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  • 专利说明
  • 权利要求
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  • 优先权
    • 专利摘要:
    In a process for the recovery of uranium from a wet-process phosphoric acid, comprising treating in an extraction step the preliminarily oxidized acid first with an organic solvent consisting essentially of a dialkylphosphoric acid and a trialkyphosphine oxide dissolved in an inert and unreactive organic solvent whereby there are obtained a uranium-free phosphoric acid and an organic extract consisting essentially of the solvent containing the major portion of uranium; then, in a reextraction step, separating the uranium from the organic extract as ammonium uranyl tricarbonate by reacting the organic extract with ammonium hydroxide and ammonium carbonate; and recycling the uranium-free solvent to the extraction step; an improvement comprises treating the organic extract in a reextraction apparatus having at least two stages, by (a) introducing the extract at the head of the first stage; (b) countercurrently introducing ammonia or ammonium hydroxide solution at the bottom of the first stage; the pH of the first stage being controlled and maintained at a value of 8.0 to 8.5; (c) introducing an ammonium carbonate aqueous solution at the bottom of the last stage; the amount of ammonium carbonate employed being 50-80 percent by weight of the theoretical molar quantity which is necessary to neutralize the dialkylphosphoric acid contained in the solvent and to convert the uranium to ammonium uranyl tricarbonate; and (d) regenerating the ammoniated solvent obtained after the reextraction step by treating it with an acid before recycling it to the extraction step.
    公开号:SU858572A3
    申请号:SU782632550
    申请日:1978-07-05
    公开日:1981-08-23
    发明作者:Франсуа Алэн；Сиалино Анжело
    申请人:Компани Женераль Де Матьер Нюклеэр /Кожема/С.А. (Фирма)；Апц - Азот Э Продюи Шимик С.А. (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF URANIUM EXTRACT
    one
    The invention relates to the hydrometallurgical cnoco6aNi extraction of metals, namely to the extraction of uranium from solutions by extraction.
    A known method of extracting uranium from phosphoric acid solutions, including extraction with a mixture of dialkylphos "foric acid and oxide of trialkylphosphine, in particular with a mixture of di (2 ethylhexyl) phosphoric acid and oxide of tri-N-octylphosphine, in an inert diluent, reextraction of uranium from an organo, organo. ammonium, ammonium uranyltricarbonate and. recycling the organic phase. The recovery of uranium is 88-95% l.
    f
    The disadvantage of this method is the formation of an emulsion due to incomplete separation of the phases and contamination of ammonium ions with phosphoric acid after reextraction.
    The purpose of the invention is the possibility of utilization of ammonium ions in the form of ammonium phosphates by improving the phase separation and the absence of emulsion formation and the production of defused phosphoric acid not contaminated with ammonium ions.
    This goal is achieved in that according to the method of extracting uranium from phosphate solutions, including extraction with a mixture of dialkylphosphoric acid and trialkylphosphine oxide in an inert diluent, reextraction with ammonia and ammonium carbonate, the ammonium uranyltricarbonate obtained is separated and recycled
    10 of the organic phase, the reextraction is carried out in two or three stages with the flow of ammonia countercurrent in the lower part of the first stage to a pH of 8.0-8.5 and a solution of ammonium carbonate in the lower
    15 part of the last stage in the amount of 50-80% of the stoichiometrically necessary for the conversion of uranium into uranyl tricarbonate ammonium and the neutralization of disalkylphosphoric acid.
    20
    The essence of the method lies in the fact that at least two steps are necessary for the separative introduction of extragent agents. Simultaneous addition of two reagents is not allowed. It does produce a good separation of iron that is in the uranium or solvent.
    Predominantly use three
    30 steps to get a good system adjustment. In the first stage, a portion of the processed organic phase and ammonia are introduced in the form of a gas or an aqueous solution, and the aqueous phase enriched in uranium is separated. At this stage, the ferric hydroxide containing solution is separated by settling, filtered and recycled the aqueous solution obtained after filtration in the first stage in the stripping apparatus, in the third step ammonium carbonate is introduced and the organic phase uranium is used. If a reextraction apparatus containing more than three stages is used, the separation of the hydroxide containing trivalent iron from the aqueous phase containing ammonium uranyltricarbonate is impaired.
    In the first stage, ammonium hydroxide or ammonia gas is introduced to a pH of 8.0-8.5. At pH below 8.0, the reextraction coefficient decreases and the reextraction system is removed from equilibrium, the uranium is concentrated in the aqueous phase of the second stage, which causes the aqueous phase to be depleted at the output of the first stage.
