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INVENTION
Patent of the Russian Federation RU2260063
EXTRUDENT FOR EXTRACTION OF METALS AND METHOD OF ITS PRODUCTION
The name of the inventor: Semeniy Valery Yakovlevich (UA); Koryakov Vladimir Borisovich (UA); Pinchuk Alexander Mihajlovich (UA)
The name of the patent owner: Semen Valery Yakovlevich (UA)
Address for correspondence: 02218, Kyiv, ul. Raduzhnaya, 69, ap. 43, V.Ya. Seeds
Date of commencement of the patent: 2003.10.15
The inventions relate to the field of chemistry of organophosphorus compounds, namely extractants for metal recovery, and can be used in the chemical industry for the production of extractants, in the hydrometallurgy of non-ferrous, rare, rare-earth metals, uranium and nuclear fuel processing.
The technical result is the creation of an extractant by selecting components that have in their totality a synergistic effect allowing to achieve a high separation factor and a high capacity for the recovered metal. For this purpose, the extractant for metal recovery contains di- (2-ethylhexyl) phosphoric acid and further contains tris- (2-ethylhexyl) phosphate at a ratio of said components (0.5-1.25): 1. The method of extracting the extractant involves adding to the 2-ethylhexanol of the phosphorus oxychloride at a ratio of (4.5-5.1): 2.0, and at the parameters determined by the achievement of completeness of the reaction, after which the reaction mixture is maintained until the hydrogen chloride formed is completely removed, then 1 mole of water is added to the resulting mixture, the mixture is maintained until the hydrolysis is complete. The mixture is then washed and the aqueous layer separated from an organic residue containing di-2- (ethylhexyl) phosphoric acid and tris (2-ethylhexyl) phosphate.
DESCRIPTION OF THE INVENTION
The invention relates to the field of chemistry of organophosphorus compounds and hydrometallurgy. It concerns the method of obtaining an extractant - a synergistic mixture:
In the molar ratio (0.5-1.25): 1.0 and the method of its use in the hydrometallurgy of non-ferrous, rare, rare-earth, uranium metals and reprocessing spent nuclear fuel.
Organophosphorus extractants are known: tributyl phosphate (TBP), (C 4 H 9 O) 3 PO and di- (2-ethylhexyl) phosphoric acid (D2EHPK) (D-2), which are widely used in hydrometallurgy [1-3].
The closest analogue of the invention in terms of the set of essential features, the purpose of the extractant and the method of its preparation is [7] SU 480716 (IPC C 01 F 9/08, published on 03.11.1975), in which an extraction extractant for metals containing di- (2 Ethylhexyl) phosphoric acid and a process for preparing an extractant for the recovery of metals containing di- (2-ethylhexyl) phosphoric acid, with the addition of phosphorus oxychloride to the alcohol. However, the extractant obtained by this method does not contain a trialkyl phosphate, which affects the relatively low capacity of the recovered metal. In addition, the method is low-tech.
The disadvantage is also the necessity of preliminary obtaining separate components of TBP and D-2 in separate chemical processes, but also a low distribution coefficient and low capacity for the extracted element.
The disadvantages of the prototype are eliminated by the proposed invention.
The technical result of the invention is the development of a one-stage process for the production of a synergistic extractant and an increase in the separation and capacity of the recoverable metal by 20-25%. The technical result is achieved by the fact that the extraction extractant for metals containing di- (2-ethylhexyl) phosphoric acid additionally contains tris- (2-ethylhexyl) phosphate at a component ratio (0.5-1.25): 1 in moles, and in that It is used for the extraction of non-ferrous, rare and rare-earth metals and uranium. And a method for obtaining an extractant for the recovery of metals containing di- (2-ethylhexyl) phosphoric acid, comprising adding phosphorus oxychloride to the alcohol, and characterized in that phosphorus oxychloride is added to 2-ethylhexanol at a ratio of (4.5-5.1): 2.0, The parameters determined by the achievement of completeness of the reaction, after which the reaction mixture is kept until the hydrogen chloride formed is completely removed, then 1 mole of water is added to the resulting mixture, the mixture is maintained until the hydrolysis is complete, then the mixture is washed and the aqueous layer is separated from the organic residue containing di- (2 -ethylglycyl) phosphoric acid and tris (2-ethylhexyl) phosphate, while phosphorus oxychloride is added to 2-ethylhexanol at a pressure of 50-70 mm Hg, temperature (10 ± 5) ° C for 1-1.5 hours; The obtained reaction mixture is maintained at a pressure of 50-70 mm Hg, temperature (10 ± 5) ° C for 2-3 hours; The reaction mixture after aging at a temperature of (10 ± 5) ° C is held at a temperature of 45-55 ° C for 2-3 hours; Washing of the reaction mixture is carried out with a salt reagent.
