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    1467174 Isotopic enrichment of uranium COMMISSARIAT A L'ENERGIE ATOMIQUE 27 Feb 1974 [27 Feb 1973] 8918/74 Heading C1A Uranium isotopic exchange is effected by contacting a compound of UIII with a compound of UIV unreactive therewith, at least one of the compounds being in a liquid phase and the other being in solid or liquid phase under conditions such that no net transfer of U in either valence state or oxidation of UIII occurs whereby UIV compound becomes enriched in the lighter isotope and separating the compounds. In a preferred embodiment an aqueous phase, e.g. UCl 3 in HCl is contacted with an organic phase containing UIV in a multistage extraction, the isotopically enriched UIV is extracted from the organic phase leaving the last stage of the cascade into the depleted aqueous phase leaving the first stage, the U content of the resulting aqueous solution is reduced to UIII and the solution is recycled to the last stage of the exchange cascade and conversely oxidizing depleted UIII in aqueous phase from the first stage to UIV, transferring it to the organic phase which has been depleted of UIV and recycling to the first stage. The reduction of UIV to UIII may be effected by contact with a solid reductant, e.g. Zn or Zn amalgam or by electrolysis. The oxidation of UIII to UIV may be achieved by electrolysis or bubbling an oxidizing gas through the solution. Net transfer of UIV during isotope exchange may be prevented by inclusion of a "salting out agent", e.g. HCl which when added to an aqueous solution of an organic compound causes separation. This agent is removed from the aqueous phase before UIV extraction from the organic phase. Oxidation of UIII during exchange may be prevented by providing an electrically insulating surface throughout the device (except in the oxidizing circuit and reducing circuit electrodes) and by maintaining content of Ni, Co and Cu ions below 1 p.p.m. in aqueous phase. In an alternative, one phase is solid, e.g. UIV on an anionic ion exchange resin or VIII on a cationic resin.
    公开号:SU867283A3
    申请号:SU742004326
    申请日:1974-02-26
    公开日:1981-09-23
    发明作者:Дельваль Пьер
    申请人:За витель；
    IPC主号:
    专利说明:

    organic solvent or on a solid substrate, followed by oxidation of the obtained 1 solution of uranium (III) to uranium (PG) and returning it to the beginning of the process.5
    It is possible to form solutions containing uranium in the state of valence and T, in which this state of valence can be metastable (even in an acidic medium) for a long time sufficient to carry out the isotopic exchange by an industrial route; these solutions are kept out of contact with conductors and 15 are practically separated from ions of other metals, such as alkali and alkaline-earth metals (or from groups III-G1H in accordance with the classification of the periodic table). 20
    For each type of metal ion of the fl; I-yi II groups of the periodic system of elements (not uranium), it is possible to experimentally determine the minimum proportions, called catalytic proportions, over which a rapid transformation of the U ions contained in the solutions under consideration is observed. ions and. These catalytic sites are very small (on the order of part per million with respect to uranium) for ions of metals such as nickel, copper or cobalt.
    The proposed method is 35 in repeating a cycle consisting of the following steps:
    a) an isotope exchange in the counterfocus between the aqueous phase containing the salting out substance and U, and the organic phase containing uranium with the valence of TU under such conditions that the passage of uranium with the valence TU of the organic phase into the aqueous phase
    the phase is very small; five
    b) extraction and (IV) from the organic phase B of the pre-eluted aqueous phase and in the reduction
    c) oxidation of the U of the aqueous phase to U, d. and transfer of oxidized uranium to an organic pre-depleted phae.
    Uranium with the valency of TU can be directly extracted from the organic phase using a predetermined liquid phase.
    In order for the transfer to be nearly complete, this can be done by reducing the content of the salting out agent. Extraction and from one phase can be carried out after oxidation to U using the organic phase chosen so that the transition is almost complete.
    The aqueous phase, which contains in solution, must contain U and allow the extraction of uranium with the valency of TU using the organic phase, and for this it must be possible to take a salting out agent, which is a supplier of halogen ions; in this case, uranium is present in the aqueous phase as a halide, which greatly facilitates the oxidation and reduction operations; the resulting halogen and hydrogen acid during reduction are used for secondary oxidation. C 1 ion can be used as a salting out substance, and as a salt of uranium in the aqueous phase, however, other non-reducing salting out substances can also be used.