    If, for example, ammonium hydroxide is introduced in such an amount that the pH is 7.5 in the Stripping Apparatus for processing an organic extract containing 0.24 g / l of uranium, then the concentration of uranium in the second phase water phase is approximately 500 times higher. than the concentration of uranium in the aqueous phase of the first stage, which reaches only 0.014 g / l instead of about 3.2 g / l.
    For a pH above 8.5, the amount of ammonium hydroxide introduced into the reaction, without observing an increase in the reextraction coefficient of uranium, is increased. Also, in this case, the formation of emulsions is observed, which makes phase separation difficult, even impossible. Ammonium hydroxide solutions used have a molar concentration of 6.5 M to 7.5 M.
    Ammonium carbonate in the form of an aqueous solution is introduced to the third stage of the stripping apparatus. The amount of ammonium carbonate is such that the total amount of ammonium ions introduced as carbonate is 5080% of the stoichiometric amount needed to neutralize the dialkyl phosphoric acid contained in the solvent and to convert uranium to uranyl ammonium tricarbonate. Applying an amount of ammonium carbonate above 80% of the stoichiometric amount results in very high alkalinity in the stripping apparatus, which causes the previously described disturbances for pH above 8.5. The introduction of ammonium carbonate in amounts below 50% of the stoichiometric amount also leads to disturbances in the system, causing the uranium to be depleted in the liquid phase of the first stage.
    The ammoniacal solvent, leaving the reextraction apparatus, is recovered by acidification. The acid used may be phosphoric or hydrochloric, but predominantly use is a fraction of both ester phosphoric acid leaving the extraction step. In this latter case, the reduction is carried out by adding from 1 to 10% by volume of the defused phosphoric acid to the ammonia solvent. After this treatment, on the one hand, an organic phase is obtained which is formed by a solvent that does not contain more ammonium ions and which again contains the initial amount of water and, on the other hand, an aqueous phase containing an ammonium salt.
    A solution of phosphoric acid with a concentration equal to or lower than 35% contains mainly from 0.05 to 0.20 g / l of uranium, from 2.0 to 5.6 g / l of iron and a maximum of 2 g / l of calcium.
    The solution is oxidized in such a way as to convert all uranium to hexavalent (uranyl ion). Simultaneously, iron enters the trivalent state (trivalent iron). This oxidation can be carried out by any known method, such as sparging with air or by the addition of chlorite or water saturated with oxygen. Oxygenated water is preferably used, since its use allows for a quick reaction to minimize reagent. For example, approximately 1.8-1.9 liters of water saturated with oxygen per 160 volumes of 1 m of phosphoric acid are used.
    The oxidized phosphoric acid is sent to the extractor where it contacts the countercurrent with an extractant with a mixture of dialkylphosphoric acid, in particular di- (2-ethylhexyl) -phosphoric acid, with trialkylphosphine oxide, in particular, tri-And-octylphosphine in solution in a solvent, immiscible c and non-reactive, such as benzene, I-heptane, and in particular a mixture of hydrocarbons, such as kerosene. The ratio of the volume of phosphoric acid to the extractant mainly lies between 1 and 10.
    The concentration of di- (2-ethylhexyl) -phosphoric acid is most often 0.1-1 mol / l of solvent and the concentration of tri-n-octylphosphine oxide is 0.025-0.25 mol / l of solvent.
    The extraction is carried out in any apparatus of a known type, such as a mixer-settler at 25-b5C, preferably close to.
    The dehydrated phosphoric acid is removed from the extractor through a conduit.
    The largest part is sent for ordering, and one fraction is sent to the tank. The sieve rich in uranium and contaminated with metal ions, in particular ferric ions, is sent to a washing unit, where mainly phosphoric acid ions trapped in the solvent are removed.
    The solvent, enriched in uranium and washed, is sent to a reextraction unit,
    Installation of Stripping contains mainly three stages. The solvent enriched in uranium is introduced
    to the first stage of the installation of stripping through the pipeline and it circulates right there under the influence of gravity. Also at the first stage is introduced a solution of hydroxide a№.5 They or gaseous ammonia. The consumption of agfuni hydroxide or ammonia is regulated, for example, by means of a valve controlled by a pH meter in such a way as to maintain the pH value of 8.0 and 8.5. At the last stage of the stripping apparatus, a solution of ammonium carbonate or a mixture of gas containing carbon and a1-lmiac, previously dissolved in water in an amount close to 50-80% of the stoichiometric amount that was previously determined, is introduced.
