EP0100744A1 - Verfahren zur Extraktion von Uran aus Phosphorsäuren durch Alkylpyrophosphorsäuren - Google Patents

Verfahren zur Extraktion von Uran aus Phosphorsäuren durch Alkylpyrophosphorsäuren Download PDF

Info

Publication number
EP0100744A1
EP0100744A1 EP83420127A EP83420127A EP0100744A1 EP 0100744 A1 EP0100744 A1 EP 0100744A1 EP 83420127 A EP83420127 A EP 83420127A EP 83420127 A EP83420127 A EP 83420127A EP 0100744 A1 EP0100744 A1 EP 0100744A1
Authority
EP
European Patent Office
Prior art keywords
extraction
uranium
extracting
acid
alkylpyrophosphoric
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.)
Granted
Application number
EP83420127A
Other languages
English (en)
French (fr)
Other versions
EP0100744B1 (de
Inventor
Antoine Floreancig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uranium Pechiney
Original Assignee
Uranium Pechiney
Pechiney Ugine Kuhlmann SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Uranium Pechiney, Pechiney Ugine Kuhlmann SA filed Critical Uranium Pechiney
Publication of EP0100744A1 publication Critical patent/EP0100744A1/de
Application granted granted Critical
Publication of EP0100744B1 publication Critical patent/EP0100744B1/de
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02Obtaining thorium, uranium, or other actinides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02Obtaining thorium, uranium, or other actinides
    • C22B60/0204Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/026Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents

Definitions

  • the invention relates to an improved method of extraction using an agent, consisting of alkylpyrophosphoric acids, of uranium present in phosphoric acid solutions, method which makes it possible to maintain the extraction power over said agent over time. by limiting its degradation.
  • alkylpyrophosphoric acids as uranium extraction agent, used in a form dissolved in an organic diluent, such as that petroleum cut, kerosene, etc .
  • the most commonly used extraction agent being alkylpyrophosphoric acid obtained by reaction of P 2 O 5 with octanol 2.
  • recovering the uranium contained in phosphoric acid at a rate of 90 to 200 milligrams of uranium oxide U 3 0 8 per liter consists first of all in contacting the solution of phosphoric acid with the extraction aqent most commonly constituted by octylpyrophosphoriqiie acid in solution in kerosene, the extraction of uranium being carried out against the current in a group of mixing and sedimentation tanks in cascade .
  • the phase organic containing in solution the octylpyrophosphorioue acid charged in uranium, separated from the solution of phosphoric acid is treated by contact by means of hydrofluoric acid giving the uranium fluoride (UF 4 ) and the deuraniated octylpyrophosphoric acid.
  • alkylpyrophosphoric acids as uranium extraction agent, and in particular octylpyrophosphoric acid, lies in the fact of their strong extracting power, even when they are used in organic solution very diluted, allowing them to extract, with a very good yield, the uranium present, even in very small quantity, in solutions of phosphoric acids.
  • French patent 2,423,545 describes a process for extracting uranium from phosphoric acid solutions whose extracting agent is a pyrophosphoric acid diester such as dicaproyl pyrophosphate or dioctyl pyrophosphate, a process according to which the hydrolysis of said extracting agent would be strongly dimine, while the re-extraction of uranium present in the organic phase is carried out by means of an alkaline solution and no longer by means of hydrofluoric acid.
  • a pyrophosphoric acid diester such as dicaproyl pyrophosphate or dioctyl pyrophosphate
  • the process according to the invention for the extraction of uranium contained in phosphoric acid solutions by means of an extraction agent consisting of an alkylpyrophosphoric acid, which consists in bringing the mineral phase of phosphoric acid and an organic phase containing the extraction agent by creating an emulsion is characterized in that, in an extraction unit comprising n cascade stages, for each extraction stage, the emulsion is produced during '' a first step by simultaneously subjecting the two phases for a time T1 to an intense mechanical shearing action corresponding to a shear coefficient of at least 5000 second-l in order to increase the contact surfaces between these two phases, then said emulsion during a second step is suddenly broken in a time T 2 , the total time required for the completion of the two steps being at most 20 minutes.
  • the extraction unit has a number of stages n of between 2 and 20.
  • the mineral and organic phases must be subjected to an intense mechanical shearing action corresponding to a very high shear coefficient.
  • this shear coefficient is chosen in the interval 5000 seconds to 50,000 seconds but preferably in the interval 10,000 seconds to 25,000 seconds.
  • the total time required to carry out the two stages according to the invention is preferably at most equal to 10 minutes for an extraction stage.
  • the times T 1 and T 2 of execution of the two stages can vary within wide limits, their ratio T 1 / T 2 can be chosen within the limits 1/100 to 5/1 and preferably within the limits 1 / 25 to 2/1.
  • the emulsion between the two organic and mineral phases is produced by any means known to those skilled in the art, making it possible to quickly and vigorously obtain the finest emulsion possible, in order to multiply the surfaces of contact and obtain a very high extraction yield.
  • the rapid separation of the organic and mineral phases can be obtained by physical means using any known means allowing rapid rupture of said emulsion.
  • the extracting agent, entrained by the desuranic phosphoric acid can be recovered by a physical separation of centrifugation for example and joined to the recycled extraction agent after re-extraction of the uranium .
  • the uranium extracting agent is chosen from the well-known group of alkylpyrophosphoric acids, the alkyl radical of which is a carbon chain corresponding to the C 7 to C 13 alcohols obtained by oxo synthesis, such as for example octanol 2, ethylhexanol, decanol.
  • the preparation of alkylpyrophosphoric acid can be carried out in a known manner by adding P 2 0 5 to the abovementioned alcohol, used alone or as a mixture with a hydrocarbon.
  • the preparation temperature of the alkylpyrophosphoric acid is generally between 30 ° C and 80 ° C, but preferably between 30 ° C and 40 ° C.
  • the uranium extraction agent is generally dissolved in an alphatic and / or aromatic hydrocarbon, such as kerosene for example.
  • the mixture thus formed constitutes the organic phase of extraction of uranium, which contains from 5 to 100 g / l but preferably from 20 to 50 g / l of alkylpyrophosphoric acid.
  • the phosphoric acid solutions resulting from the attack on phosphate ores generally contain from 30 to 200 milligrams of uranium per liter, this uranium being partly in the form U IV and for the other in the form U VI.
  • the uranium VI is then reduced to uranium IV by the treatment of the solutions of phosphoric acids by means of iron, which is in the form of powder when the reduction treatment is carried out in a reactor or also in the form of scrap metal when the reduction treatment is carried out in a column.
  • the phosphoric acid solutions containing suspended solids are subjected to a separation operation, before being brought into contact with the extraction agent in solution in an aliphatic and / or aromatic hydrocarbon.
  • the two mineral and organic phases to be extracted and extracting are then brought into intimate contact in the form of a fine emulsion which is quickly broken in order to separate the organic phase loaded with uranium from the mineral phase with deuranied acid.
  • the organic phase loaded with uranium is then treated with an aqueous hydrofluoric acid solution, this solution containing 10 ° or 20%, but preferably 14 to 18% by weight of free HF.
  • the temperature at which the uranium is re-extracted by hydrofluoric acid is between 0 ° C and 60 ° C but preferably between 10 ° C and 30 ° C, temperature at which the degradation of the alkylpyrophosphoric acid remains low (less than 2%).
  • the uranium then precipitates in the form of UF 4 , which is separated from the liquid medium by any means chosen from those known to those skilled in the art.
  • the desuranized alkylpyrophosphoric acid is then recycled directly to the extraction of the uranium contained in the phosphoric acid solutions after optional recharging with new alkylpyrophosphoric acid, while the desuranized phosphoric acid solutions are themselves subjected to centrifugation to recover the mechanically driven extractant.
  • This example illustrates the method of extracting uranium according to the invention, using alkylpyrophosphoric acids compared to the extraction method most commonly used in the processes belonging to the prior art.
  • This acid is reduced either by powdered iron in a stirred tank for tests 1 to 4, or in a column by plate iron for tests 5 and 6.
  • the reduced phosphoric acid contains Fe II and Fe III in an Fe II / Fe III ratio between 5 and 5.3.
  • the phosphoric acid is treated with the extracting agent in solution in kerosene at a rate of 30 g / l.
  • the reduced phosphoric acid flow rate was 200 l / h while that of the extractant solution was 20 l / h.
  • the desuranized solvent was recycled to extraction after adding a fraction of an hour of the extractant.
  • Test No. 1 which illustrates the prior art, was carried out in an industrial installation, the extraction unit of which consisted of a battery of 4 mixer-settlers - extraction unit in which the cumulative times T l and T 2 for 4 stages as defined in the method according to the invention, is equal to 14 hours.
  • Test No. 2 illustrating the invention was carried out in an industrial installation, the extraction unit of which consisted of a 4-stage multi-stage centrifugal extractor, rotating at the speed of 2800 revolutions per minute, a unit in which the cumulative residence times T 1 and T 2 for 4 floors was less than two minutes.
  • Test No. 3 illustrating the prior art, differs from Test No. 1 in the nature of the extractant which in this case was a solution of ethylhexylpyrophosphoric acid.
  • Test No. 4 illustrating the invention, differs from Test No. 2 in the nature of the extractant which was ethylhexylpyrophosphoric acid.
  • Test n ° 5 differs from test n ° 1 only in the mode of reduction of phosphoric acid (on platelets in column).
  • Test n ° 6 differs from test n ° 2 by the mode of reduction of phosphoric acid and by the constitution of the extraction unit which included four single stage centrifugal extractors in battery - unit in which the cumulative residence times T 1 and T 2 was less than two minutes.
  • This example illustrates the method of extracting uranium according to the invention, using alkylpyrophosphoric acids, compared to the extraction method most commonly used in methods belonging to the prior art.
  • the phosphoric acid treated had the following composition:
  • Test No. 8 which illustrates the invention, was carried out like test 2, but using a battery comprising 3 single-stage centrifugal extractors.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP83420127A 1982-07-30 1983-07-20 Verfahren zur Extraktion von Uran aus Phosphorsäuren durch Alkylpyrophosphorsäuren Expired EP0100744B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8213820 1982-07-30
FR8213820A FR2531102B1 (fr) 1982-07-30 1982-07-30 Procede d'extraction de l'uranium des acides phosphoriques par les acides alkylpyrophosphoriques