    In the irrigated cascade, the organic and aqueous phase costs will be selected depending on the uranium concentrations of both phases so that the uranium consumption in both phases is approximately the same. The exchange conditions and the salting out content of the aqueous phase are chosen so that at least 5% of the uranium with a valency of 1U passes from the organic phase to the aqueous phase. Practically in most cases there will not be a transition of uranium with valency 1II from the aqueous phase to the organic phase due to the fact that there are very few agents for the formation of an intracomplex compound of uranium with the valency of IG.
    The aqueous phase can be contained in the solution only if it has a minimum acidity (which depends on the concentration of ions and) in the absence of such uranium precipitates as a hydroxide. However, it is often possible to re-extract C1 from the organic phase with water, which is acidified, absorbing the acid contained in the organic phase.
    The aqueous phase, when in contact with the organic phase, must contain a salting out substance. Noli assume that this salting out substance consists of C6, then in the U-containing phase, it is necessary to have a large concentration of hydrochloric acid or chloride. In the latter case it would not be possible to use whatever toner was chloride. It is necessary to exclude any kind of cation that is a component of the Redox pair, whose normal potential exceeds the potential of the system if it reacts with a sufficiently high speed (this condition must be observed in the same phase) and having the following characteristics if the second component of the pair is metal, In this case, the metal will be reduced with uranium and, as a rule, will again be acidified. It is necessary to resort to a process with a catalytic property that will lead to rapid oxidation and, if major ion process oche present in small quantities, for example the nickel ions, copper and cobalt, the content of which must be maintained less than parts per million in comparison with cheers prefecture. But not only the phase containing, should be freed from some ions, but any aqueous solution containing 11 should be out of contact with electrically conductive walls. Contact of valences IIf and PG can occur in a variety of ways. Phases containing uranium bivalences can be miscible, partially miscible or immiscible. One of the phases (or the phase in the case of a uniform exchange) will be liquid. The other phase can be liquid or solid; the latter case is the methods using ion exchange resins. The liquid phase or each of the liquid phases, containing uranium in the form of ions or in a complex state (this state is often related to the organic phase), can be aqueous, organic or mixed. Hroshb izg. solvents and (V) that can perform this function are known. The aqueous phase is understood to mean an aqueous solution of an inorganic or organic or uranium salt in a dissociated state. The aqueous phase containing and is usually a solution of water-: native acid, the hydrogen ion of which will play the role of a salting out agent. Thus, only non-acidic acids will be suitable. Hydrochloric solution is usually used; HCC is a less expensive strong acid, although other hydrogen acids and (to a lesser extent) strong non-oxidizing acids can be used. The organic phase is understood to mean a solution in an organic solvent (or a mixture of solvents) of a salt or complex compound of uranium with a valence of 111 or IV, sometimes with the addition of a diluent, if, for example, they want to change the viscosity, density and / or surface tension of the organic phase and act on various parameters, such as decanting. A variety of liquid organic solvents are used, which are used in the treatment of irradiated nuclear fuel. Organic solvents can be selected depending on the selected uranium salt; sometimes it is necessary to add a diluent to it, which can be selected from among aliphatic or aromatic hydrocarbons and their derivatives, for example benzene, toluene, dodecane ,. kerosene, xylene / at ambient temperature. Solvents are organic compounds containing oxidative impurities that are organophosphoric neutral compounds that have a function that provides complex compounds with uranium salts, including several ligands per uranium molecule. The compounds consist of phosphates of the type a (RO) P (.0) or ROROROR (0) 4 radicals R, R and R are aliphatic or aromatic carbon, linear or branched chains; eg; tributyl phosphate (TBP), triisobutyl phosphate (TIBP), tripropyl phosphate (TPP) triethyl-12-butyl phosphate (TEBP), tri-2-methyl-butyl phosphate (T2MBP), tri-2-ethylbutylphosphate (T2EBPhfct) (T2MBP), tri-2-ethylbutylphosphate (T2EBPhfAf 3) 3-tfpf (T2MBP), tri-2-ethylbutylphosphate (T2ETPH-tfpfpf) ), tributoxyethyl. phosphate (TBEP). The compounds also contain phosphines oxides R. Among phosphine oxides, a special class can be distinguished in which one of the chains has the function of the ether of the general formula YO (CHA) P (0) P, P, where K, TR are radicals, TOPOC, triocty phosphine oxide, TPFO, tributylphosphine oxide, TBFO, oxide -M-propylmethoxy. octylphosphine, di-M-butylethyl-2-methoxy-isobutylphosphine oxide, diisobutylmethoxymethyloctylphosphine oxide, triamylphosphine oxide (drawback: can dissolve in water), oxix trihexylphosphine. Phosphonates of the formula di-isobutylhexylphos phonate di-isobutylisoamylphosphonate, di-isobutyloctylphosphonate, di-isobuty ethylhexaphosphonate, di-isobutylmethoxy lorylphosphonate; these phosphonates can be diluted, for example with dodecane or xylol i. Phosphinates of the formula RORR P (O), which are also intermediate intermediates between phosphates to phosphine oxides | R, R and R have all the same values; from the number of phosphinates, g can be called: di-isobutylphosphinate (diluted in toluene), dihexylhexylphosphate (diluted with kerosene R), dibutylisobutylphosphinate (diluted with toluple), di-isobutylbutylphosphinate (diluted with toluene, jer, div, de, tseol), and jer. kerosene R), di-octyl isobutyl phosphinate (diluted with kerosene R). At present, phosphates and phosphonates are used as solvents giving the best results they contain (extraction speed, ease of separation, etc.) according to the proposal Isotopic exchange can occur between two different uranium compounds (in) or uranium compounds (1TG) and uranium (TU). The isotope exchange can also take place in a liquid water phase system, i.e., if uranium compounds are contacted in a homogeneous phase, or in a two-phase system, i.e. when the uranium compounds are in two different phases of the liquid and solid, or two liquid immiscible phases. If the isotopic exchange is carried out by a water-phase system, then after enrichment it is necessary to separate or deplete the compound, or ennoe compound, creating a two-phase system, which complicates the process and makes it less economically advantageous. When exchanging, an aqueous solution with 0.1-2.5 M / l of U IlHUCl in hydrochloric solution is limited to 2 M / l (a concentration of 1.5 M / l gives good results) and the organic phase with 0.1-1 M / l UTY. Apply UCC (Practically, it is possible to reach 0.5 N / l at ambient temperature using the above-mentioned agents for the formation of intracomplex compounds. Contents close to I M / l require the process to be carried out at temperatures exceeding the ambient temperature, reducing the diluent ratio. Installation isotope exchange for enrichment of uranium into one of its isotopes from an exchange battery with several stages, each of which contains a contactor between two, m phases containing both (GT1) and (PG), and devices for the circus The removal of one phase in the opposite direction to the other phase in the barrel of an oxidizing reflux circuit, consisting of „full extractor1B1H and (PT) devices, from the phase that it contains at the end of the battery, where this phase goes, oxidation and ) and (TU) and transfer of oxidized uranium to another phase to enter it into the same end of the battery of the regenerating reflux loop, consisting of full extraction devices and (PG) from the phase that it contains at the other end of the battery, full recovery and (1U) in and (T1G) and transfer of recovered uranium to one th phase for inputting it to another end of the battery} contact surface and (1TG) zlektroizolirovany. Means for reducing uranium (IV) to uranium (THT) are provided to trap extraneous ions. Thus, the necessary purity is maintained, provided that the content of irns is in parts per million, and the reflux is almost complete, i.e. the cascade is almost square. Uranium can be supplied to a cascade with a valence of P1 or TU, but in most cases the initial loading of the cascade requires a special arrangement of the compounds U (TTf) and (TU).
    Uranium (TP) is obtained from uranium (PG) or from its compounds by reducing uranium (TU) electrolytically by chemical means (using zinc or its amalgam) j can be used to etch the uranium metal with acid under certain yuv x, or dissolve it dsily other salts of uranium with valency IG) obtained by the dry method.
    Figures 1 and 2 depict a general scheme of an isotopic protective cascade in which the proposed method is applied.
    The cascade is intended for the isotopic enrichment of natural uranium to isotope 235 (in accordance with the invention, by the method of exchange between the aqueous phase containing uranium (TTT) and the organic phase containing uranium (IV).
    The exchange battery of the 11th cascade consists of p identical steps, which are denoted by ... n, p. At step p, the aqueous phase containing and coming from step n + 1 is mixed with the organic phase containing and and coming from step n-lj after separating the aqueous and organic phases, respectively, in 3 and 4, the phase containing and (IV) ) is enriched in the light isotope 235U. If fb is a step enrichment factor, and Rts is the ratio of the prevalence of 235 U (238U), presumably equal at outputs 1 and 2, then the organic phase at the output has a prevalence of R.piB 235 U,
    FIG. Figure 1 also shows schematically rich reflux 7, in which U (PG), enriched at 235 U, is restored to the U (lir) state and reintroduced into the aqueous phase; depleted reflux 8 performs various functions: oxidation, passage of the aqueous phase-organic phase, and reintroduction into step 1.