    If the stripping unit is operational, the solvent enriched in uranium or iron, which is first in contact with ammonium hydroxide, is gradually converted into an ammonium hydrochloride. The aqueous phase which is transported countercurrently is enriched with uranium and iron, ammonium carbonate forms uranyl with ammonium tricarbonate with uranium, which remains in solution, and iron precipitates B precipitate. In the form of hydroxide. This precipitate is separated by settling the aqueous phase. It is extracted continuously or periodically, filtered and the solution obtained in the stripping unit is returned to the in-cycle. The aqueous phase containing uranyl tricarbonate exits the stripping unit through a conduit.
    The stripped extractant, which is released as a salt of amgloni after stripping, is sent through a pipeline to a connection tank, where the phosphoric acid fraction from the extractor is also introduced. The purified extractant, leaving the acidification tank through the pipeline, is recycled to the extraction unit. The decomposition of the ammonium salt in the extractant using phosphoric acid leads to the formation of ammonium phosphate, which is marketed. The latter can be separated by crystallization, the resulting mother liquors are recycled mainly to the acidification tank.
    The aqueous phase, which contains the urayl ammonium tricarbonate in a quenched form, leaves the reextractor through a pipeline, and the uranium is recovered. In the process, either as an oxide or as sodium uranate in accordance with the treatment, which is applied to the uranyl ammonium tricarbonate. For example, uranium trioxide (VO) is obtained by exposing the ammonium tricarbonate uranyl solution to the reactor under a bubbling process of air at a temperature between EO-UO C for about 6 hours. After filtration, washing with water, drying at 120 ° C and burning at 400 ° C get trioxide
    5 uranium.
    Sodium uranate is obtained by neutralizing sodium hydroxide at a temperature of about 80 ° C from a solution of uranyl ammonium tricarbonate previously degassed bar Coating air to eliminate carbon-containing gas and ammonia. Uranium is precipitated by addition of sodium hydroxide in solution, for 1 hour. After filtration and washing with water, sodium uranate is collected, which can be further converted to ammonium diuarant or to uranium trachoxide.
    Example, a 2.5m solution of phosphoric acid at a temperature of about 60 ° C has a concentration of 345 g / l, its uranium content is about 0.06 g / l, its iron content is about 1.91 g / l, is poured into the tank,
    5 is cooled to, oxidized with the help of 4.5 liters of hydrogen peroxide with 160 volumes in such a way that all the uranium goes into oxidation state TB, iron is oxidized into ferric iron. Finish oxidation
    0 peregleshivanem solution for.
    The resulting solution is transferred at a temperature of about 40 ° C to an extractor at 25.6 l / h. Extractant is administered
    5 to 7.05 l / h. The extractant containing 0.5 M of di- (2-ethylhexyl) phosphoric acid and 0.125 M of tri-L-octylphosphine oxide in kerosene is introduced at 7.05 l / h into the extractor formed by five stages of the settling mixers.
    The aqueous solution exiting the extractor through the pipeline at a rate of about 25.6 l / h and 0.8 l / h is sent to the acidification tank to recover the organic phase at the end of the extraction cycle. The organic phase from the extractor through the pipeline passes to the washing installation with two stages of the settling mixers, where
    0 exclude some impurities, in particular phosphoric acid ions. The flushing was countercurrent at 40 ° C, the flush water flow was 1.3 l / h. Extractant, purified
    5 and enriched with ions of uranyl and ferric iron, goes into a reextractor. It contains 0.27 g / l of uranium and 0.350 g / l of iron,
    The reextractor is composed of three stages of settling mixers, fu} countercurrent. Reextraction was performed at 40 ° C. B. The first stage mixer serves the enriched organic phase at a rate of about 7.05 l / h and inject the ammonium hydroxide solution in countercurrent to a pH of 8.5 at the first stage of the reextractor. For this purpose, an ammonium hydroxide solution (7 M) is used with a flow rate of 0.22 l / h. A solution of ammonium carbonate at a concentration of 140 g / l with a flow rate of about 0.9 l / h is injected into the third stage mixer of the reextractor, which corresponds to 74% of the stochnometrically necessary amount for the conversion of uranium into uranium ammonium carbonate and neutralization. Both extract-1 extractant exits from; reextractor with a consumption of oKon - and l h & : o Concentration by (g / l. Extractant apra | ККK D 1Acid of acidification, with a rate of 7.60 l / h | and oOsrj SffiifcaB aJ & T fraction of the acidic strain of 8o ,,, and ycheide | (extractor, with a flow of y sdd 0, 80 l / h. The regenerated .organic phase is returned to the extraction.
