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  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    A METHOD FOR EXTRACTING SIXTIVALENT URANIUM by extracting it from an aqueous solution with an organic electrolyte consisting of di- (ethyl-2-hexyl) phosphoric acid and trioctylphosphine oxide in kerosene, followed by injecting an acidic acid. By the fact that, in order to simplify and speed up the process with minimal electric power consumption, the water phase is divided into two streams, which are subjected to electrochemical treatment in the KfeM6paHHOM electrolyzer, respectively of cathodic and anodic kameipax, followed by mixing rastjBopa the cathode cell with the body: Ceska phase and feeding it to extraction.
    公开号:SU1058511A3
    申请号:SU792800306
    申请日:1979-08-15
    公开日:1983-11-30
    发明作者:Неннер Томас；Форэзон Доминик
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    ABOUT
    P1
    X)
    : l
    The invention relates to methods for the recovery of uranium, co; (Yergate in the organic complexing phase, and more specifically, to the concentration and purification of uranium that is extracted wet from phosphoric acid.
    A method is known for extracting uranium from aqueous solutions with a low concentration of uranium by treating minerals by liquid extraction followed by chemical treatment to isolate uranium and extract it as a high-frequency oxide used as a source of nuclear fuel. This method is used to extract uranium from phosphate rocks (with This produces fbsoric acid) or from minerals of other origin with a high content of uranium in the form of oxides. The method consists in treating the mineral with a strong concentrate. acid bath, such as sulfuric, phosphoric, hydrochloric, nitric for po-; radiation of an aqueous solution containing uranyl ions in a very dilute form together with other impurity ions, from where uranium is extracted.
    According to the method of extracting a shesgivalent uranium by extracting it from an aqueous solution with an organic extractant consisting of di- (ethyl-2-hexyl) phosphoric acid and trioctylphosphine oxide in kerosene, followed by the introduction of a mixture of salts of divalent and trivalent iron in a solution of phosphoric acid, into the extract and phase separation.
    The stock solution, in which the uranium is in the oxidized state of U (), is subjected to the first cycle of uranium recovery by means of an organic solvent consisting of a synergistic mixture of extractants, di- (2-ethyl-hexyl) phosphoric acid (NDENR) and trioctyphosphine oxide (TOPO). ), diluted in a kerosene-type hydrocarbon .- .. Uranium is transferred to an organic solvent in the form of a uranyl complex formed between uranium ions (YI) and a synergistic mixture of extractants. The uranium is then extracted from the organic phase into which it was extracted, by contact with an aqueous solution of phosphoric acid containing enough iron (II) ions to convert the uranium (YI) to uranium (lY), which is not extracted with organic solvent. dit in the aqueous phase. This; phase is acidified again to produce uranium with an oxidation state (YI), then subjected to a second extraction cycle of the organic phase containing a synergistic mixture of extractors of NDENRTORO for the final
    obtaining after repeated extraction of uranium with a solution of ammonium carbonate, a sufficiently pure mixed uranium carbonate and ammonium 1.
    However, repeated reductive extraction in the first cycle requires the addition of an iron (II) ion by exposure to phosphoric acid, which is a slow and difficult reaction, or the introduction of an iron (II) salt, which entails the introduction of an additional anion. All this interferes with the subsequent cleaning cycle of uranium.
    In addition, the second. Extraction cycle is carried out on an acidified aqueous solution and treatment with an oxidizing agent is necessary. If oxidation is carried out with air, the operation becomes slow — and requires additional equipment; if this oxidation is carried out through chemical oxidation, it requires the introduction of harmful foreign ions, for example, the introduction of chlorate ions is accompanied by the recovery of chlorine ions, which are active corrosive agents; however, the use of oxygenated water is expensive.
    The purpose of the invention is to simplify and speed up the process with minimal electric power consumption.
    The goal is achieved by the method of extracting hexavalent uranium by extracting it from an aqueous solution with an organic electrolyte consisting of di (ethyl-2-hexyl) phosphoric acid and trioctylphosphine oxide in kerosene, followed by the introduction of a mixture of salts of bivalent and trivalent iron in a solution of phosphorus acids into the extract and separation of the phases, the aqueous phase is divided into two streams, which are subjected to electrochemical treatment in a membrane electrolyzer, respectively, in the cathode and anode chambers, followed by mixing solution from the cathode chamber with the organic phase and feed it to the Extraction
    The organic phase, if necessary, contains an organic diluent (inert with respect to the extractant) to improve the hydrodynamic properties of the organic phase.
    The concentration of the aci extractant in the solvent can vary from 0.05 mol to pure extractant. However, from a practical point of view, an extractant solution of 1-2 mol is usually used. In case of using the extractant together with a synergistic extraction agent, the solution contains 0.1-2 mol for extracts nt and 0.1-2 mol for the synergistic agent, resulting in the initial organic phase contains uranium in an oxidized state (YI), and also other chemicals depending on existing conditions. The concentration of uranium in the organic phase is 20–3000 kg per liter of the phase (preferably 50–500 mg / l).
    The aqueous solution also contains a redox agent for converting uranium (YI) to uranium (IV), and the agent is in a reducing state. The electrochemical potential of the aforementioned redox pair in the aqueous solution under consideration is lower than the potential of the uranium (YI) uranium (IY) pair in this solvent. A typical redox pair is an iron (III iron (II) pair. Consequently, when using this pair, an aqueous solution contains iron in an oxidized state (II). In order to shift the equilibrium of the reaction between the V (YI) and Fe ions (ll ), on the one hand, and V (IY) and Fe (III), on the other hand, in the direction of preferential production of V (lY) ions, it is necessary that the solution contain a significant excess of iron (II) ions with respect to uranium ions.
    The concentration of the iron solution in the oxidized state (II) is 0.5 to 100 g / l. The concentration of strong acid in the solution may vary widely. However, in practice, in order to maximize the use of uranium in an organic solution, the concentration should be chosen taking into account the phase and temperature used. When a strong complexing acid in an aqueous solution is phosphoric acid, its concentration in the solution should be between 18 and 70% (preferably more than 35% by weight). The solution may also contain iron ions in an oxidized state (III). The ratio of the concentration of iron (II) ions to the concentration of iron (III) ions varies over very wide limits. However, in practice, this value is greater than 0.1 (preferably greater than 10).
    The organic phase containing uranium in an oxidizing state (YI and the above-described aqueous solution is brought into contact in a liquid-liquid apparatus. This contact can be made in an x-settler mixer, in packed or pulsed columns or in any other suitable apparatus, contact in flow or countercurrent. Temperature during contact 20 - (preferably about 50 s),: The ratio of the flow rates of the organic phase and the extraction water
    The solution entering the contact zone is not critical, but it must be kept as high as possible so that uranium can be recovered as a concentrated solution.
    When contacting occurs, the equilibrium distribution of uranium (YI) between the organic phase and the aqueous solution is established quickly, while the reduction of uranium (YI) in aqueous solution with a reducing agent is slow. Knowledge of the kinetics of this reduction and the equilibrium isotherms V (YI) and V (YI) between the two phases allows the various parameters of the contact to be adjusted in order to maximize the extraction.
    After separation, the water phase, leaving the contact zone, containing the V (IY) ions and the redox agent, in a partially oxidized state, is divided into two streams, each of which feeds a mambran electrolyzer. The first stream feeds the cathode compartment of the DC cell, due to which the redox agent is electrolytically reduced. Thus, using iron (III) - iron (II) vapor as an oxidation-reducing agent, iron (III) ions are converted to iron ions (II ). Then the first current is again supplied to the zone of contact with the organic phase in order to form a closed circulation system. Before introducing the first stream into the cathode compartment of the electrolytic cell, an aqueous solution containing a strong complexing acid and ions of a redox pair is poured into it in amounts appropriate to be drained into the second stream in order to balance the balance of substances. When using the proposed method for treating an organic phase containing uranium (YI) and forsoric acid obtained by a wet method, the aqueous solution added to the first stream contains phosphoric acid at a concentration equivalent to the concentration of the aqueous solution circulating in a closed system. When used as a redox agent, the pair iron (III) - iron (II-), iron added into this solution may be in the form of iron ions (II) or iron (III) and may occur on iron present in phosphorus xlob libre from a salt of iron (II) or iron (ill) added to this solution, or exposure to iron phosphoric acid.
