CA1197382A - Process for separating the actinides and lanthanides present in the trivalent state in an acid aqueous solution - Google Patents
Process for separating the actinides and lanthanides present in the trivalent state in an acid aqueous solutionInfo
- Publication number
- CA1197382A CA1197382A CA000406707A CA406707A CA1197382A CA 1197382 A CA1197382 A CA 1197382A CA 000406707 A CA000406707 A CA 000406707A CA 406707 A CA406707 A CA 406707A CA 1197382 A CA1197382 A CA 1197382A
- Authority
- CA
- Canada
- Prior art keywords
- actinides
- extracting
- acid
- extracting agent
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052768 actinide Inorganic materials 0.000 title claims abstract description 26
- 150000001255 actinides Chemical class 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 20
- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 16
- 150000002602 lanthanoids Chemical class 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000007767 bonding agent Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- FZRJLAPPFMJMCZ-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene;sodium Chemical group [Na].C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 FZRJLAPPFMJMCZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 238000009826 distribution Methods 0.000 description 15
- LXQXZNRPTYVCNG-UHFFFAOYSA-N americium atom Chemical compound [Am] LXQXZNRPTYVCNG-UHFFFAOYSA-N 0.000 description 14
- 229910052695 Americium Inorganic materials 0.000 description 13
- 229910052693 Europium Inorganic materials 0.000 description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- -1 transuranic elements Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052685 Curium Inorganic materials 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- FCQJEPASRCXVCB-UHFFFAOYSA-N flavianic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FCQJEPASRCXVCB-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- NIWWFAAXEMMFMS-UHFFFAOYSA-N curium atom Chemical compound [Cm] NIWWFAAXEMMFMS-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KHFUBCQSFWTWEG-UHFFFAOYSA-L disodium;1,2-di(nonyl)naphthalene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 KHFUBCQSFWTWEG-UHFFFAOYSA-L 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- 238000001730 gamma-ray spectroscopy Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/007—Recovery of isotopes from radioactive waste, e.g. fission products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G56/00—Compounds of transuranic elements
- C01G56/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/34—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing sulfur, e.g. sulfonium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/406—Mixtures at least one compound thereof being a heterocyclic compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
ABSTRACT
A process for the separation of the actinides and lanthanides present in the trivalent state in an acid aqueous solution, wherein the actinides present in such aqueous solution are extracted selectively in an organic solvent by bringing the solution into contact with an organic solvent comprising a first extracting agent formed by an organic bonding agent having an electron-donor nitrogen atom and a second extracting agent formed by an acid organosoluble organic compound able to exchange its H+ ions for metal ions or by metallic salt of such compound.
Application to the nuclear industry, inter alia in the field of the treatment of aqueous effluents containing lanthanides and actinides, such an transuranic elements.
A process for the separation of the actinides and lanthanides present in the trivalent state in an acid aqueous solution, wherein the actinides present in such aqueous solution are extracted selectively in an organic solvent by bringing the solution into contact with an organic solvent comprising a first extracting agent formed by an organic bonding agent having an electron-donor nitrogen atom and a second extracting agent formed by an acid organosoluble organic compound able to exchange its H+ ions for metal ions or by metallic salt of such compound.
Application to the nuclear industry, inter alia in the field of the treatment of aqueous effluents containing lanthanides and actinides, such an transuranic elements.
Description
~ 73~-3 MDT
~73~2 Technical Title:
PROCESS FOR SEP~R~TI~G THE A~ll ~lL~S A~D L~L~NIDES ~ ~N'l' I~ THE TRIVALE~T
STATE IN ~N ACID AQ~EOUS SOL~TION
Inventors: Claude Musikas and Pierre Vitorge of the Co~nmissariat a ~'Energie ~tomique and Michele ~onnin of the Société de Mécanique "Pee-ters"
~he invention relates to a process for the separation oP the actinides and lanthanides present in the trivalent state in an acid aqueous solution, which can be used inter alia for the treatment of radioactive effluents.
In the lluclear industr~, inter alia in the field of the treatment of aqueous e~fluents containing lan-th~n;de~s and actinides, such as transuranic elements, it is very advantageous to separate the actinides from the lanthanides before conditioning such radioactive wastes with a view to their long-term storage, for instance, by vitrification~
The fact is that the lanthanides which are ~ and Y emitting fission products have much shorter periods -than certain actinides, which are ~ emitting elements wi-th a much longer life. It is therefore preferable to condition wastes not containing shor-t-life emi-t-ters which more rapidly become inactive, since this is less of a problem as regards long-term storage.
Moreover, -the recovery of the actinides is very advantageous, ~ince they can be used in various fields, for instance, for making radioactive sources.
It is also very advantageous to separate the actinides from the lan-thanides, on -the one haud to recover -the actinides, and on -the other hand to treat with a view to long-term storage only the short~life fission products, which _r .
represent less danger.