After washing the reaction mixture with 10-20% solution of common salt and separating the aqueous layer in the organic residue, a synergistic extractant (T-2: D-2) is obtained in a molar ratio (0.5-1.25): 1.0. The yield (90-95)%. The finished product containing 1-5% of mono- (2-ethylhexyl) phosphoric acid is used in the extraction process.
The extraction of the extractant is carried out by reacting 2-ethylhexanol with phosphorus oxychloride by the equation:
A characteristic feature of synthesis of a synergetic extractant is that, by adjusting the ratio in moles of 2-ethylhexanol and phosphorus oxychloride, it is possible to obtain a synergistic mixture of T-2: D-2 of different composition in moles (1: 1), (1: 2), (1 : 3). This is important in the sense that, for example, for the extraction separation of Co and Ni, a mixture of 10-30% solution of D-2 and 5% of T-2 solution in kerosene is used (p.166 [6]). When extracting vanadium, a mixture of 6% D-2 solution and 3% T-2 solution in kerosene is used, separating it from uranium, iron, molybdenum (page 291 [6]). Extraction separation of uranium, thorium, rare earths, iron, calcium, aluminum is successfully carried out by the extractant 0.1 M D-2 and 0.1 M TBF in kerosene (p.299 [6]). Using a synergistic mixture of T-2: D-2 in a ratio of 0.1 M in kerosene allows achieving similar results.
D-2, TBP (analogs), a synergistic mixture of D-2 + TBP (p. 255 [6]) and a synergistic mixture D-2 + T-2 (subject of the invention) were used in the comparative extraction experiments. Solutions of extractants were prepared on the lighting kerosene "KO-30" (organic phase).
 |
For the extraction of uranium, solutions of the following composition were used: H 2 SO 4 0.1-300 g / l, HNO 3 0-30 g / l, Fe 3+ 0-10 g / l, Extraction was carried out in countercurrent mode in a 6-chamber mixer-settler (the volume of the mixing chamber was 0.5 liters, the settling chamber was 2.5 liters, the total phase productivity in all cases was 10.5 liters per hour). In all cases, the phase ratio B: 0 = 4: 3. The extraction isotherms were removed by the cross current method. The phase delamination rate was determined from the rate of separation of the aqueous phase after the stirrer was stopped. |
0.8-30 g / l (water phase). In the course of the studies, uranium extraction and uranium / iron (III) separation were determined. Uranium extraction isotherms are shown in the figure, the concentration of uranium and iron (III) in the saturated organic phase, and the rates of delamination are shown in Table 1.
| Table 1. Some technological indicators of uranium extraction by analog, prototype and (T-2-D-2 in the ratio 1: 1) | ||||||
| No. | Extractor | U in us. OF, g / l | Fe (III) in us. OF, g / l | Coefficient. U / Fe | The speed of the intersections. Mm / min | The third phase,% |
| 1 | 0.14 M D-2 | 8.6 | 39 | 2.0 · 10 1 | 39 | There. |
| 2 | 0.14 M D-2 + 0.14 M TBF | 15.5 | 0.02 | 7.1 · 10 4 | 32 | There. |
| 3 | 0.14 M D-2 + 0.07 M T-2 | 15.2 | 3.9 | 3.6 · 10 2 | 35 | There. |
| 4 | 0.14 M D-2 + 0.14 M T-2 | 20.3 | 0.02 | 9.4 · 10 4 | 32 | There. |
As follows from the data in the drawing and in Table 1, in double mixtures with D-2, tris- (2-ethylhexyl) phosphate significantly improves the technological characteristics of the synergetic extractant - the capacity of the organic phase for uranium increases by 20-30%, the separation coefficient of U / Fe and Increases by 20%, in addition, delamination improves, the formation of the "third" phase during extraction is not observed in any of these systems.
