Method for extraction separation of tantalum and niobium from acid fluoride-sulfate solution

FIELD: metallurgy of rare and dispersed metals, chemical technology.

SUBSTANCE: invention relates to a method for extraction separation of tantalum and niobium. Method involves extraction separation of tantalum from niobium with organic solvent. As an organic solvent method involves using a mixture of methyl isobutyl ketone taken in the amount 40-80 vol.% with aliphatic (C7-C9)-alcohol taken in the amount 20-60 vol.%. At the extraction process tantalum transfers into organic phase and niobium - into aqueous phase. Then organic and aqueous phases are separated. Invention provides enhancing the extraction degree of tantalum into organic phase and to enhance the separation degree of tantalum and niobium in extraction.

EFFECT: improved separating method.

5 tbl, 5 ex

 

The invention relates to the field of metallurgy of rare and trace elements. It can be used for extraction of the extraction and concentration of tantalum from acidic fluoride-sulfate solutions, complex chemical composition. These solutions can be obtained, for example, by leaching tantalite and kolombatovich concentrates solutions containing a mixture of hydrofluoric and sulfuric acids. Now for the extraction of tantalum and niobium from such technological solutions used extraction method that enables the concentration of tantalum and cleaned of impurities, including niobium.

The known method of extraction recovery and separation of tantalum and niobium extraction with tributyl phosphate (TBP) [Korovin S., D.V. Drobot, Fedorov P.I. Rare and trace elements. Chemistry and technology. - M.: MISA, 1999. - 464 C.]. The extraction was carried out from strongly acidic solutions (at least 8M H2SO4in the presence of a large excess of fluoride ions. The coefficients of the separation of tantalum and niobium does not exceed 100.

The disadvantages of this method are the high acidity of the aqueous phase, a relatively low degree of extraction and separation of tantalum and niobium, low speed separation of organic and aqueous phases. This leads to the necessity of using a large number of extras is czynnik apparatus, a significant loss of organic chemicals aqueous solutions and, therefore, increase costs when using solvent extraction process.

The method for extracting tantalum and separation from niobium from acidic fluoride-sulphate solutions by extraction of aliphatic alcohols With7-C9[Glubokov, Y.M., Travkin V.F., Ilyin Mrs x and other / non-ferrous metallurgy, 2001, No. 10, p.23-27]. The process involves three stages: the extraction of metals, washing the organic phase with water at the volume ratio between organic and aqueous phases O:≥20:1, reextraction tantalum water.

The disadvantage of this method is the need for the extraction process at high acidity of the aqueous phase, a relatively low degree of extraction of metals and the value of the coefficient of separation of tantalum and niobium.

The closest analogue in essential characteristics and purpose is a method of extraction separation of tantalum and niobium using as extractant organic phase containing methyl isobutyl ketone (MIBK) [Zelikman A.N., Kites astray freight metallurgy of rare metals. - M.: Metallurgy. 1991. - 432 S.]. The extraction was carried out from the fluoride-sulphate solutions containing more than 300 g/l of sulfuric acid. Comparison of all parameters of the extraction of the prototype and the proposed method are shown in table 5.

p> The disadvantage of this method is the relatively low degree of extraction of tantalum, niobium and other impurities, low speed extraction of metals, the high acidity of the aqueous phase (the content of sulfuric acid of more than 300 g/l). This leads to the necessity of using a large number of extraction units, increase their size and therefore increase the costs when using this process. In addition, the disadvantage of this method is the relatively high solubility MILK in the aqueous phase and the water in it, as well as its high volatility. This leads to a significant loss of expensive organic reagent and requires special measures to reduce these losses and aqueous solutions from the presence of organic substances. All this also causes a significant appreciation of the process.

The technical task of the present invention is to increase the degree of separation of tantalum and niobium, increasing the degree of extraction of tantalum and speed of extraction of the metal in the organic phase, and reducing the acidity of the aqueous phase and loss of reagents for extraction.