~i~;lAr]y -the process can be applied to the production of transuranic elements by the neutron irradiation of lighter isotope targets, for instance, for -the production o~ americium 4 and c~rium 44 origina-ting from irradiated plutonium.
~owever, the problem of separating the actinides and the lanthanides is difficul-t to solve, since the lanthanide (III) ions and actinide (III) ions ha~e very similar chemical properties, their ionic radiuses are close to one another, and the majority of complexes formed ~rom lanthanides or ac-tinides have a marked ionic character.
~he prior art processes for separating àctinides from lanthanides have numerous disadvantages, since they require the use of concentrated saline media, for instance, 10 M IcCl s~lutions, or rela-tively high pH values, so that they are diEEicult to perform.
It is an object of the invention to provide a process for the separation of the actinides and l~nthanides present in the trivalent state in an aqueous solu-tion which obvia-tes these disadvantages and moreover enables the actinides and lanth~n;~es to be separated quantitatively.
In the process according to the invention for separating the ac-tinides and the lanthanides present in the trivalent state in an acid aqueous solution, the ac-tinides present in such agueous solution are extracted selectively in an organic solvent by bringing the solution into contact with an organic solven-t comprising a first extracting agent formed by an organic bonding agent having an electron-donor atom and a second extracting agent formed by an acid organosoluble organic compound able -to ~chAnge its H~ ions for metal ions or by metallio salt o such compound.
3~3~
~ccording to an advan-tageous fea-ture of -the pr0cess according to the inventlon, the bonding agen-t with an electron-donor ni-trogen atom forming the first extracting agent is a heterocyclic compound, such as 2,~,6-tri (2-pyridyl)-1, 3 9 5 triazine, 1,10 orthophenanthroline and ~,7 diamyl orthophenanthroline.
Preferably, use is made of 2,4,6-tri(2-pyridyl) 193,5 tr;~.~.;ne (TPTZ).
According to the invention, the second extracting agent is an acid organosolubl_ organic compound which is capable of e~ch~ng;n~ its H ions for metal ions and which preferably has as low an acidity constant as possible, for example, a Pka less than 40 ~se can also be made of the metal salts of the acid compounds meeting these charac-teristics, more particularly their ~lk~.l;ne metal salts, such as sodium.
Acid compounds which can be used are, for example, di-nonyl naphthalene sulphonic acid, a-bromo caproic acid, caproic acid, and the ~.lk~l ;n~ salts of such acids.
Preferably the second extracting agent is di-nonyl naphthalene sulphonic acid (HD~S) or sodium di-nonyl naphthalene sulphonate (NaD~S).
Due to -the use o~ an organic solvent containing not only a bonding agent with an electron-donor nitrogen atom, but also an acia compound, the trivalent actinide ions which are more heavily complexed than the trivalen-t lanthanide ions by the bonding agent having an electron-donor nitrogen atom can be extracted selectively in the organio solven-t. This influence of -the acid compound on extraction can be attribu-ted to a more considerable participation of the covalent; links in the stability of the actinide complexes. The fact is that the use of a second acid extracting agen-t able to exchange its H ions for me-tal ions preserves electric neutrality be-tween the a~ueous phase and the organic phase during the formation of the complex by one of the following reac-tion s~hemes:
M3+ ~ 3~ + nL -~ ~A3Ln M3-~ ~ mI~I ~ (3-m) A~ ~ 3~ + MLmA3_m where M3+ denotes the actinide ions, L denotes the ni-trogenous bonding agent, L~ denotes an acid nitrogenous bonding agent, A~ denotes the oxganosoluble acid extracting agent and n and m denote integers.
The ~mA3 m or ~A3In complex formed ls a neutral complex whose sphere of co-ordina-tion is saturated; it will therefore possibly comprise in addition neutral molecu]es, such as molecules of water, or o-ther molecules presen-t in the medium~
~o put into effect the process according to the invention as a rule -the system of ex-tracting agents is diluted in an inert solvent, such as tertiobutyl benzene Advan-tageously the concentrations of the extracting agents in the organic solvent are such that the molar ratio between the first extracting agent (the nrg~nl~ bonding agent wi-th an electron-donor nitrogen atom) and the second extracting agent (the acid compound) is about 2:3 to 4:1.
It should be noted -that -the process ~ccording to -the inven-tion can be put in-to effect in any conventional extracting apparatus, such as batteries of decanting mixes, pulsed columns, centrifugal extractors, etc.
