent, and the concentration of titanium in the titanium-rich liquid reaches 100 g/L;
the extraction rate of chromium is more than or equal to 98 percent, the back extraction rate is more than or equal to 97 percent, and the chromium concentration in the chromium-rich liquid reaches 90 g/L.
Example 2
Step one, the tantalum concentration in the tantalum raffinate is 0.5g/L, the titanium content is 10g/L, and the chromium content is 8g/L, H2SO4150g/L of tantalum raffinate and 20g/L of HF, and extracting with 1 (15% N)19235 percent of secondary octanol to 80 percent of sulfonated kerosene) according to the ratio of 2: 1, oscillating for 10min at normal temperature, extracting titanium in a three-stage countercurrent manner, and selectively extracting titanium from tantalum raffinate to obtain a titanium loaded organic phase and titanium raffinate;
step two, introducing titanium raffinateChlorine gas for 2 hours, and Cr in the solution3+Oxidation to Cr6+Then with extractant 2 (6% N-octyl pyridinium chloride ([ OPy)]Cl) ionic liquid-94% n-amyl alcohol) are mixed according to the ratio of 2: 1, and are vibrated for 10min at normal temperature, chromium is selectively extracted from titanium raffinate, and a chromium-loaded organic phase and chromium raffinate are obtained;
thirdly, carrying out normal-temperature oscillation on the loaded organic phase of the titanium obtained in the first step and a stripping agent 1(3mol/L sulfuric acid solution + 15% hydrogen peroxide) for 15min, wherein the stripping stage number is five, and the ratio is 2: 1, carrying out stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the first step for recycling;
and step four, carrying out five-stage back extraction on the chromium-loaded organic phase obtained in the step two and a back extractant 2(3mol/L ammonium chloride solution) in a ratio of 1: 1 to obtain chromium-rich slag, and returning the organic phase to the step two for recycling after regeneration.
As a result:
the extraction rate of titanium is more than or equal to 97 percent, the back extraction rate is more than or equal to 99 percent, and the concentration of titanium in the titanium-rich liquid reaches 110 g/L;
the extraction rate of chromium is more than or equal to 99 percent, the back extraction rate is more than or equal to 96 percent, and the chromium concentration in the chromium-rich liquid reaches 95 g/L.
Example 3
Step one, the tantalum concentration in the tantalum raffinate is 0.3g/L, the titanium content is 9g/L, and the chromium content is 8g/L, H2SO4160g/L of tantalum raffinate and 30g/L of HF, and extracting with 1 (10% N)19235 percent of secondary octanol to 85 percent of sulfonated kerosene) according to the ratio of 2: 1, oscillating for 10min at normal temperature, extracting titanium in a three-stage countercurrent manner, and selectively extracting titanium from tantalum raffinate to obtain a titanium loaded organic phase and titanium raffinate;
step two, introducing chlorine gas into the titanium raffinate for 3 hours, and adding Cr in the solution3+Oxidation to Cr6+Then with extractant 2 (7% N-octyl pyridinium chloride ([ OPy ]]Cl) ionic liquid-93% n-amyl alcohol) are mixed according to the ratio of 1: 1, and are vibrated for 10min at normal temperature, chromium is selectively extracted from titanium raffinate, and a chromium-loaded organic phase and chromium raffinate are obtained;
thirdly, carrying out normal-temperature oscillation on the loaded organic phase of the titanium obtained in the first step and a stripping agent 1(3mol/L sulfuric acid solution + 10% hydrogen peroxide) for 10min, wherein the stripping stage number is five, and the ratio is 3: 1, carrying out stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the first step for recycling;
and step four, carrying out five-stage back extraction on the chromium-loaded organic phase obtained in the step two and a back extractant 2(4mol/L ammonium chloride solution) in a ratio of 1: 1 to obtain chromium-rich slag, and returning the organic phase to the step two for recycling after regeneration.
As a result:
the extraction rate of titanium is more than or equal to 99 percent, the back extraction rate is more than or equal to 99 percent, and the concentration of titanium in the titanium-rich liquid reaches 120 g/L;
the extraction rate of chromium is more than or equal to 98 percent, the back extraction rate is more than or equal to 97 percent, and the chromium concentration in the chromium-rich liquid reaches 90 g/L.