The technical result is achieved by the fact that in the proposed method of extraction separation of tantalum and niobium from the acidic fluoride-sulfate solutions, including extraction of tantalum organic phase, sod is Rasa methyl isobutyl ketone, characterized in that the organic phase is injected 20-60 vol.% aliphatic alcohol With7-C9while the mixture charge in the amount of 4-80%. The essence of the proposed method is illustrated by the following examples.

Example 1. Spend extraction separation of tantalum and niobium from the fluoride-sulphate solution containing 28,7 g/l of tantalum and 4.1 g/l niobium. The concentration of free sulfuric acid 286 g/l, and is associated with the metal fluoride-ion - of 22.3 g/l, which corresponds to the stoichiometric ratio of the metal:the fluoride ion is 1:7. The organic phase is a mixture of MIBK and octanol-1 with different ratio with each other. The extraction is carried out at a volume ratio between organic and aqueous phase A:B=1:1 and a temperature of 21°C. table 1 presents data on the influence of the composition of the organic phase on the separation of tantalum and niobium.

Table 1

The influence of the composition of the organic phase to the extraction and separation of tantalum and niobium
The composition of the organic phase,% vol.The distribution coefficient of the metalThe ratio of separation, βTA/Nb
The octanol-1MIBKDTaDNb
10007,40,8 42
9559,60,1659,8
901015,00,17at 88.1
802018,11,1995,0
703039,30,19207
60402410,171420
70304620,153080
40608430,165270
30703570,201870
20801330,17780
109019,10,18106
010015,20,1993,5

From the above results it follows that the high recovery of tantalum and its separation from niobium is achieved in the concentration range MIBK and aliphatic alcohol: 40-80% vol. MIBK and 20-60 vol.% the alcohol.

Example 1. Spend extraction separation of tantalum and niobium from the fluoride-sulphate solution containing 28,7 g/l of tantalum and 4.1 g/l niobium. Coderzoneforum-ion does not exceed the total content of metals in a stoichiometric ratio of no greater than 7:1, the content of sulfuric acid varies within the range of 100-400 g/l as the organic phase used a mixture of 60 vol.% MIBK and 40% vol. octanol-1 and undiluted 100% MIBK (prototype). The extraction is carried out at a volume ratio between organic and aqueous phase A:B=1:1 and the temperature 21,8°C. the contact Time of the phases is 5 minutes table 2 shows data on the influence of acidity of the aqueous phase on the extraction of tantalum and niobium in the organic phase.

Table 2

The influence of acidity of the aqueous phase on the extraction of tantalum and niobium
The concentration of H2SO4, g/lThe distribution coefficient of the metal
100% MIBK (prototype)60% MIBK+40% octanol-1
DTheDNbDTaDNb
1003,40,055,80,07
1508,10,0810,20,08
20010,20,13240,12
25014,30,188100,15
28015,20,19843 0,16
30016,50,188900,17
35090,20,25>12000,61
4002100,86>13000,95

From the table 2 data shows that when used as an extractant mixture MIBK and aliphatic alcohol extraction of metals is much higher than for MILK, when the content of sulfuric acid of more than 250 g/L.

Example 3. The process of extraction separation of tantalum and niobium are in accordance with the conditions of example 1. As the organic phase used a mixture of 60 vol.%) with the addition of 40 vol.% aliphatic alcohols ROH, where R6- hexanol,7- heptanol, C8- octanol-2, C9- nonanol and C10- decanol). Table 3 shows data on the impact of the nature of alcohol on the efficiency of the separation of tantalum and niobium.

Table 3.

The effect of the nature of alcohol on the efficiency of the separation of tantalum and niobium
Concentration

H2SO4, g/l
The separation factor, βTA/Nb
HexanolHeptanolThe octanol-2onanole Decanol
1002981857335
15046941029163
20078180210160102
250710130013501230850
280700132014001270840
300750134015101280860
350740135015201300870
400520920980910750

From the table 3 data shows that the most effective use as an additive alcohols with the length of the radical in the aliphatic chain With7-C9. In addition, the use of hexanol (R-C6) leads to large losses of alcohol due to its high solubility in the aqueous phase. When using decanol (R-C10) there has been a sharp deterioration of the process of separation of organic and aqueous phase.