Other fea-t~es and advantages of the invention will be more clearl~ gathered from the ~ollowing description of embodiments given, of course, merely by way of non-limitative illustration, with reference to the accompanying drawings, wherein 3~
- ~'ig.l is a ~r~ph showing the variations in the coefficien-ts of dis-tribution DAm of americium (curve 1) and DEU of europium (curve 2) as a function of the TPTZ and HDNNS concentrations of the organic solven-t, the total concentration 1 being of extracting agen-ts being 0.01 mole 1 , and the aqueous solution/formed by 0.117 N nitric acid, - Fig.2 is a graph showing the variations in -the coefficients of distribu-tion DAm (curves 3 and 5) and DEU (curves 4 and 6) as a function of the pH ~f the aqueous starting solution for two systems of solvents, and - ~ig.3 is a graph showing the variations in the coefficient of distribution of americium DAm (curve 7) and europium DEU (cuxve 8) as a function of the to-tal concentration of solven-t in ex-tracting agents.
In all the examples, tertiobu-tyl benzene was used as -the diluting agent, and the coefficients of distribution of americium and europium were determined by gamma spectrometry. Agitation was performea ~or 2 minutes.
It should be noted that the coefficient of distribution of an element is equal to -the ratio between the concentration of such element in -the organic phase a~d the concentration of the same element in the aqueous phase.
EXAMPIE I
This example relates to the separation of americium (III) and europium (III) by means of an organic solvent comprising as the first extracting agen-t
~73~2 Technical Title:
PROCESS FOR SEP~R~TI~G THE A~ll ~lL~S A~D L~L~NIDES ~ ~N'l' I~ THE TRIVALE~T
STATE IN ~N ACID AQ~EOUS SOL~TION
Inventors: Claude Musikas and Pierre Vitorge of the Co~nmissariat a ~'Energie ~tomique and Michele ~onnin of the Société de Mécanique "Pee-ters"
~he invention relates to a process for the separation oP the actinides and lanthanides present in the trivalent state in an acid aqueous solution, which can be used inter alia for the treatment of radioactive effluents.
In the lluclear industr~, inter alia in the field of the treatment of aqueous e~fluents containing lan-th~n;de~s and actinides, such as transuranic elements, it is very advantageous to separate the actinides from the lanthanides before conditioning such radioactive wastes with a view to their long-term storage, for instance, by vitrification~
The fact is that the lanthanides which are ~ and Y emitting fission products have much shorter periods -than certain actinides, which are ~ emitting elements wi-th a much longer life. It is therefore preferable to condition wastes not containing shor-t-life emi-t-ters which more rapidly become inactive, since this is less of a problem as regards long-term storage.
Moreover, -the recovery of the actinides is very advantageous, ~ince they can be used in various fields, for instance, for making radioactive sources.
It is also very advantageous to separate the actinides from the lan-thanides, on -the one haud to recover -the actinides, and on -the other hand to treat with a view to long-term storage only the short~life fission products, which _r .
represent less danger.
~i~;lAr]y -the process can be applied to the production of transuranic elements by the neutron irradiation of lighter isotope targets, for instance, for -the production o~ americium 4 and c~rium 44 origina-ting from irradiated plutonium.
~owever, the problem of separating the actinides and the lanthanides is difficul-t to solve, since the lanthanide (III) ions and actinide (III) ions ha~e very similar chemical properties, their ionic radiuses are close to one another, and the majority of complexes formed ~rom lanthanides or ac-tinides have a marked ionic character.
~he prior art processes for separating àctinides from lanthanides have numerous disadvantages, since they require the use of concentrated saline media, for instance, 10 M IcCl s~lutions, or rela-tively high pH values, so that they are diEEicult to perform.
It is an object of the invention to provide a process for the separation of the actinides and l~nthanides present in the trivalent state in an aqueous solu-tion which obvia-tes these disadvantages and moreover enables the actinides and lanth~n;~es to be separated quantitatively.
In the process according to the invention for separating the ac-tinides and the lanthanides present in the trivalent state in an acid aqueous solution, the ac-tinides present in such agueous solution are extracted selectively in an organic solvent by bringing the solution into contact with an organic solven-t comprising a first extracting agent formed by an organic bonding agent having an electron-donor atom and a second extracting agent formed by an acid organosoluble organic compound able -to ~chAnge its H~ ions for metal ions or by metallio salt o such compound.
3~3~
~ccording to an advan-tageous fea-ture of -the pr0cess according to the inventlon, the bonding agen-t with an electron-donor ni-trogen atom forming the first extracting agent is a heterocyclic compound, such as 2,~,6-tri (2-pyridyl)-1, 3 9 5 triazine, 1,10 orthophenanthroline and ~,7 diamyl orthophenanthroline.
Preferably, use is made of 2,4,6-tri(2-pyridyl) 193,5 tr;~.~.;ne (TPTZ).