    At all stages of the extractor, and in particular at the first stage, a precipitate of iron hydroxide (2.9 kg of wet sediment per 2.5 m of processed acid) is formed.
    The aqueous phase containing ak-adoni uranyl tricarbonate, approximately 3.55 g / l of uranium, and the precipitated iron is extracted at regular intervals or filtered, then the clean solution returns to the cycle. Ammonium uranyl tricarbonate at 5 95 s is bubbled through air for 6 hours, filtered, washed with water, dried at 120 ° C and calcined at to produce a iron-iron concentrate formed by uranium trioxide, containing 142 g of uranium. This concentrate contains only 0.25% iron in relation to uranium. The total yield for uranium is about 95%.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    5 A method of extracting uranium from phosphoric acid solutions, which includes extraction with a mixture of dialkyl phosphoric acid and trialkylphosphine oxide in an inert diluent, reextraction with ammonia and ammonium carbonate, separating the resulting ammonium and uranyl tricarbonate and recycling of the red w / t, after the rest, and is notime on the al- rum, he is al- tifluorized wth, and is notime on the case, after the recovery of the organic phase, by removing the uranyltricarbonate of ammonium and recycling of the ammonium carbonate, and recirculating the free matter, and is notime on the case for example, after the recovery of the iodine with ammonium and ammonium carbonate; ammonium in the form of ammonium phosphate, the reextraction is carried out in two or three steps with a countercurrent feed in the lower part of the first stage to a pH of 8.0-8.5 and an ammonium carbonate solution in the lower part of the last 50-80% of the stoichiometrically necessary for the conversion of uranium to uranyl tri-carbonate and neutralization of dialkyl phosphoric acid.
    Sources of information taken into account in the examination
    1, Metallurgists of non-ferrous and rare metals. M. VINITI}, m. B, c. 100-104.
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    同族专利:
    公开号 | 公开日
    JPS5442322A|1979-04-04|
    DE2829306C2|1984-09-27|
    CA1106616A|1981-08-11|
    NL175323C|1984-10-16|
    JPS5930649B2|1984-07-28|
    US4238457A|1980-12-09|
    FR2396803A1|1979-02-02|
    BR7804296A|1979-02-28|
    PL111715B1|1980-09-30|
    TR20717A|1982-05-20|
    NL7806490A|1979-01-09|
    GB2014120B|1982-03-10|
    DE2829306A1|1979-01-18|
    YU42928B|1989-02-28|
    YU156278A|1982-08-31|
    AU3755178A|1980-01-03|
    FR2396803B1|1980-01-18|
    PL208156A1|1979-04-23|
    NL175323B|1984-05-16|
    ZA783145B|1979-06-27|
    GB2014120A|1979-08-22|
    AU517756B2|1981-08-27|
    ES471423A1|1979-05-16|
    JO1084B1|1982-07-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2859094A|1957-02-07|1958-11-04|John M Schmitt|Uranium extraction process using synergistic reagents|
    US3711591A|1970-07-08|1973-01-16|Atomic Energy Commission|Reductive stripping process for the recovery of uranium from wet-process phosphoric acid|FR2459205B2|1979-06-15|1983-09-16|Commissariat Energie Atomique|
    US4374806A|1980-06-17|1983-02-22|Wyoming Mineral Corporation|Raffinate wash of second cycle solvent in the recovery of uranium from phosphate rock|
    US4544530A|1980-10-10|1985-10-01|Institute Of Nuclear Energy Research|Separation process for the recovery of uranium from wet-process phosphoric acid|
    US4652431A|1981-02-26|1987-03-24|Prodeco, Inc.|Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution|
    US4652432A|1981-02-26|1987-03-24|Prodeco, Inc.|Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution|
    FR2539549B1|1983-01-17|1988-10-14|Rhone Poulenc Chim Base|PROCESS FOR GLOBAL RECOVERY OF URANIUM, YTTRIUM, THORIUM AND RARE EARTH CONTAINED IN AN ORGANIC PHASE|
    US5419880A|1993-10-08|1995-05-30|Falconbridge, Ltd.|Controlled acid-strong acid strip process|
    FR2990206B1|2012-05-07|2014-06-06|Commissariat Energie Atomique|NOVEL BIFUNCTIONAL COMPOUNDS USEFUL AS LIGANDS OF URANIUM , METHODS OF SYNTHESIS AND USES THEREOF|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7720552A|FR2396803B1|1977-07-05|1977-07-05|
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