    The second stream is fed to the anode chamber of the electrolyzer, and the levels in both compartments are equal, thereby collecting the aqueous phase with a high concentration of uranium in the form of uranium (U1), which also contains the oxidation-reduction agent in an oxidized state. The aqueous phase exiting the anode chamber with a high concentration of uranium (VI) in the oxidized state is subjected to a subsequent physical and chemical treatment to extract the uranium.
    A porous substance {ceramic or plastic) made porous by sintering or introducing a pore-forming agent or an ion-exchange membrane (preferably a cation-exchange membrane consisting of a perfluorinated polymer with sulfonic acid groups) is used in the electrolyzer. The anode consists of graphite or a metal with an electroactive coating titanium - an alloy of precious metals. The cathode can be composed of platinum, lead, a pair of titanium - an alloy of precious metals.
    PRI me R. The organic phase containing kerosene as the inert diluent is introduced into the solution containing uranium (VI). This phase contains in a concentration of 0.5 mol di: - (ethyl-2-hexyl) phosphoric acid 0.127 mol trioxophosphine, the uranium content (YI) is 190 ml / l. The flow rate of the phase is 5 l / h. The organic phase at 50 ° C is in contact with an aqueous solution of 35% phosphoric acid, g / l: 0.85; 7.15} uranium (lY) 6.62. .
    After decantation, the outgoing aqueous phase 17 is divided into two streams, one with a flow rate of 4.87 l / h, the second 0, 13 l / h.
    To the first stream is added a stream consisting of an aqueous solution of 35% phosphoric acid containing B g / l of ferric iron with a flow rate of 0.13 l / h.
    The resulting stream feeds the cathode chamber of the membrane electrolyzer, the membrane is made of perfluorosulfone polymer. The electrolyzer consists of two 7x20 cm chambers with flat electrodes, an anode made of graphite, a cathode made of lead. The distance from the cathode to the membrane is 3 mm, and from the anode to the membrane 3 mm.
    The anodic chamber is equipped with jumps, located in a staggered order, allowing to extend the electrolyte path and increase its speed, a constant current of 1 A is passed through the cell, a voltage of 2 V is applied to the terminals.
    The organic phase after extraction contains 18 mg / l of uranium.
    The second stream after the division. Pita em cathode chamber. Electrolytic cells.
    A 35% phosphoric acid solution containing ions, g / l, is collected: Fe-8f, 94; 0.68.
    The consumption of electrical energy in the electrolytic cell required to process 1 kg of uranium, 2 kW / h.
    Thus, according to the proposed method, the savings in equipment cost are 50%, since more than one cell of the electrolyzer is used, and, in addition, all equipment (tank, pumps, sewage, etc.) necessary for the circulation of the solutions is excluded.
    In the proposed method, significant savings in raw materials are achieved, since there is no need to introduce foreign substances.
    The concentration of V according to the proposed method is higher in comparison with the method where two electrolysers are used, thus the productivity is higher.
    In addition, the voltage in the electrolyzer is higher than the voltage in one
    the cell of the electrolyzer, since the aggregate of the anodic reaction corresponds to the oxidation of aqueous g solution, carried out at a high anodic potential, and leads to the formation of oxygen (the cathodic reaction
    in both cases x corresponds to Fe c).