According to the invention, the second extracting agent is an acid organosolubl_ organic compound which is capable of e~ch~ng;n~ its H ions for metal ions and which preferably has as low an acidity constant as possible, for example, a Pka less than 40 ~se can also be made of the metal salts of the acid compounds meeting these charac-teristics, more particularly their ~lk~.l;ne metal salts, such as sodium.
Acid compounds which can be used are, for example, di-nonyl naphthalene sulphonic acid, a-bromo caproic acid, caproic acid, and the ~.lk~l ;n~ salts of such acids.
Preferably the second extracting agent is di-nonyl naphthalene sulphonic acid (HD~S) or sodium di-nonyl naphthalene sulphonate (NaD~S).
Due to -the use o~ an organic solvent containing not only a bonding agent with an electron-donor nitrogen atom, but also an acia compound, the trivalent actinide ions which are more heavily complexed than the trivalen-t lanthanide ions by the bonding agent having an electron-donor nitrogen atom can be extracted selectively in the organio solven-t. This influence of -the acid compound on extraction can be attribu-ted to a more considerable participation of the covalent; links in the stability of the actinide complexes. The fact is that the use of a second acid extracting agen-t able to exchange its H ions for me-tal ions preserves electric neutrality be-tween the a~ueous phase and the organic phase during the formation of the complex by one of the following reac-tion s~hemes:
M3+ ~ 3~ + nL -~ ~A3Ln M3-~ ~ mI~I ~ (3-m) A~ ~ 3~ + MLmA3_m where M3+ denotes the actinide ions, L denotes the ni-trogenous bonding agent, L~ denotes an acid nitrogenous bonding agent, A~ denotes the oxganosoluble acid extracting agent and n and m denote integers.
The ~mA3 m or ~A3In complex formed ls a neutral complex whose sphere of co-ordina-tion is saturated; it will therefore possibly comprise in addition neutral molecu]es, such as molecules of water, or o-ther molecules presen-t in the medium~
~o put into effect the process according to the invention as a rule -the system of ex-tracting agents is diluted in an inert solvent, such as tertiobutyl benzene Advan-tageously the concentrations of the extracting agents in the organic solvent are such that the molar ratio between the first extracting agent (the nrg~nl~ bonding agent wi-th an electron-donor nitrogen atom) and the second extracting agent (the acid compound) is about 2:3 to 4:1.
It should be noted -that -the process ~ccording to -the inven-tion can be put in-to effect in any conventional extracting apparatus, such as batteries of decanting mixes, pulsed columns, centrifugal extractors, etc.
Other fea-t~es and advantages of the invention will be more clearl~ gathered from the ~ollowing description of embodiments given, of course, merely by way of non-limitative illustration, with reference to the accompanying drawings, wherein 3~
- ~'ig.l is a ~r~ph showing the variations in the coefficien-ts of dis-tribution DAm of americium (curve 1) and DEU of europium (curve 2) as a function of the TPTZ and HDNNS concentrations of the organic solven-t, the total concentration 1 being of extracting agen-ts being 0.01 mole 1 , and the aqueous solution/formed by 0.117 N nitric acid, - Fig.2 is a graph showing the variations in -the coefficients of distribu-tion DAm (curves 3 and 5) and DEU (curves 4 and 6) as a function of the pH ~f the aqueous starting solution for two systems of solvents, and - ~ig.3 is a graph showing the variations in the coefficient of distribution of americium DAm (curve 7) and europium DEU (cuxve 8) as a function of the to-tal concentration of solven-t in ex-tracting agents.
In all the examples, tertiobu-tyl benzene was used as -the diluting agent, and the coefficients of distribution of americium and europium were determined by gamma spectrometry. Agitation was performea ~or 2 minutes.
It should be noted that the coefficient of distribution of an element is equal to -the ratio between the concentration of such element in -the organic phase a~d the concentration of the same element in the aqueous phase.
EXAMPIE I
This example relates to the separation of americium (III) and europium (III) by means of an organic solvent comprising as the first extracting agen-t
2,4,6-tri(2 pyridyl) 1,3,5-triazine (~PTZ) and as -the second extracting agent di-nonyl naph-thaLene sulphonic acid (HDNNS), in solution in tertiobuty:L benzene, the total ooncentration of extracting agents of the organic solvent being 0.01 mole 1-1.
~o perform extraction, this or~anic solvent is brought into contact with a 0.117 N aqueous nitric solution containing 240 mg/l of americium and 150 mg/l of
~o perform extraction, this or~anic solvent is brought into contact with a 0.117 N aqueous nitric solution containing 240 mg/l of americium and 150 mg/l of
3~
europium. Af-ter agi~tation, and the decantation of the two phases, the americium ~nd europium content of each phase is measuxed to determine -the coefficients of distribution DAm and DEU.
Fig.l illustrateæ the variations in the coefficient of distribution DAm (curve l) and DE (curve 2) as a function of the content of the solvent in bonding agent with an electron-donor nitrogen atom, expressed in molar percentage of the mi~ture of extra¢ting agents, the tatal content of the solvent in extracting agents being 0.01 mole 1 l.
This figure shows -tha-t the best results are obtained when the molar ratio of the first or second extracting agents is close to 1. It will also be noted that good results are obtained when the molar ratio between the TPTZ and the HD~MS is in the range 2:3 to 4:1.
EXAMR~E 2 In this ex~mple, use is made as the solvent either of system I formed b~
tertiobutyl benzene containing lO 2 mole 1 l of MaD~S - i.e., sodium di-nonyl naphthalene sulphate and lO 2 mole 1 1 of TP~Z - i.e., system II
formed by tertiobutyl benzene containing 4.10 3 mole 1 1 of ~DNNS and 6.10 3 mole 1 1 of ~p~z, extraction being performed in the same conditions as those of example l, bu-t varying the pH of the a~ueous solution of nitric acid.
The coefficients of distribution of americium and europium are determined as before. ~he results ob-tained are shown in ~ig.2, in which curves 3 and 4 illustrate respectively the variations in the coefficient of distribution DAm and D~u as a function of -the pH for solvent sys-tem no.I and curves 5 and 6 illustrate respectively the variations in the coefficient of distribution DAm and DEU as a f~lctlon of the pH for solven-t system no.II.
3~3~
~his figure shows tha-t -the separation is better in the ca~e of solvent sys-te~
no.I, and that good results are obtained in both cases when the pH is abou-t 1.
EX~PLE 3 In this e~ample -the organic solvent used is tertiobutyl benzene containing ~P~Z and NaD~NS, with a molar ratio of the TP~Z or NaDNNS equal to 1, and the content of solvent ex-tracting agent is varied. Fxtraction is performed in the same conditions as those in ~xample 1, with a 0.1 N aqueous nitric phase containing americium ~ld europium. ~he coefficients of distribution of americium and europium are determined.
~he results obtained are shown in ~ig.3, in which curves 7 and a illustrate respectivel~ the variations in the coefficients of distribution DAm and DE
as a function of -total concentration in extracting agents of the organic solvent, expressed in mole 1 1 F~AMPLE 4 In this example use is made of a ba-tter~ of decanter-mixers comprising seven extraction stages and seven washing stages, an aqueous phase being made to circulate in the bat-ter~ which is formed by 0.1 N nitric acid containing europium, americium, cerium, gadolinium, terbium and curium in counter-c~rrent with an organic phase formed by tertiobut~l benzene containing 0.05 mole 1 1 of NaDNNS and 0.05 mole 1 1 of ~p~z, with a volumetric ra-tio of organic phase to aqueous phase of 0.5 in the extraction stages and 1 in the washing stages.
On leaving the bat-tery the solvent contains 99.7% actinides and 0.05% lanthanide~
In these conditions -the coefficients of distribution of europium, americium, OeriuM III, gadoliniuM III, terbium III and curiuM III are respec-tively 0.4; 6.0; o.67; 0.53; 0.3 and 4.6. In this way a satisfacto~ separation 7~
of -the actinides and lan-thanides is obtained. ~le actinides can be re-extracted by bringing the organic solvent in-to contact with a 2N aqueous nitric solu-tion in a batte~y of decan-ter-mixers comprising 5 sta~es with a volumetric ra-tio of organic phase to aqueous phase of about 3. In these condi-tions the coefficient of distribution of americium is 0.015 and the organic solvent leaving the re-extrac-tion battery wi:L1 no longer contain more than about 0.001%
of the actinides.
In this example use is made of a bat-tery of decanter-mixers comprising 7 extraction stages and 9 washing stages. Circulating in counter-current in -the ba-ttery is a 0.05 N aqueous nitric solution containing americium, cur~um, terbium, cerium and gadolinium~ and an organic solvent formed by tertiobu-tyl benzene containing 0.05 mole 1 1 of DNNS and 0.05 mole 1 of ~PTZ, with a volumetric ratio of the organic phase to the aqueous phase of 0.4 in the extraction stages and 0.2 in -the washing stages.
In these conditions we obtain the ~ollowing distribution coefficients:
Am 7; DCm 13; DTb = 1-06; Dce = 1.34 and DCd = o.6.
at We therefore obtain/the outlet from -the battery a solvent containing more than 99.5% actinides and less than 0.2~/o lanthanides. The actinides are re-extracted in a 2N nitric solution, as in Example 4.
.,
europium. Af-ter agi~tation, and the decantation of the two phases, the americium ~nd europium content of each phase is measuxed to determine -the coefficients of distribution DAm and DEU.