Example 4. The process of extraction separation is antal and niobium carried out at different contact time of the phases. The organic phase: 60% vol. MIBK and 40% vol. octanol-1. The composition of the aqueous phase described in example 1. The extraction is carried out at a volume ratio between organic and aqueous phase A:B=1:1 and a temperature of 21.1°C. table 4 shows data on the influence of the contact time of the phases for the extraction of tantalum and niobium.

Table 4

The influence of the contact time of the phases for the extraction of tantalum and niobium
The contact time of the phases, minutesThe distribution coefficient of the metal
100% MIBK(prototype)60% MIBK+40% octanol-1
DTaDNbDTaDNb
111,30,127900,12
212,60,138500,16
312,40,118200,16
413,10,178350,17
515,20,198430,16
1015,10,188650,16
2015,30,16 8400,17
3015,80,178500,15
9014,90,188610,18

From the data in table 4 suggests that, while extraction with an organic reagent containing a mixture of 60 vol.% MIBK and 40% vol. octanol-1, to achieve the values of the distribution coefficients of tantalum and niobium, close to equilibrium, it is enough for 2-3 minutes contact phases, while using 100% MIBK need at least 5 minutes

Example 5. Spend extraction separation of tantalum and niobium fluoride from water-sulphate solution extractant containing 60 vol.% MIBK and 40% vol. octanol-1. The composition of the aqueous phase (g/l): tantalum - 31,2; niobium - 6,9; sulfuric acid - 264; the fluoride ion - 39,2. The extraction is conducted at temperatures 21,0°C. the Conditions of the extraction process, washing of the organic phase and Stripping are shown in table 5.

The example shows that the total extraction of tantalum, and the coefficient of separation of tantalum and niobium (βTA/Nb) according to the claimed method is higher than on the prototype method. When using the proposed method reduces the consumption of reagents through the use of on the operations of washing and Stripping of the water, and not water solutions of chemicals (sulfuric acid or Hydra is ammonium) in the case of use as the organic phase undiluted MILK. In addition, the reagent consumption is reduced through the use of extraction solutions containing a smaller amount of sulfuric acid (about 250 g/l)than when using 100% MIBK (not less than 300 g/l of sulfuric acid). Finally the efficiency of the extraction process is enhanced by reducing the cost of extraction equipment due to reduced contact time of the phases.

Thus, using the proposed method improves the extraction of tantalum, to increase the selectivity of the extraction process for the separation of tantalum and niobium, to speed up the process and reduce the cost of reagents and extraction equipment.

Table 5.

Main indicators of the process of separation of tantalum and niobium
IndexThe proposed methodThe placeholder
The composition of the extractant60% vol. MIBK and 40% vol. octanol-1100% MIBK
Extraction
The number of stages of counter-current34
The ratio of the volumes of the phases Of:1,1:11,2:1
The content of tantalum in the raffinate, g/l0,0070,140
Removing the tantalum in the extract, % of 99.9799,5
Flushing
The composition of the leaching solutionWater50 g/l H2SO4
The number of stages of counter-current33
The ratio of the volumes of the phases O:P30:130:1
Reextracted
The composition reextracted solutionWater10% NH3
The number of stages of counter-current44
The ratio of the volumes of the phases O:P5:15:1
The content of tantalum in reextract173146
Removing the tantalum in the reextract, %99,799,0
The separation factor, βTa/Nb7300210
Loss MIBK for extraction (g/kg TA)39
Loss alcohol7-C9when extraction (g/kg TA)2-

Method of extraction separation of tantalum and niobium from the acidic fluoride-sulfate solutions, including extraction of tantalum organic phase containing methyl isobutyl ketone, characterized in that the organic phase is injected 2-60% vol. aliphatic alcohol With 7-C9while the mixture charge in the amount of 40-80%vol.