Method and results of experiments on uranium back-extraction and obtaining of U 2 O 3 .
The uranium from the saturated extractant samples was reextracted with 10% (NH 4 ) 2 CO 3 + 3% NH 4 NO 3 (O: B = 3: 1, T = 35 ° C, 
= 1 hour). After the extrusion, the phases were separated in a separatory funnel, the ammonium uranyl tricarbonate crystals (AUTC) were separated from the mother liquor and washed with a reextraction solution that had been previously saturated with uranyl nitrate to an equilibrium concentration.
The degree of reextraction was calculated from the residual concentration of uranium in the organic phase. For all the extractants studied, the values of the degree of reextraction were in the range 99.2-99.6%.
The samples of the washed AUTK were calcined at T = 700 ° C ( = 1 hour), the obtained uranium oxide-oxide was analyzed for the content of phosphorus and iron, since it is these elements that are the main limiting impurities in U 3 O 8 - iron is in considerable quantities always present in commercial commodity solutions, the source of phosphorus can be the organophosphorous Extractants. The results of analyzes of oxide-oxide samples are presented in Table 2.
| Table 2. The content of the main limiting impurities in uranium oxides. | ||
| Component | Technical Requirements | Content in samples |
| Phosphorus,% | <0-08 | <0.01 |
| Iron,% | <0-03 | <0.01 |
Thus, the tested extractants provide U 3 O 8 with the required purity. Tris-2-ethylhexyl phosphate is significantly superior to TBP by its technological properties. The mixed extractant D-2 + T-2 has a capacity for uranium of 20-30% more than D-2 + TBF, and an increased selectivity of extraction. The rate of delamination is not worse than in the system with D-2 + TBF.
In all cases, as a result of the stripping, uranium oxide-uranium oxide of the required degree of purity is obtained from the main limited impurities.
Extraction separation of cobalt and nickel from sulfuric acid solutions was carried out with a synergistic mixture of D-2 + TBP = 10-30%: 5% prototype in kerosene (p.166 [6]). The initial sulfuric acid solutions had a pH of 5-6. The Co / Ni ratio in the aqueous phase is 1: 1. The extraction was carried out at a temperature of 60 ° C. 95.7% recovery of cobalt is obtained at a ratio in the organic phase of Co / Ni = 17.4. The use of a synergistic mixture of T-2: D-2 = 0.5-1.0 in moles (or 4% T-2 solution and 10% D-2 solution) in kerosene made it possible to achieve a Co / Ni = 18.6 separation when cobalt was recovered into the organic phase of 96% .
When extracting vanadium from sludge cast iron foundry and oil ash, uranium-vanadium ores, titanium-ferrous magnesites, sulfuric acid solutions are obtained. As a result of heating them with a powder of iron, vanadium passes into a 4-valence state.
Extraction is carried out in six stages of the settler mixer, using a solution of 6% D-2 and 3% TBP in kerosene (p. 291 [6]) (prototype). The reextraction is carried out in 4 stages with sulfuric acid of 140 g / l at a temperature of 38-50 ° C. The re-extract contains 55-65 g / l of V 2 O 5 . Vanadium is converted to sodium hexavanadate (red cake), which is converted by calcination to 98% vanadium pentoxide.
The use of the synergistic mixture T-2-D-2 in this process gives similar results.