Fig.l illustrateæ the variations in the coefficient of distribution DAm (curve l) and DE (curve 2) as a function of the content of the solvent in bonding agent with an electron-donor nitrogen atom, expressed in molar percentage of the mi~ture of extra¢ting agents, the tatal content of the solvent in extracting agents being 0.01 mole 1 l.
This figure shows -tha-t the best results are obtained when the molar ratio of the first or second extracting agents is close to 1. It will also be noted that good results are obtained when the molar ratio between the TPTZ and the HD~MS is in the range 2:3 to 4:1.
EXAMR~E 2 In this ex~mple, use is made as the solvent either of system I formed b~
tertiobutyl benzene containing lO 2 mole 1 l of MaD~S - i.e., sodium di-nonyl naphthalene sulphate and lO 2 mole 1 1 of TP~Z - i.e., system II
formed by tertiobutyl benzene containing 4.10 3 mole 1 1 of ~DNNS and 6.10 3 mole 1 1 of ~p~z, extraction being performed in the same conditions as those of example l, bu-t varying the pH of the a~ueous solution of nitric acid.
The coefficients of distribution of americium and europium are determined as before. ~he results ob-tained are shown in ~ig.2, in which curves 3 and 4 illustrate respectively the variations in the coefficient of distribution DAm and D~u as a function of -the pH for solvent sys-tem no.I and curves 5 and 6 illustrate respectively the variations in the coefficient of distribution DAm and DEU as a f~lctlon of the pH for solven-t system no.II.
3~3~
~his figure shows tha-t -the separation is better in the ca~e of solvent sys-te~
no.I, and that good results are obtained in both cases when the pH is abou-t 1.
EX~PLE 3 In this e~ample -the organic solvent used is tertiobutyl benzene containing ~P~Z and NaD~NS, with a molar ratio of the TP~Z or NaDNNS equal to 1, and the content of solvent ex-tracting agent is varied. Fxtraction is performed in the same conditions as those in ~xample 1, with a 0.1 N aqueous nitric phase containing americium ~ld europium. ~he coefficients of distribution of americium and europium are determined.
~he results obtained are shown in ~ig.3, in which curves 7 and a illustrate respectivel~ the variations in the coefficients of distribution DAm and DE
as a function of -total concentration in extracting agents of the organic solvent, expressed in mole 1 1 F~AMPLE 4 In this example use is made of a ba-tter~ of decanter-mixers comprising seven extraction stages and seven washing stages, an aqueous phase being made to circulate in the bat-ter~ which is formed by 0.1 N nitric acid containing europium, americium, cerium, gadolinium, terbium and curium in counter-c~rrent with an organic phase formed by tertiobut~l benzene containing 0.05 mole 1 1 of NaDNNS and 0.05 mole 1 1 of ~p~z, with a volumetric ra-tio of organic phase to aqueous phase of 0.5 in the extraction stages and 1 in the washing stages.
On leaving the bat-tery the solvent contains 99.7% actinides and 0.05% lanthanide~
In these conditions -the coefficients of distribution of europium, americium, OeriuM III, gadoliniuM III, terbium III and curiuM III are respec-tively 0.4; 6.0; o.67; 0.53; 0.3 and 4.6. In this way a satisfacto~ separation 7~
of -the actinides and lan-thanides is obtained. ~le actinides can be re-extracted by bringing the organic solvent in-to contact with a 2N aqueous nitric solu-tion in a batte~y of decan-ter-mixers comprising 5 sta~es with a volumetric ra-tio of organic phase to aqueous phase of about 3. In these condi-tions the coefficient of distribution of americium is 0.015 and the organic solvent leaving the re-extrac-tion battery wi:L1 no longer contain more than about 0.001%
of the actinides.
In this example use is made of a bat-tery of decanter-mixers comprising 7 extraction stages and 9 washing stages. Circulating in counter-current in -the ba-ttery is a 0.05 N aqueous nitric solution containing americium, cur~um, terbium, cerium and gadolinium~ and an organic solvent formed by tertiobu-tyl benzene containing 0.05 mole 1 1 of DNNS and 0.05 mole 1 of ~PTZ, with a volumetric ratio of the organic phase to the aqueous phase of 0.4 in the extraction stages and 0.2 in -the washing stages.
In these conditions we obtain the ~ollowing distribution coefficients:
Am 7; DCm 13; DTb = 1-06; Dce = 1.34 and DCd = o.6.
at We therefore obtain/the outlet from -the battery a solvent containing more than 99.5% actinides and less than 0.2~/o lanthanides. The actinides are re-extracted in a 2N nitric solution, as in Example 4.
.,
Claims (6)
1. A process for the separation of the acti-nides and lanthanides present in the trivalent state in an acid aqueous solution, wherein the actinides present in such aqueous solution are extracted selectively in an organic solvent by bringing the solution into contact with an organic solvent comprising a first extracting agent formed by an organic bonding agent having an electron-donor nitrogen atom and a second extracting agent formed by an acid organosoluble organic compound able to exchange its H+ ions for metal ions or by metallic salt of such compound.