    Figure 2 shows a cascade that consists of an exchange battery, where instead of an exchange between U (ril) and (IV), an exchange between the liquid inorganic phase of uranium (1T1) and the organic phase of uranium (THG) is used. The use of these organic solvents, which cannot form a complex and (CG), is excluded. The exchange battery may have a structure similar to that described in Fig. 1, but phlegmy have a different character.
    The phases are followings.
    Organic phase. Uranium as a complex compound s is a dissolved organic solvent that can be converted into uranium (III) in the form of a complex compound, for example, a phosphonate. At ambient temperature, an inert aliphatic or aromatic thinner, such as dodecane, kerosene, or xylene, is added to the solvent. The organic phase O can be used consisting of phosphonate a (50%), for example, dibutylbutylphosphonate DMBP, xylene (50%) and (1P) 0.005 M.
    Inorganic phase. Uranium has a concentration of 60ii in the aqueous phase.
    In this phase, a strong salting out agent intended to keep the complex compound charged in the organic phase must be added without fail. If the uranium is in the form of an IC & 5, the precipitating agent may be a high concentration of Cu in the form of HCE and / or alkaline or alkaline earth chloride. As the aqueous phase A, 0.2 M can be used in the form of UCC,, NSB 5-8N, preferably 7 N.
    The aqueous phase enters the batteries 11 through line 12. The cylindrical 13 acidity of the aqueous phase is increased from 0.5 to 7 N due to hydrochloric acid coming from
    separator 1.4 along the line, 15.
    After the isotopic exchange, the 13 one phase comes from the exchange battery 11 to the extractor 17 via line 16. In the extractor, the aqueous phase A comes into contact with DBBP 50% depleted in xylene. Uranium (III) is completely transferred from the aqueous phase to the organic phase. The aqueous phase is low in uranium and then goes to separator 14. In separator 14, hydrochloric acid is separated and fed to line 15, where the aqueous phase is formed, containing an HC8 of 0.5N. Hydrochloric acid is withdrawn into cylinder 13 through line 15, and the 0.5 M aqueous phase depleted in uranium is discharged through line 18 to secondary extractor 19, where it comes into contact with the organic phase O coming from the exchange battery 11. The entire Uranium (Ill) passes from the organic phase to the 118 aqueous phase in which the salting out substance is practically no longer present. The saturated aqueous phase A then enters via line 21 to installation 20, where the uranium, part of which is oxidized, is entirely reduced to the valency of IP. Finally, the water phase enters via line 22 into cylinder 13 where HC2 is injected, which plays the role of the evaporating agent. The organic phase O, after the isotope exchange and the exchange battery P, is directed along line 23k to extractor 19, where the uranium is extracted by the aqueous phase. The depleted organic phase, leaving extractor 19 through line 24, is directed to extractor 17, where the uranium contained in the aqueous phase goes into the non-existent, into the spent organic phase due to the presence of a salting out agent in the aqueous phase. For example, uranium depleted organic phase enters batteries 1 1 through line 25. Natural uranium is supplied in very small portions via N, removal of depleted uranium to D and selection of enriched uranium to B, Example 1. Uranium (11T) uranium exchange (TU ) in a two-phase system, and (T11): in an aqueous medium, 0.4 M hydrochloric medium 7. and (IV): 0.4 M in the organic benzene phase and TBP. Temperature, exchange time 15 s. Partition coefficient d 1.0030, Example 2, Exchange of liquid-liquid in a mixer sump with backflow. Water phase: and (111) 0, 2 M, carried 7 N, Organic phase: and (TU) 0.2 M, TBP (50%) in a mixture of dodecane - toluene 40% -10%, Contact time from 49 to 132 with. Split ratio, 00121, 0026, depending on contact time and mixing. Example 3, Consecutive exchange in a countercurrent cascade with a common reflux, t, e, 4-curved square cascade in accordance with FIG. 1, Three rotations were made. Isotopic analyzes allowed us to trace the rise to the equilibrium of such a cascade, uniformly filled with natural uranium at the beginning. The phases had the following characteristics: Aqueous phase: UCljO, 4 M, HSE-8N. Organic phase: UC1-0.4 M, TBF50% in benzene. The contact time of each operation is 5 min. D.l, 0026. Examples of complete cascades are shown in the table.