    权利要求:
    Claims (1)
    [1]
    METHOD FOR EXTRACTING HEXVALENT URANIUM by extracting it from an aqueous solution with an organic electrolyte consisting of di- (ethyl-2-hexyl) phosphoric acid and trioctylphosphine oxide in kerosene, followed by introducing a mixture of salts of ferrous and ferric iron in a solution of phosphoric acid into the extract and phase separation *, characterized in that, in order to simplify and accelerate the process with minimal energy consumption, the aqueous phase is divided into two streams, which are subjected to electrochemical treatment in a membrane electrolyzer, respectively of a cathode and 'anode chambers, followed by mixing of the cathode chamber solution with the organic phase and feeding it to extraction. ''
    I
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    同族专利:
    公开号 | 公开日
    AT187T|1981-09-15|
    FI68664B|1985-06-28|
    EG14862A|1985-06-30|
    JPS5541992A|1980-03-25|
    EP0008552B1|1981-09-02|
    JPS6135256B2|1986-08-12|
    BR7905261A|1980-05-06|
    ES483424A1|1980-05-16|
    IL58056A|1983-05-15|
    US4341602A|1982-07-27|
    FI68664C|1985-10-10|
    ZA794288B|1980-09-24|
    FR2433587A1|1980-03-14|
    MA18565A1|1980-04-01|
    EP0008552A1|1980-03-05|
    FI792545A|1980-02-18|
    FR2433587B1|1981-01-09|
    CA1127995A|1982-07-20|
    DE2960742D1|1981-11-26|
    GR69708B|1982-07-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2843450A|1955-01-18|1958-07-15|Jr Harold W Long|Method of recovering uranium mineral values|
    US2790702A|1955-06-21|1957-04-30|Robert F Mccullough|Acid treatment of phosphate rock to recover phosphates and uranium|
    FR1397587A|1964-05-04|1965-04-30|Le Ministre De La Defense|Improvements in uranium extraction processes|
    US3616276A|1969-04-14|1971-10-26|Allied Chem|Process for changing the valence of a metal of variable valence in an organic solution|
    US3737513A|1970-07-02|1973-06-05|Freeport Minerals Co|Recovery of uranium from an organic extractant by back extraction with h3po4 or hf|
    US3711591A|1970-07-08|1973-01-16|Atomic Energy Commission|Reductive stripping process for the recovery of uranium from wet-process phosphoric acid|
    US3770612A|1970-08-24|1973-11-06|Allied Chem|Apparatus for electrolytic oxidation or reduction, concentration, and separation of elements in solution|
    BE771350R|1971-08-16|1971-12-31|Allied Chem|Metal transfer - from organic soln to aqs soln by electrochemical oxidation or reduction|
    BE771349R|1971-08-16|1971-12-31|Allied Chem|Concentrating metals - by preferential soln for different valencies of the metal|
    DE2261018C3|1972-12-13|1981-02-05|Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe|Countercurrent extraction column for liquid-liquid extraction with simultaneous electrolysis|
    DE2449590C3|1974-10-18|1980-06-12|Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe|Process for the purification of actinides in low oxidation states|
    US4234393A|1979-04-18|1980-11-18|Amax Inc.|Membrane process for separating contaminant anions from aqueous solutions of valuable metal anions|FR2450233B1|1979-02-28|1984-10-12|Rhone Poulenc Chim Base|
    US4397820A|1980-07-24|1983-08-09|Wyoming Mineral Corporation|Method to maintain a high Fe+2 /Fe+3 ratio in the stripping system for the recovery of uranium from wet process phosphoric acid|
    US4578249A|1983-09-02|1986-03-25|International Minerals & Chemical Corp.|Process for recovery of uranium from wet process H3 PO4|
    DE3345199C2|1983-12-14|1989-09-21|Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe, De|
    GB8719045D0|1987-08-12|1987-10-07|Atomic Energy Authority Uk|Liquid treatment process|
    US8883096B2|2008-07-31|2014-11-11|Urtek, Llc|Extraction of uranium from wet-process phosphoric acid|
    KR101389877B1|2008-07-31|2014-04-29|우르텍, 엘엘씨|Extraction of uranium from wet-process phosphoric acid|
    FR2965056B1|2010-09-16|2013-05-10|Areva Nc|METHOD FOR MEASURING THE URANIUM CONCENTRATION OF AQUEOUS SOLUTION BY SPECTROPHOTOMETRY|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7823950A|FR2433587B1|1978-08-17|1978-08-17|
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