Example 1 . Synthesis of synergetic extractant T-2-D-2 (ratio 1: 1)
In a 4-necked 0.5 liter glass reactor with a stirrer, thermometer, dropping funnel, air bubbler passed through a phosphoric anhydride tube, and a vacuum connection, 150 g of 2-ethylhexanol are charged. The reactor is cooled to a temperature of + 5 ° C and with stirring and blowing dry air through the barbater under a vacuum of 50-70 mm Hg. 36.6 ml of phosphorus oxychloride are added over an hour. At the end of the addition, the reaction mixture is kept under the same conditions for 2 hours, then the temperature of the mass is raised to 45-55 ° C and kept under these conditions for another 2 hours.
After that, 10 ml of water are added to the reactor at a temperature of 45-55 ° C and held for 1 hour. The reaction mixture is cooled to a temperature of 20-25 ° C., 100 ml of a 10% aqueous solution of NaCl is added, the mixture is stirred and, after peeling, separated. The organic residue is washed with 100 ml of water and separated.
In the organic residue, 145 g of a synergistic mixture of tris (2-hexylethyl) phosphate and di- (2-ethylhexyl) phosphoric acid.
The yield is 95.7%.
Analysis: D-2 - 37.5%, mono-2 EGFK - 2.8%, 2-ethylhexanol - 5.2%, tris- (2-ethylhexyl) phosphate - 54.5%.
Ratio: (T-2: D-2) = (0.11: 0.1) g / mol.
Chem. NMR shifts: T-2 
31 Р - 1,200 ppm; D 2 - 31 Р - 0.7 ppm; Mono-2 EGFK 31 P - (-10.79 ppm)
Example 2 . Synthesis of synergetic extractant T-2 ÷ D-2 (ratio 0.5: 1).
The synthesis was carried out at the plant as described in Example 1. The reagent ratio in moles used 2-ethylhexanol: phosphorus oxychloride 4.66: 2. 150 g of 2-ethylhexanol are charged into the reactor, cooled to a temperature of + 5 ° C and with stirring and blowing dry air through the barbater, under a vacuum of 50-70 mm Hg. Art. 45 ml of phosphorus oxychloride are added over 1 hour. At the end of the addition, the reaction mixture is kept under the same conditions for 3 hours, then the temperature is raised to 45-55 ° C. and held for an additional 2 hours under these conditions. After that, 10 ml of water is gradually added to the reactor at a temperature of 45-55 ° C. After 1 hour of cooling to 20-25 ° C., the reaction mixture is washed (2 × 50 ml) with 10% NCl solution, then (2 × 50 ml ) With a 5% solution of ammonium bicarbonate and water. After keeping the organic residue in vacuo at a temperature of 60-80 ° C for 1.5-2 hours, a synergistic mixture of T-2 composition is obtained: D-2 = 0.5: 1 in moles, yield 162 g (91%).
Analysis: D-2 58.1%, T-2 32%, "-ethylhexanol-3.2%, mono-2 EGFK-4.7%, 2-ethylhexyl chloride-1.9%.
ChemSwedge 31 P corresponds to Example 1.
Example 3 . Extraction of uranium with the use of extractants
The extraction was carried out in a 6-chamber extractor as described above. The solutions were prepared on a lighting kerosene of the brand "KO-30" (organic phase).
Uranium was extracted from the industrial solution with the following composition: U-15/8 g / l, Fe 3+ - 1.45 g / l, H 2 SO 4 - 125 g / l, HNO 3 - 12 g / l (water phase).
During the research, uranium extraction and uranium / iron III separation were determined.
A) Extractant 0.14 M D2 EGFK (analog)
Saturated extractant - 8.65 g / l U, 48 mg / l Fe 3+ , raffinate - 9.3 g / l U. Extraction of U in RP - 41.1%, separation factor U / Fe = 19.8.
B) Extractant 0.14 M D2 EGF + 0.14 M TBP (prototype)
The saturated extractant is 15.6 g / l U, 0.04 mg / l Fe 3+ , raffinate -4.11 g / l U. The recovery of U in the OP is 74%, the separation factor U / Fe = 35800
C) Extractant 0.14 M D2EGFK + 0.14 M T2EGF (subject of the invention).
Saturated extractant - 20.6 g / l U, 0.02 mg / l Fe 3+ , raffinate - 0.34 g / l U. The extraction of U in the OP is 97.8%, the separation factor is U / Fe = 94600.
Example 4 . The extraction separation of cobalt and nickel from sulfuric acid solutions was carried out with a synergistic mixture of D-2: TBP = (10-30)%: 4% in kerosene (prototype) compared to the synergetic mixture D-2: T-2 (subject of the invention).
The starting sulfuric acid solutions had a pH of 5-6. The Co / Ni ratio in the aqueous phase is 1: 1. The extraction was carried out at a temperature of 60 ° C. 95.7% was obtained, the recovery of cobalt at a ratio of Co / Ni = 17.4.
The use of a synergistic mixture of D-2: T-2 = (0.5: 1) in moles (or 10% solution of D-2 and 4% T-2 solution) in kerosene made it possible to achieve a Co / Ni = 20.6 separation in RP, with the extraction of cobalt 96% in the PF.
Thus, the proposed invention has a number of advantages. First, the extractant provides a high metal recovery in the PF and a higher metal separation factor, which represents an economic advantage.
In addition, the method for obtaining the extractant is one-step, which simplifies its production technology and gives a significant economic effect.
USED BOOKS
1. Burger LL, Wagner RM Chem. Engng. Data Series, 3, 2, 310 (1958).
2. A.c. USSR 202101, September 14, 1967.
3. "Modern radiochemistry", Vdovenko V.М. Moscow: Atomizdat, 1969, p.106.
4. Coleman CF, Blake CA, Brown KB, Talanta. 9, 3, 297 (1962).
5. "Modern Radiochemistry", Vdovenko V.М. Moscow: Atomizdat, 1969, p.116].
6. GM Ritchi, AV Eshbruk, "Extraction" M .: Metallurgy, 1983, p.166, 257, 291, 299.
7. Bliznyuk NK, Protasova LD, Klopkova RS, SU 480716 (IPC C01 F 9/08, published on 03.11.1975).
CLAIM
1. Extractant for extracting metals containing di- (2-ethylhexyl) phosphoric acid, characterized in that it additionally contains tris- (2-ethylhexyl) phosphate at a component ratio (0.5-1.25): 1.0 in moles.
2. Extractor according to claim 1, characterized in that it is used for the extraction of non-ferrous, rare, rare-earth metals and uranium.
3. A process for the preparation of an extractant for the recovery of metals containing di- (2-ethylhexyl) phosphoric acid, comprising adding phosphorus oxychloride to the alcohol, characterized in that phosphorus oxychloride is added to 2-ethylhexanol at a ratio of (4.5-5.1): 2.0 and The parameters determined by the achievement of completeness of the reaction, after which the reaction mixture is kept until the hydrogen chloride formed is completely removed, then 1 mole of water is added to the resulting mixture, the mixture is maintained until the hydrolysis is complete, then the mixture is washed and the aqueous layer is separated from the organic residue containing di- (2 -ethylglycyl) phosphoric acid and tris (2-ethylhexyl) phosphate.
4. A process according to claim 3, characterized in that 2-ethylhexanol is added with phosphorus oxychloride at a pressure of 50-70 mm Hg, a temperature of (10 ± 5) ° C for 1-1.5 hours.
5. A process according to claim 4, characterized in that the resulting reaction mixture is maintained at a pressure of 50-70 mm Hg. And temperature (10 ± 5) ° С for 2-3 hours.
6. A process according to claim 5, characterized in that the reaction mixture is kept at a temperature (45 ± 55) ° C for 2-3 hours after aging at a temperature of (10 ± 5) ° C.
7. A process according to any one of claims 3 to 6, characterized in that the washing mixture is washed with a salt reagent.
print version
Date of publication 15.03.2007гг
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