    13
    14
    867283 Continuation of the table
    The ratio of the power consumption to the total consumption in the device
    Temperature of isotope exchange section, С
    Recovery
    Oxidation
    Exit distiller torus-71. The output of the oxidant -69 HC1
    isz
    权利要求:
    Claims (3)
    [1]
    1. US patent number 2787587 cl. 204-1.5.1957.
    [2]
    2. US patent number 2835687, CP. 260-429.1.1958.
    [3]
    3.Patent of Great Britain No. 1120208 В 01 D 59/00, 1968.
    FS./
    & g.1
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    同族专利:
    公开号 | 公开日
    FR2298361A1|1976-08-20|
    IE38936B1|1978-07-05|
    US4012480A|1977-03-15|
    SE405652B|1978-12-18|
    US4237100A|1980-12-02|
    ES423689A1|1977-03-01|
    JPS5940490B2|1984-10-01|
    NL7402633A|1974-08-29|
    AT357654B|1980-07-25|
    NO740677L|1974-08-28|
    FR2298361B1|1977-04-29|
    CA1026932A|1978-02-28|
    JPS59112826A|1984-06-29|
    DK146792C|1984-06-18|
    JPS49125211A|1974-11-30|
    NL172030B|1983-02-01|
    NO142430C|1980-08-20|
    DK146792B|1984-01-09|
    DE2409413C3|1978-10-05|
    AU6608074A|1975-08-28|
    CH593709A5|1977-12-15|
    DE2409413A1|1974-09-26|
    NO142430B|1980-05-12|
    FI56774C|1980-04-10|
    DD114248A5|1975-07-20|
    JPS544038B2|1979-03-01|
    BE811573A|1974-08-26|
    OA04609A|1980-06-30|
    YU49374A|1984-06-30|
    FI56774B|1979-12-31|
    ES446097A1|1977-12-16|
    IE38936L|1974-08-27|
    BR7401383D0|1974-11-05|
    DE2409413B2|1978-02-02|
    LU69497A1|1974-10-09|
    NL172030C|1983-07-01|
    ATA161274A|1979-12-15|
    GB1467174A|1977-03-16|
    引用文献:
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    US2835687A|1952-03-25|1958-05-20|Glenford H Clewett|Isotope fractionation process|
    GB1120208A|1964-07-30|1968-07-17|Japan Atomic Energy Res Inst|A method for enriching uranium isotopes by means of ion exchange|
    DE1905519C3|1969-02-05|1973-02-01|Kernforschung Gmbh Ges Fuer|Method and device for separating uranium and plutonium compounds by liquid-liquid extraction|
    US3869536A|1970-11-12|1975-03-04|Atlantic Richfield Co|Displacement chromatographic method for separating uranium isotopes|
    US3773889A|1971-06-30|1973-11-20|Us Interior|Ion exchange process|
    US3953568A|1971-07-22|1976-04-27|Maomi Seko|Method of simultaneous concentration and dilution of isotopes|
    FR2298361B1|1973-02-27|1977-04-29|Pierre Delvalle|FR2298361B1|1973-02-27|1977-04-29|Pierre Delvalle|
    FR2340766B1|1976-02-13|1981-11-13|Commissariat Energie Atomique|
    CA1091034A|1976-05-28|1980-12-09|Norito Ogawa|Continuous separation of uranium isotopes|
    JPS5949052B2|1977-09-14|1984-11-30|Asahi Chemical Ind|
    IL58726A|1978-11-28|1982-12-31|Commissariat Energie Atomique|Recovery of uranium from phosphoric acid solutions|
    FR2442797B1|1978-11-28|1982-10-15|Commissariat Energie Atomique|
    US4909939A|1984-06-16|1990-03-20|American Cyanamid Company|Process for solvent extraction using phosphine oxide mixtures|
    US4814046A|1988-07-12|1989-03-21|The United States Of America As Represented By The United States Department Of Energy|Process to separate transuranic elements from nuclear waste|
    DE4438174C2|1994-10-26|1996-08-29|Bayer Ag|Use of diethyl dodecane phosphonate for the extraction of acids and metal salts from aqueous solutions|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7306881A|FR2298361B1|1973-02-27|1973-02-27|
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