EP0109327B1 - Verfahren zur vollständigen Rückgewinnung von Uran, Thorium, Yttrium und seltenen Erdmetallen aus Phosphaterz während der Herstellung von Nassverfahrensphosphorsäure - Google Patents

Verfahren zur vollständigen Rückgewinnung von Uran, Thorium, Yttrium und seltenen Erdmetallen aus Phosphaterz während der Herstellung von Nassverfahrensphosphorsäure Download PDF

Info

Publication number
EP0109327B1
EP0109327B1 EP83402114A EP83402114A EP0109327B1 EP 0109327 B1 EP0109327 B1 EP 0109327B1 EP 83402114 A EP83402114 A EP 83402114A EP 83402114 A EP83402114 A EP 83402114A EP 0109327 B1 EP0109327 B1 EP 0109327B1
Authority
EP
European Patent Office
Prior art keywords
attack
yttrium
phosphoric acid
silica
uranium
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
Application number
EP83402114A
Other languages
English (en)
French (fr)
Other versions
EP0109327A1 (de
Inventor
Jean Fava
André Lambert
Jean-Paul Tognet
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.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Rhone Poulenc Chimie de Base 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 Rhone Poulenc Chimie SA, Rhone Poulenc Chimie de Base SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0109327A1 publication Critical patent/EP0109327A1/de
Application granted granted Critical
Publication of EP0109327B1 publication Critical patent/EP0109327B1/de
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/0278—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries by chemical methods
    • C22B60/0282—Solutions containing P ions, e.g. treatment of solutions resulting from the leaching of phosphate ores or recovery of uranium from wet-process phosphoric acid
    • 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
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • 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
    • C22B59/00—Obtaining rare earth metals
    • 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
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium

Definitions

  • the present invention relates to a process for the overall recovery of uranium, yttrium, thorium and rare earths contained in a phosphate ore during the preparation of phosphoric acid by wet process.
  • phosphate ores used for the manufacture of phosphoric acid contain significant amounts of uranium, yttrium, thorium and rare earths.
  • yttrium represents in quantity approximately half of the whole.
  • silica hinders the filtration of the attack slurry during the separation of the gypsum and the phosphoric acid.
  • silica can prove to be a nuisance in the subsequent stages of a process for manufacturing phosphoric acid, in particular during liquid-liquid extractions.
  • the object of the invention is to further improve the solubilization of rare earths, of yttrium and of thorium on attack without harming the subsequent progress of the process for the manufacture of phosphoric acid.
  • the process according to the invention for the overall recovery of uranium, yttrium, thorium and rare earths contained in a phosphate ore, during the preparation of phosphoric acid by wet process, is characterized in that during the acid attack of the ore, optionally carried out in the presence of silica, aluminum is added to the attack medium in trivalent form and / or a ferric compound in such a way that the amount of aluminum and / or iron present in this attack medium varies between 0.8% and 1.5% by weight expressed as A1 2 0 3 and / or Fe 2 O 3 relative to the ore subjected to attack.
  • the process of the invention makes it possible to reach percentages of solubilization of the above-mentioned elements greater than those of silica while keeping a shorter filtration time.
  • the attack on the phosphate ore which can be carried out more particularly with sulfuric acid takes place under known and usual conditions of temperature and concentration of acids.
  • Aluminum or iron can be introduced either with the attack acid or in the attack slurry.
  • Aluminum is added in the form of a salt of this element, for example in the form of a sulfate, a phosphate, an alumina or any other precursor capable of releasing the aluminum ion under the conditions of 'attack. It is the same for iron which can in particular be added in the form of sulfate, of oxide, such as ferric oxide.
  • aluminum and iron can be added in the form of aluminum-calcium phosphates containing iron such as Thies phosphates and Ta ⁇ ba fines, so that the proportions of aluminum and iron in the attack medium are within the limits indicated in claim 1.
  • the amounts of aluminum, iron and silica used depend on the type of ore processed, the attack conditions that one wishes to observe and the type of acid that one wishes to obtain.
  • the resulting porridge is filtered.
  • a residue or primary gypsum is obtained in the case of a sulfuric attack and a phosphoric acid solution.
  • the whole solid obtained after this filtration is called gypsum here.
  • the phosphoric acid solution notably includes uranium in almost the entire quantity present in the starting ore and a significant proportion of yttrium, thorium and rare earths.
  • the acid is brought into contact with an organic phase comprising a di (alkylphenyl) phosphoric acid, dissolved in an inert organic solvent and in the presence of a trialkylphosphine oxide.
  • organic phase is reextracted using a solution containing hydrofluoric acid and phosphoric acid.
  • a Kouribga phosphate ore of the following composition 31.07% P 2 0 5 ; 344 ppm yttrium; 140 ppm uranium; Ce0 2 : 42 ppm; LaC0 3 : 132 ppm; Tb 4 O 7 : 9 ppm; Yb 2 O 3 : 21 ppm.
  • This mineral is attacked with sulfuric acid without any additives, then in another series of tests in the presence of precipitated silica in variable quantity and in a third series of tests in the presence of aluminum sulphate and d '' a mixture of aluminum sulphate and silica in variable quantity.
  • the amount of aluminum is calculated as AI z 0 3 .
  • the filtration times given were obtained by measuring the filtration time on buchner of the attack slurry and the filtration time of the cake after addition of a representative quantity of washing water. of the quantity of washing water used industrially. The sum of these two times for each test corresponds to the time indicated in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (6)