Example 4
Step one, tantalum concentration in tantalum raffinate is 0.4g/L, titanium content is 5g/L, chromium content is 10g/L, H2SO4 content is 150g/L, HF content is 50g/L, tantalum raffinate and extracting agent 1 (5% N)19235 percent of secondary octanol-90 percent of sulfonated kerosene) according to the ratio of 1: 1, shaking for 10min at normal temperature, extracting titanium by three-stage countercurrent, and selectively extracting titanium from tantalum raffinate to obtain a titanium loaded organic phase and titanium raffinate;
step two, introducing chlorine gas into the titanium raffinate for 3 hours, and adding Cr in the solution3+Oxidation to Cr6+Then with extractant 2 (8% N-octyl pyridinium chloride ([ OPy ]]Cl) ionic liquid-92% n-amyl alcohol) are mixed according to the ratio of 3: 1, and are vibrated for 30min at normal temperature, chromium is selectively extracted from titanium raffinate, and a chromium-loaded organic phase and chromium raffinate are obtained;
thirdly, carrying out normal-temperature oscillation on the loaded organic phase of the titanium obtained in the first step and a stripping agent 1(2mol/L sulfuric acid solution + 10% hydrogen peroxide) for 10min, wherein the stripping stage number is five, and the ratio is 2: 1, carrying out stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the first step for recycling;
and step four, carrying out five-stage back extraction on the chromium-loaded organic phase obtained in the step two and a back extractant 2(5mol/L ammonium chloride solution) in a ratio of 2: 1 to obtain chromium-rich slag, and returning the organic phase to the step two for recycling after regeneration.
As a result:
the extraction rate of titanium is more than or equal to 99 percent, the back extraction rate is more than or equal to 97 percent, and the concentration of titanium in the titanium-rich liquid reaches 100 g/L;
the extraction rate of chromium is more than or equal to 96 percent, the back extraction rate is more than or equal to 98 percent, and the chromium concentration in the chromium-rich liquid reaches 100 g/L.
Example 5
Step one, the concentration of tantalum is 1g/L, titanium is 7g/L, and chromium is 8g/L, H2SO4200g/L of tantalum raffinate and 40g/L of HF, and extracting with 1 (10% N)192310 percent of secondary octanol to 80 percent of sulfonated kerosene) according to the ratio of 1: 1, oscillating for 10min at normal temperature, extracting titanium in a three-stage countercurrent manner, and selectively extracting titanium from tantalum raffinate to obtain a titanium loaded organic phase and titanium raffinate;
step two, introducing chlorine gas into the titanium raffinate for 1h, and adding Cr in the solution3+Oxidation to Cr6+Then with extractant 2 (10% N-octyl pyridinium chloride ([ OPy ]]Cl) ionic liquid) are mixed according to the ratio of 1: 1, and are subjected to normal-temperature oscillation for 10min, so that chromium is selectively extracted from the titanium raffinate, and a chromium-loaded organic phase and a chromium raffinate are obtained;
thirdly, carrying out normal-temperature oscillation on the loaded organic phase of the titanium obtained in the first step and a stripping agent 1(4mol/L sulfuric acid solution + 20% hydrogen peroxide) for 10min, wherein the stripping stage number is five, and the ratio is 2: 1, carrying out stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the first step for recycling;
and step four, carrying out five-stage back extraction on the chromium-loaded organic phase obtained in the step two and a back extractant 2(5mol/L ammonium chloride solution) in a ratio of 1: 1 to obtain chromium-rich slag, and returning the organic phase to the step two for recycling after regeneration.
As a result:
the extraction rate of titanium is more than or equal to 99 percent, the back extraction rate is more than or equal to 99 percent, and the concentration of titanium in the titanium-rich liquid reaches 120 g/L;
the extraction rate of chromium is more than or equal to 99 percent, the back extraction rate is more than or equal to 99 percent, and the chromium concentration in the chromium-rich liquid reaches 100 g/L.
The above-disclosed features are not intended to limit the scope of practice of the present disclosure, and therefore, all equivalent variations that are described in the claims of the present disclosure are intended to be included within the scope of the claims of the present disclosure.