 

Same patents:

FIELD: metallurgy; methods of preparation of charges for production of niobium-bearing material.

SUBSTANCE: the invention is dealt with production of niobium-bearing materials used for production of special steels. The technical result is an increased degree of transition of niobium into an alloy, decreased share of impurities in the alloy, decreased production costs. For this purpose the charge for production of a niobium-bearing material contains the raw material containing niobium pentaoxide, a nickel-bearing material, aluminum, calcium oxide, calcium fluoride and an exothermic oxidative additive. At that in the capacity of the exothermic oxidative additive it contains potassium chlorate with moisture of 2-12% at the following ratio in shares in respect to the total weight of the charge: niobium pentaoxide - 0.470-0.520, nickel - 0.190-0.270, aluminum - 0.180-0.200, calcium oxide - 0.030-0.040, calcium fluoride - 0.003-0.004, potassium chlorate with moisture of 2-12% - 0.043-0.049. At preparation of the charge after mixing of components it is exposed to compaction in the crucible up to the value of the plastic strength of 0.4-10.0 MPa.

EFFECT: the invention ensures an increased degree of niobium transition into an alloy, decreased share of impurities in the alloy, decreased production costs.

2 cl, 1 tbl, 3ex

FIELD: electrometallurgy, namely processes for producing high-purity niobium ingots used in power generation plants operating with use of low-temperature superconductivity effect.

SUBSTANCE: method comprises steps of electron-beam refining of consumable niobium blank; using blank of niobium of given kind containing niobium uniformly distributed along its length and produced by iodide refining as consumable blank in order to produce niobium ingots with predetermined (in range 200 - 500) relation of specific resistances at temperature values 193K and 9.2K; determining mass relation of niobium of given kind and niobium produced by iodide refining according to relation of specific resistances at temperature values 193 K and 9.2 K with use of expression mn/mu = (500 - ρ2939.2)/(800 + 2 x ρ2939.2) where mn - mass of niobium of given kind, g; mu - mass of niobium produced by iodide refining, g; ρ293 - specific resistance of niobium at temperature 193K, ohm x m2/m ; ρ9.2 - specific resistance of niobium at temperature 9.2K, ohm x m2/m.

EFFECT: enhanced efficiency of process, lowered cost price of high-purity niobium ingots.

2 tbl, 2 ex

FIELD: production of pure niobium.

SUBSTANCE: method includes reducing fusion of niobium pentoxide with aluminum and calcium to provide crude ingots followed by heat treatment and multiple electron beam refining. As an additional raw material in step of reducing fusion sublimates (preferably in non-oxidized form) from second and subsequent electron beam refining are used. Such sublimates are obtained by subsequent cooling of furnace smelting chamber under residual pressure of 10-2-10-4 mmHg for 1.0-3.0 h, letting-to-helium under 1-3 mmHg for 1.0-3.0 h, and letting-to-air for 20-40 min. Sublimates are added in amount of 4.5 % based to feeding niobium pentoxide. Claimed method affords the ability to increase niobium pentoxide consumption by 73 kg in respect to 1000 kg of pure niobium in crude ingots.

EFFECT: production of pure niobium with increased effectiveness without deterioration of refined niobium quality.

2 cl, 1 tbl

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FIELD: metallurgy of rare and dispersed metals, chemical technology.

SUBSTANCE: invention relates to a method for extraction separation of tantalum and niobium. Method involves extraction separation of tantalum from niobium with organic solvent. As an organic solvent method involves using a mixture of methyl isobutyl ketone taken in the amount 40-80 vol.% with aliphatic (C7-C9)-alcohol taken in the amount 20-60 vol.%. At the extraction process tantalum transfers into organic phase and niobium - into aqueous phase. Then organic and aqueous phases are separated. Invention provides enhancing the extraction degree of tantalum into organic phase and to enhance the separation degree of tantalum and niobium in extraction.

EFFECT: improved separating method.

5 tbl, 5 ex

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