1. Verfahren zur vollständigen Gewinnung des in einem phosphathaltigen Mineral enthaltenen Urans, Yttriums, Thoriums und der Seltenen Erden bei der Herstellung von Phosphorsäure auf dem nassen Wege, dadurch gekennzeichnet, daß man bei dem sauren Aufschluß des Minerals, der gegebenenfalls in Gegenwart von Kieselsäure durchgeführt wird, zu dem Aufschlußmilieu Aluminium in dreiwertiger Form und/oder eine Eisenverbindung in der Weise zusetzt, daß die Menge an Aluminium und/oder Eisen in dem Aufschlußmilieu zwischen 0,8 Gew.% und 1,5 Gew.% liegt, ausgedrückt als A1203 und/oder Fe203, bezogen auf das dem Aufschluß unterworfene Mineral.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Aluminium in Form des Sulfats, des Phosphats oder in Form von Tonerde eingesetzt wird.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Eisen in Form eines Eisen (111) sulfats oder eines Eisen (111) oxids eingesetzt wird.
4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Zugabe an Aluminium und/oder Eisen zur Erzielung der vorangehend genannten Mengen dieser Elemente in dem Aufschlußmilieu in Form eines eisenhaltigen Aluminium-Calcium-Phosphats vorgenommen wird.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man den Aufschluß in Gegenwart von zusätzlich Siliciumoxid durchführt.
6. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß man den Aufschluß in Gegenwart von Aluminium und Kieselsäure durchführt.
EP83402114A 1982-11-10 1983-10-28 Verfahren zur vollständigen Rückgewinnung von Uran, Thorium, Yttrium und seltenen Erdmetallen aus Phosphaterz während der Herstellung von Nassverfahrensphosphorsäure Expired EP0109327B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8218910 1982-11-10
FR8218910A FR2535702B1 (fr) 1982-11-10 1982-11-10 Procede de recuperation globale de l'uranium, de l'yttrium, du thorium et des terres rares contenus dans un minerai phosphate au cours de la preparation d'acide phosphorique par voie humide

Publications (2)

Publication Number Publication Date
EP0109327A1 EP0109327A1 (de) 1984-05-23
EP0109327B1 true EP0109327B1 (de) 1986-12-30

Family

ID=9279094

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83402114A Expired EP0109327B1 (de) 1982-11-10 1983-10-28 Verfahren zur vollständigen Rückgewinnung von Uran, Thorium, Yttrium und seltenen Erdmetallen aus Phosphaterz während der Herstellung von Nassverfahrensphosphorsäure

Country Status (15)