Claims (10)

1. A method for recovering valuable metals from tantalum raffinate comprises the following steps:
mixing tantalum raffinate with an extracting agent 1 according to a certain ratio, and selectively extracting titanium from the tantalum raffinate to obtain a titanium-loaded organic phase and titanium raffinate;
step two, introducing chlorine into the titanium raffinate for 1-3 hours, mixing the titanium raffinate with an extracting agent 2 according to a certain ratio, and selectively extracting chromium from the titanium raffinate to obtain a chromium-loaded organic phase and a chromium raffinate;
step three, mixing the loaded organic phase of the titanium obtained in the step one with a stripping agent 1 according to a certain ratio, performing stripping to obtain a titanium-rich liquid, and returning the regenerated organic phase to the step one for recycling;
step four, mixing the chromium-loaded organic phase obtained in the step two with a stripping agent 2 according to a certain ratio, performing stripping to obtain chromium-rich slag, and returning the regenerated organic phase to the step two for recycling;
and fifthly, carrying out defluorination treatment on the chromium raffinate.
2. The method of recovering valuable metals from tantalum raffinate according to claim 1,
the tantalum concentration in the tantalum raffinate is 0.1-1 g/L, the titanium concentration is 1-10 g/L, the chromium concentration is 1-10 g/L, and H2SO4The content is 150-200 g/L, and the HF content is 10-50 g/L.
3. The method of recovering valuable metals from tantalum raffinate according to claim 1,
the extractant 1 comprises an extraction titanium extractant, a modifier and a diluent;
the extraction titanium extractant is at least one of primary amine extractant or secondary amine extractant;
the modifier is sec-octanol or isoamylol;
the diluent is sulfonated kerosene.
4. The method of recovering valuable metals from tantalum raffinate according to claim 1,
the composition of the extracting agent 1 is as follows by volume fraction: 10 to 20 percent of primary amine or secondary amine extractant, 3 to 5 percent of sec-octanol or isoamylol and 75 to 87 percent of sulfonated kerosene;
the primary amine or secondary amine extractant is N1923At least one of Alamine 21F81, Primene JMT or N-dodecylamine.
5. The method of recovering valuable metals from tantalum raffinate according to claim 1,
in the first step, the ratio is 1-3: 1, the normal temperature oscillation time is 10-30 min, and the extraction stage number is five.
6. The method for recovering valuable metals from tantalum raffinate according to claim 1,
the extractant 2 comprises a pyridine ionic liquid extractant and an n-amyl alcohol diluent;
the extraction agent of the pyridine ionic liquid comprises N-octyl pyridinium chloride ([ OPy ] Cl) ionic liquid.
7. The method of recovering valuable metals from tantalum raffinate according to claim 1,
the extracting agent 2 is composed of 5-10% volume fraction N-octyl pyridine chloride salt ([ OPy ] Cl) ionic liquid, and 90-95% proportion of N-amyl alcohol.
8. The method of recovering valuable metals from tantalum raffinate according to claim 1,
in the second step, the ratio is 1-3: 1, the normal temperature oscillation time is 10-30 min, and the extraction stage number is five.
9. The method of claim 1, wherein the tantalum raffinate is recycled with valuable metals,
in the third step, the stripping agent 1 is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 2-5 mol/L;
the molecular mass ratio of the hydrogen peroxide dosage to the titanium content in the loaded organic phase is 2-4, the ratio is 1-5: 1, the normal-temperature oscillation time is 10-30 min, and the back extraction stage number is five.
10. The method of recovering valuable metals from tantalum raffinate according to claim 1,
in the fourth step, the stripping agent 2 is an ammonium chloride solution, the concentration is 2-5 mol/L, and the stripping ratio is 1-5: 1; the oscillation time at normal temperature is 10-30 min, and the back extraction stage number is five.
CN202210191023.XA 2022-02-28 2022-02-28 Method for recovering valuable metal from tantalum raffinate Pending CN114540642A (en)

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CN106048257A (en) * 2016-07-08 2016-10-26 贵州鑫亚矿业有限公司 Method for extracting and recycling scandium and titanium from acid leaching solution containing scandium and titanium
CN107475540A (en) * 2017-08-30 2017-12-15 河南理工大学 A kind of technique of titanium white devil liquor recovery vanadium and titanium
CN108823408A (en) * 2018-07-17 2018-11-16 东北大学 A method of utilizing vanadium chromium in pyridine ionic liquid extraction and separation vanadium chromium slag
CN110510671A (en) * 2019-09-18 2019-11-29 广东先导稀材股份有限公司 A method of recycling prepares high-purity tantalum pentoxide from waste and old tantalum target
CN113005298A (en) * 2021-03-11 2021-06-22 广东先导稀材股份有限公司 Method for recovering and separating tantalum, chromium and titanium from tantalum-chromium-titanium target material waste

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* Cited by examiner, † Cited by third party
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CN103952568A (en) * 2014-05-13 2014-07-30 李翔 method for treating titanium-containing blast furnace slag
CN106048257A (en) * 2016-07-08 2016-10-26 贵州鑫亚矿业有限公司 Method for extracting and recycling scandium and titanium from acid leaching solution containing scandium and titanium
CN107475540A (en) * 2017-08-30 2017-12-15 河南理工大学 A kind of technique of titanium white devil liquor recovery vanadium and titanium
CN108823408A (en) * 2018-07-17 2018-11-16 东北大学 A method of utilizing vanadium chromium in pyridine ionic liquid extraction and separation vanadium chromium slag
CN110510671A (en) * 2019-09-18 2019-11-29 广东先导稀材股份有限公司 A method of recycling prepares high-purity tantalum pentoxide from waste and old tantalum target
CN113005298A (en) * 2021-03-11 2021-06-22 广东先导稀材股份有限公司 Method for recovering and separating tantalum, chromium and titanium from tantalum-chromium-titanium target material waste

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