Publications (2)

Publication Number Publication Date
EP0100744A1 true EP0100744A1 (de) 1984-02-15
EP0100744B1 EP0100744B1 (de) 1985-12-18

Family

ID=9276723

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83420127A Expired EP0100744B1 (de) 1982-07-30 1983-07-20 Verfahren zur Extraktion von Uran aus Phosphorsäuren durch Alkylpyrophosphorsäuren

Country Status (16)

Country Link
US (1) US4510122A (de)
EP (1) EP0100744B1 (de)
KR (1) KR870002187B1 (de)
BR (1) BR8304067A (de)
CA (1) CA1209808A (de)
ES (1) ES8404419A1 (de)
FI (1) FI832749A (de)
FR (1) FR2531102B1 (de)
GR (1) GR78860B (de)
IL (1) IL69342A (de)
JO (1) JO1260B1 (de)
MA (1) MA19852A1 (de)
OA (1) OA07505A (de)
PH (1) PH19136A (de)
PT (1) PT77136B (de)
YU (1) YU157783A (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2573415B1 (fr) * 1984-11-16 1986-12-12 Pechiney Uranium Procede de recuperation sous forme de fluorure tetravalent de l'uranium extrait de solutions phosphatees
US5463177A (en) * 1994-08-23 1995-10-31 General Electric Company Solvent extraction process
KR100675919B1 (ko) * 2005-11-08 2007-06-04 정영기 원심분리기를 이용한 우라늄 동위원소 분리방법
US8883096B2 (en) 2008-07-31 2014-11-11 Urtek, Llc Extraction of uranium from wet-process phosphoric acid
US8226910B2 (en) * 2008-07-31 2012-07-24 Urtek, Llc Extraction of uranium from wet-process phosphoric acid

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2847275A (en) * 1955-01-04 1958-08-12 James H Yeager Uranium recovery process
GB860428A (en) * 1958-01-29 1961-02-08 Ca Atomic Energy Ltd Liquid-liquid contact extractor
FR1572021A (de) * 1967-07-14 1969-06-20
FR2374931A1 (fr) * 1976-12-27 1978-07-21 Exxon Research Engineering Co Membranes liquides et procede permettant de recuperer l'uranium
FR2376688A1 (fr) * 1977-01-10 1978-08-04 Anglian Water Authority Procede et appareil pour former une dispersion aqueuse stable de produits a base de silicate
FR2423545A1 (fr) * 1977-08-25 1979-11-16 Minemet Rech Sa Procede pour la recuperation de l'uranium contenu dans des solutions phosphatees
FR2449648A1 (fr) * 1979-02-21 1980-09-19 Wyoming Mineral Corp Procede pour la purification de solutions acides contenant des metaux

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180545A (en) * 1977-03-25 1979-12-25 Tennessee Valley Authority Uranium recovery from wet-process phosphoric acid
US4154698A (en) * 1977-06-08 1979-05-15 Nalco Chemical Company Resolution of oil-in-water emulsions containing uranium
US4243637A (en) * 1977-10-11 1981-01-06 Occidental Petroleum Company Uranium recovery from pre-treated phosphoric acid
US4311676A (en) * 1978-09-08 1982-01-19 Minemet Recherche Process for the recovery of uranium contained in phosphated compounds
US4293529A (en) * 1978-10-27 1981-10-06 Uranium Recovery Corporation Process for recovering uranium from wet-process phosphoric acid using alkyl pyrophosphoric acid extractants
US4287071A (en) * 1979-10-10 1981-09-01 Occidental Research Corporation Simultaneous extraction of more than one ion by liquid membrane process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2847275A (en) * 1955-01-04 1958-08-12 James H Yeager Uranium recovery process
GB860428A (en) * 1958-01-29 1961-02-08 Ca Atomic Energy Ltd Liquid-liquid contact extractor
FR1572021A (de) * 1967-07-14 1969-06-20
FR2374931A1 (fr) * 1976-12-27 1978-07-21 Exxon Research Engineering Co Membranes liquides et procede permettant de recuperer l'uranium
FR2376688A1 (fr) * 1977-01-10 1978-08-04 Anglian Water Authority Procede et appareil pour former une dispersion aqueuse stable de produits a base de silicate
FR2423545A1 (fr) * 1977-08-25 1979-11-16 Minemet Rech Sa Procede pour la recuperation de l'uranium contenu dans des solutions phosphatees
FR2449648A1 (fr) * 1979-02-21 1980-09-19 Wyoming Mineral Corp Procede pour la purification de solutions acides contenant des metaux

Also Published As

Publication number Publication date
ES524587A0 (es) 1984-05-01
KR840005414A (ko) 1984-11-12
BR8304067A (pt) 1984-03-07
PT77136A (fr) 1983-08-01
PH19136A (en) 1986-01-10
FR2531102A1 (fr) 1984-02-03
FR2531102B1 (fr) 1986-08-14
FI832749A0 (fi) 1983-07-29
IL69342A (en) 1986-07-31
US4510122A (en) 1985-04-09
JO1260B1 (en) 1985-04-20
GR78860B (de) 1984-10-02
PT77136B (fr) 1986-01-24
YU157783A (en) 1986-04-30
ES8404419A1 (es) 1984-05-01
KR870002187B1 (ko) 1987-12-28
EP0100744B1 (de) 1985-12-18
FI832749A (fi) 1984-01-31
MA19852A1 (fr) 1984-04-01
OA07505A (fr) 1985-03-31
CA1209808A (fr) 1986-08-19

Similar Documents

Publication Publication Date Title
EP0156735B1 (de) Verfahren zur Trennung von seltenen Erden durch Flüssig-Flüssig-Extraktion
EP0079258B1 (de) Verfahren zur Extraktion und Trennung von Uran, Thor und seltenen Erden durch Behandeln wässriger Lösungen der Chloride dieser Elemente
WO1982000664A1 (en) Process for selective extraction of germanium
CA2025152A1 (fr) Procede de traitement de minerais contenant des terres rares
EP0090692B1 (de) Verfahren zur Rückgewinnung und Reinigung einer rückständigen Schwefelsäure welche Titansalze enthält
FR2954354A1 (fr) Procede de purification de l'uranium d'un concentre d'uranium naturel
EP0100744B1 (de) Verfahren zur Extraktion von Uran aus Phosphorsäuren durch Alkylpyrophosphorsäuren
EP0010044B1 (de) Verfahren zur Trennung von Americium von Curium
EP0030487B1 (de) Verfahren zur Reinigung einer Nassverfahrenphosphorsäure
EP0116483B1 (de) Verfahren zur Gewinnung von Uran, Yttrium, Thorium und seltenen Erdmetallen aus einer organischen Phase
EP0026132B1 (de) Verfahren zur globalen Gewinnung von Uran, Seltenen Erden, Thorium und Yttrium aus einer sauren Lösung
EP0284503B1 (de) Verfahren zum flüssig-flüssig Extrahieren von seltenen Erden
EP0068541A1 (de) Verfahren zur Germaniumgewinnung aus einer wässerigen Lösung
CA1134119A (fr) Procede de traitement d'un acide phosphorique impur
WO2017001494A1 (fr) Procede de separation du fer d'une phase organique contenant de l'uranium et procede d'extraction de l'uranium d'une solution aqueuse d'acide mineral contenant de l'uranium et du fer
FR2557090A1 (fr) Procede de purification de l'acide phosphorique de voie humide par elimination du cadmium
BE1007419A3 (fr) Recuperation d'indium a l'aide d'une extraction par solvant en se servant d'oxydes de trialkylphosphines.
FR2573415A1 (fr) Procede de recuperation sous forme de fluorure tetravalent de l'uranium extrait de solutions phosphatees
BE1001758A3 (fr) Recuperation d'uranium a partir d'acide phosphorique issu du procede en voie humide, en utilisant des oxydes de phosphine asymetriques.
EP0182726B1 (de) Verfahren zur Rückgewinnung von vierwertigem Uran aus phosphathaltigen Lösungen unter Zusatz von metallischen Ionen
EP0016264B1 (de) Verfahren zur Extraktion von Uran aus Phosphorsäure
EP0233121B1 (de) Verfahren zum Entfernen von Blei aus Seltenerdmetallen
FR2465687A1 (fr) Procede de recuperation globale de l'uranium, des terres rares, du thorium et de l'yttrium contenus dans une solution acide
EP0239501B1 (de) Verfahren zur Trennung von Eisen aus organischen Uranlösungen
FR2633606A1 (fr) Procede de separation par precipitation du zirconium contenu dans des solutions carbonatees uraniferes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE GB IT NL SE

17P Request for examination filed

Effective date: 19840225

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: URANIUM PECHINEY

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE GB IT NL SE

ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870731

Year of fee payment: 5

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19880721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19880731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19881122

BERE Be: lapsed

Owner name: URANIUM PECHINEY

Effective date: 19880731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19890201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
EUG Se: european patent has lapsed

Ref document number: 83420127.9

Effective date: 19890510