Country Link
US (1) US4636369A (de)
EP (1) EP0109327B1 (de)
JP (1) JPS6058175B2 (de)
KR (1) KR890004520B1 (de)
AU (1) AU559423B2 (de)
BR (1) BR8306163A (de)
CA (1) CA1222376A (de)
DE (1) DE3368689D1 (de)
ES (1) ES527101A0 (de)
FI (1) FI74491C (de)
FR (1) FR2535702B1 (de)
GR (1) GR78756B (de)
IL (1) IL70180A (de)
MA (1) MA19949A1 (de)
ZA (1) ZA838268B (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8707200A (pt) * 1987-12-23 1989-08-15 Pirelli Brasil Sintese de supercondutores a partir da xenotima
JP3731786B2 (ja) * 1998-02-19 2006-01-05 三菱電機株式会社 ワイヤ放電加工装置
CN100439239C (zh) * 2006-10-12 2008-12-03 贵州宏福实业开发有限总公司 降低磷酸中稀土含量的方法
CN101451200B (zh) * 2007-11-29 2011-04-20 北京有色金属研究总院 一种从磷矿中富集回收稀土的方法
CN103184356B (zh) * 2011-12-28 2014-12-17 有研稀土新材料股份有限公司 一种稀土磷矿的处理方法和富集稀土的方法
CN113332957A (zh) * 2021-06-09 2021-09-03 江西理工大学 改性磁性掺杂材的制备方法及其从稀土矿废水中回收稀土元素的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0031793A2 (de) * 1979-12-03 1981-07-08 Schweizerische Aluminium AG Verfahren zur Herstellung von Phosphorsäure, bei dem Uran in einer gewinnbaren Form erhalten wird

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425573A (en) * 1940-11-28 1947-08-12 Soddy Frederick Separation of thorium and the rareearth group from minerals
US2761758A (en) * 1950-08-04 1956-09-04 Ray S Long Process for recovery of uranium
US2789879A (en) * 1950-11-15 1957-04-23 Kaufman David Recovery of uranium from phosphoric acid
US2819145A (en) * 1952-10-15 1958-01-07 Robert F Mccullough Metal value recovery from leached zone material
US2859092A (en) * 1953-02-05 1958-11-04 Richard H Bailes Solvent extraction process for the recovery of metals from phosphoric acid
FR1104263A (fr) * 1954-05-07 1955-11-17 Comptoir Des Phosphates De L A Procédé pour la séparation, par précipitation, de l'uranium à partir d'une liqueur fortement acide
US2743156A (en) * 1954-08-06 1956-04-24 Max C Metziger Uranium recovery process
US2841467A (en) * 1955-01-18 1958-07-01 Robert F Mccullough Method for recovery of mineral values from leached zone material
US2990244A (en) * 1957-12-24 1961-06-27 Keith B Brown Extraction of thorium and uranium values from acid leach liquors
FR1585270A (de) * 1968-09-11 1970-01-16
US3937783A (en) * 1974-02-21 1976-02-10 Allied Chemical Corporation Recovery of fluorine, uranium and rare earth metal values from phosphoric acid by-product brine raffinate
DE2652766A1 (de) * 1976-03-09 1977-09-22 Robert Dr Michel Verfahren zur herstellung von phosphorsaeure aus phosphatgestein
US4284614A (en) * 1976-04-13 1981-08-18 Occidental Petroleum Corp. Process for production of high purity phosphoric acid from high alumina phosphate pebble rock
FR2423545A1 (fr) * 1977-08-25 1979-11-16 Minemet Rech Sa Procede pour la recuperation de l'uranium contenu dans des solutions phosphatees
JPS5855086B2 (ja) * 1978-04-18 1983-12-08 三菱マテリアル株式会社 リン酸液中に溶存するウランの回収方法
US4374805A (en) * 1978-05-26 1983-02-22 Uranium Recovery Corporation Reductants for reducing metals in acid media
FR2515630B1 (fr) * 1981-10-30 1985-10-04 Rhone Poulenc Spec Chim Procede d'extraction et de separation de l'uranium, du thorium et des terres rares par traitement de solutions aqueuses de chlorures de ces elements

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0031793A2 (de) * 1979-12-03 1981-07-08 Schweizerische Aluminium AG Verfahren zur Herstellung von Phosphorsäure, bei dem Uran in einer gewinnbaren Form erhalten wird

Also Published As

Publication number Publication date
ES8406374A1 (es) 1984-07-01
FR2535702A1 (fr) 1984-05-11
FI834107A0 (fi) 1983-11-09
BR8306163A (pt) 1984-06-12
DE3368689D1 (en) 1987-02-05
AU2111383A (en) 1984-05-17
IL70180A (en) 1987-10-30
US4636369A (en) 1987-01-13
AU559423B2 (en) 1987-03-12
GR78756B (de) 1984-10-02
CA1222376A (fr) 1987-06-02
KR840006508A (ko) 1984-11-30
FI74491B (fi) 1987-10-30
IL70180A0 (en) 1984-02-29
ZA838268B (en) 1984-09-26
FI834107A (fi) 1984-05-11
FI74491C (fi) 1988-02-08
MA19949A1 (fr) 1984-07-01
KR890004520B1 (ko) 1989-11-10
ES527101A0 (es) 1984-07-01
FR2535702B1 (fr) 1986-09-12
EP0109327A1 (de) 1984-05-23
JPS59116126A (ja) 1984-07-04
JPS6058175B2 (ja) 1985-12-18