2. A process according to Claim 1, wherein the first extracting agent is a heterocyclic organic bonding agent with an electron-donor nitrogen atom.
3. A process according to Claim 2, wherein the first extracting agent is 2,4,6,-tri(2-pyridyl) 1,3,5-triazine.
4. A process according to Claims 1 or 3, wherein the second extracting agent is di-nonyl naph-thalene sulphonic acid.
5. A process according to Claims 1 or 3, wherein the second extracting agent is sodium di-nonyl naphthalene sulphonate.
6. A process according to Claims 1, 2 or 3, wherein the concentrations of such extracting agents in the organic solvent are such that the molar ratio between the first and second extracting agents is about 2:3 to 4:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8113530A FR2509282A1 (en) | 1981-07-09 | 1981-07-09 | PROCESS FOR SEPARATING ACTINIDS AND LANTHANIDES PRESENT AT TRIVALENT STATE IN AQUEOUS ACID SOLUTION |
| FR8113530 | 1981-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1197382A true CA1197382A (en) | 1985-12-03 |
Family
ID=9260389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000406707A Expired CA1197382A (en) | 1981-07-09 | 1982-07-06 | Process for separating the actinides and lanthanides present in the trivalent state in an acid aqueous solution |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4496523A (en) |
| EP (1) | EP0070226B1 (en) |
| JP (1) | JPS5819453A (en) |
| CA (1) | CA1197382A (en) |
| DE (1) | DE3263252D1 (en) |
| FR (1) | FR2509282A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2607021B1 (en) * | 1986-11-21 | 1990-11-16 | Commissariat Energie Atomique | PROCESS FOR SELECTIVE EXTRACTION OF TRANSITION METALS FROM ACID SOLUTIONS BY SYSTEMS OF POLYDENT NITROGEN LIGANDS AND CATIONIC EXCHANGERS |
| FR2618165B1 (en) * | 1987-07-17 | 1991-05-10 | Rhone Poulenc Chimie | PROCESS OF REDUCTION BY ELECTROLYSIS AND SEPARATION OF EUROPIUM AND ELECTROLYSIS CELL FOR THE IMPLEMENTATION OF THIS PROCESS. |
| US4867951A (en) * | 1988-03-31 | 1989-09-19 | The United States Of America As Represented By The United States Department Of Energy | Separation of actinides from lanthanides |
| US4923630A (en) * | 1988-03-31 | 1990-05-08 | The United States Of America As Represented By The United States Department Of Energy | Extractant composition |
| FR2680363B1 (en) * | 1991-08-14 | 1994-03-04 | Commissariat A Energie Atomique | PROCESS FOR SEPARATING ACTINIDES FROM LANTHANIDES BY SELECTIVE EXTRACTION OF ACTINIDES IN AN ORGANIC SOLVENT COMPRISING A PROPANEDIAMIDE. |
| FR2684670B1 (en) * | 1991-12-05 | 1995-04-07 | Commissariat Energie Atomique | AMIDES WITH NITROGEN HETEROCYCLIC SUBSTITUTES, PROCESS FOR THEIR PREPARATION AND THEIR USE FOR SELECTIVELY EXTRACTING ACTINIDES (III) AND PARTICULARLY LANTHANIDES (III). |
| JPH07104096A (en) * | 1993-10-05 | 1995-04-21 | Japan Atom Energy Res Inst | Mutual separation method of lanthanide element and superplutonium element in acidic solution by solvent extraction. |
| GB2296917B (en) * | 1994-12-21 | 1998-08-26 | Univ Reading | Separation of actinides from lanthanides using 1,3,5-triazine derivatives |
| FR2748951B1 (en) * | 1996-05-24 | 1998-07-03 | Commissariat Energie Atomique | PROCESS FOR SELECTIVE SEPARATION OF ACTINIDES (III) AND LANTHANIDES (III) |
| JP2003242906A (en) | 2002-02-21 | 2003-08-29 | Toshiba Corp | Deflection yoke and cathode ray tube device having the same |
| FR2845616B1 (en) * | 2002-10-15 | 2004-12-03 | Commissariat Energie Atomique | CYCLIC PROCESS FOR SEPARATING CHEMICAL ELEMENTS PRESENT IN AQUEOUS SOLUTION |
| DE10339328A1 (en) * | 2003-08-25 | 2005-03-24 | Forschungszentrum Jülich GmbH | Method for separating trivalent americium from trivalent curium |
| FR2948371B1 (en) * | 2009-07-21 | 2011-08-19 | Commissariat Energie Atomique | COMPOUNDS USEFUL AS LIGANDS OF ACTINIDES, THEIR SYNTHESIS AND USES THEREOF |
| EP2459522B1 (en) | 2009-07-30 | 2013-06-26 | Secretary, Department Of Atomic Energy | Dialkyldiaza-tetraalkyloctane diamide derivatives useful for the separation of trivalent actinides from lanthanides and process for the preparation thereof |
| EP2377861B1 (en) * | 2010-04-17 | 2013-12-04 | Karlsruher Institut für Technologie | Water-soluble bis-triazinyl-pyridines, bipyridines and terpyridines, synthesis and use of same |
| JP7108519B2 (en) * | 2018-10-31 | 2022-07-28 | 日立Ｇｅニュークリア・エナジー株式会社 | Isolation method for minor actinides |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2877092A (en) * | 1947-03-26 | 1959-03-10 | William H Reas | Coordination compound-solvent extraction process for uranium recovery |
| US3004051A (en) * | 1958-08-28 | 1961-10-10 | Phillips Petroleum Co | Extraction of uranium values from aqueous solutions |
| GB1047232A (en) * | 1963-07-12 | |||
| US3243254A (en) * | 1963-08-20 | 1966-03-29 | Iii Thomas H Siddall | Method for extracting lanthanides and actinides |
| US3276849A (en) * | 1964-09-18 | 1966-10-04 | Fletcher L Moore | Method for separating members of actinide and lanthanide groups |
| US3558288A (en) * | 1965-04-15 | 1971-01-26 | Ashland Oil Inc | Extraction of metal ions from acidic aqueous solution using an amine and a carboxylic acid |
| US3323857A (en) * | 1965-12-16 | 1967-06-06 | Donald J Bauer | Selective extraction and separation of lanthanides with a quaternary ammonium compound |
| US3294494A (en) * | 1966-02-28 | 1966-12-27 | Fletcher L Moore | Method for removing lanthanides and trivalent actinides from aqueous nitrate solutions |
| US3395992A (en) * | 1967-01-13 | 1968-08-06 | Atomic Energy Commission Usa | Concentration of transplutonium actinides from dirt samples |
| US3409415A (en) * | 1967-05-31 | 1968-11-05 | Atomic Energy Commission Usa | Method of extracting soluble metal complexes using amine solvents |
| FR1534888A (en) * | 1967-06-21 | 1968-08-02 | Commissariat Energie Atomique | Process for the separation of elements from actinide and lanthanide groups |
| FR2068159A5 (en) * | 1969-11-28 | 1971-08-20 | Commissariat Energie Atomique | Separation of actinides |
| GB1282089A (en) * | 1970-10-28 | 1972-07-19 | Miles Lab | Composition for the detection of uric acid |
| US3743696A (en) * | 1971-02-04 | 1973-07-03 | Atomic Energy Commission | Separation of americium and curium |
| US4025602A (en) * | 1976-05-25 | 1977-05-24 | The United States Of America As Represented By The United States Energy Research And Development Administration | Recovery of transplutonium elements from nuclear reactor waste |
| JPS5929660B2 (en) * | 1977-12-14 | 1984-07-21 | 動力炉・核燃料開発事業団 | Wet method method for extracting uranium from phosphoric acid |
| US4162230A (en) * | 1977-12-28 | 1979-07-24 | The United States Of America As Represented By The United States Department Of Energy | Method for the recovery of actinide elements from nuclear reactor waste |
| FR2465687A1 (en) * | 1979-09-21 | 1981-03-27 | Rhone Poulenc Ind | Extraction of uranium, thorium, yttrium and rare earths from acid soln - using a di-(alkylphenyl)phosphoric acid and hydrocarbon solvent |
| US4255396A (en) * | 1979-12-18 | 1981-03-10 | Gte Products Corporation | Process for separating molybdenum values from tungsten values |
-
1981
- 1981-07-09 FR FR8113530A patent/FR2509282A1/en active Granted
-
1982
- 1982-07-02 EP EP82401250A patent/EP0070226B1/en not_active Expired
- 1982-07-02 DE DE8282401250T patent/DE3263252D1/en not_active Expired
- 1982-07-02 US US06/394,491 patent/US4496523A/en not_active Expired - Fee Related
- 1982-07-06 CA CA000406707A patent/CA1197382A/en not_active Expired
- 1982-07-09 JP JP57118718A patent/JPS5819453A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| US4496523A (en) | 1985-01-29 |
| FR2509282A1 (en) | 1983-01-14 |
| EP0070226B1 (en) | 1985-04-24 |
| EP0070226A1 (en) | 1983-01-19 |
| DE3263252D1 (en) | 1985-05-30 |
| JPS5819453A (en) | 1983-02-04 |
| FR2509282B1 (en) | 1983-11-04 |
| JPH0470370B2 (en) | 1992-11-10 |
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