Similar Documents

Publication Publication Date Title
EP0388250A1 (de) Verfahren zum Aufschluss von Erzen der seltenen Erden
EP0079258A1 (de) Verfahren zur Extraktion und Trennung von Uran, Thor und seltenen Erden durch Behandeln wässriger Lösungen der Chloride dieser Elemente
EP0109327B1 (de) Verfahren zur vollständigen Rückgewinnung von Uran, Thorium, Yttrium und seltenen Erdmetallen aus Phosphaterz während der Herstellung von Nassverfahrensphosphorsäure
BE1006385A3 (fr) Procede pour l'extraction de tantale et de niobium.
EP3833789B1 (de) Verwendung einer synergistischen mischung von extraktionsmitteln zur extraktion von seltenerdelementen aus einem phosphorsäure enthaltenden wässrigen medium
EP3856940A1 (de) Verfahren zur reinigung und zur konzentration seltener erden aus phosphogips
EP0026132A1 (de) Verfahren zur globalen Gewinnung von Uran, Seltenen Erden, Thorium und Yttrium aus einer sauren Lösung
CA1160459A (fr) Procede de valorisation de l'uranium a partir d'un minerai uranifere contenant de l'arsenic
WO2014118288A1 (fr) Procede d'extraction selective du scandium
EP0210934B1 (de) Verfahren zur Abtrennung und Verwertung seltener Erdmetalle und Uran aus Urantetrafluoridkonzentrat
EP0433107B1 (de) Verfahren zur Gewinnung von Gallium aus basischen Lösungen
JPH0394028A (ja) 希土類元素の分離方法
FR2826667A1 (fr) Procede de traitement d'un minerai de terres rares a teneur elevee en fer
FR2678644A1 (fr) Procede de recuperation globale du thorium et des terres rares en milieu nitrate.
JPS6112010B2 (de)
EP0251399A1 (de) Verfahren zum Trennen oder zum Rückgewinnen von Plutonium und nach diesem Verfahren erzeugtes Plutonium
FR2669348A1 (fr) Compositions contenant des derives hydroxydiphosphoniques pour l'extraction de cations metalliques.
EP0371832B1 (de) Extraktion von Gallium aus wässrigen Lösungen
SU408565A1 (ru) Способ рафинировани олова от примесей
KR101664625B1 (ko) 황인의 정제방법
CA1146763A (fr) Procede de reduction des pertes en solvant organique dans le traitement d'une suspension resultant de l'attaque acide d'un minerai
FR2485506A2 (fr) Procede de recuperation globale de l'uranium, des terres rares, du thorium et de l'yttrium applique au traitement de phosphogypse
WO2022117942A1 (fr) Mélanges de sels d'ammonium quaternaire pour l'extraction de l'uranium(vi) de solutions aqueuses d'acide sulfurique
FR2465687A1 (fr) Procede de recuperation globale de l'uranium, des terres rares, du thorium et de l'yttrium contenus dans une solution acide
JPS6214617B2 (de)

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 DE FR GB IT NL

17P Request for examination filed

Effective date: 19840620

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

BECN Be: change of holder's name

Effective date: 19861230

REF Corresponds to:

Ref document number: 3368689

Country of ref document: DE

Date of ref document: 19870205

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: RHONE-POULENC CHIMIE

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

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19871031

Year of fee payment: 5

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: RHONE-POULENC CHIMIE TE COURBEVOIE, FRANKRIJK.

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19891028

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19891130

Year of fee payment: 7

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

Ref country code: NL

Effective date: 19900501

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19901017

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19901211

Year of fee payment: 8

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

Ref country code: DE

Effective date: 19910702

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

Ref country code: BE

Effective date: 19911031

BERE Be: lapsed

Owner name: RHONE-POULENC CHIMIE

Effective date: 19911031

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

Ref country code: FR

Effective date: 19920630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST