EP0066419B1 - Verfahren zur Gewinnung von Uran - Google Patents

Verfahren zur Gewinnung von Uran Download PDF

Info

Publication number
EP0066419B1
EP0066419B1 EP82302567A EP82302567A EP0066419B1 EP 0066419 B1 EP0066419 B1 EP 0066419B1 EP 82302567 A EP82302567 A EP 82302567A EP 82302567 A EP82302567 A EP 82302567A EP 0066419 B1 EP0066419 B1 EP 0066419B1
Authority
EP
European Patent Office
Prior art keywords
uranium
separator
slurry
nitric acid
calcium
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
EP82302567A
Other languages
English (en)
French (fr)
Other versions
EP0066419A3 (en
EP0066419A2 (de
Inventor
Edward Jean Lahoda
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.)
CBS Corp
Original Assignee
Westinghouse Electric Corp
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 Westinghouse Electric Corp filed Critical Westinghouse Electric Corp
Publication of EP0066419A2 publication Critical patent/EP0066419A2/de
Publication of EP0066419A3 publication Critical patent/EP0066419A3/en
Application granted granted Critical
Publication of EP0066419B1 publication Critical patent/EP0066419B1/de
Expired legal-status Critical Current

Links

Images

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
    • C22B60/0208—Obtaining thorium, uranium, or other actinides obtaining uranium preliminary treatment of ores or scrap
    • 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
    • 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
    • C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
    • C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
    • C22B60/0239—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors nitric acid containing ion as active agent
    • 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
    • C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
    • C22B60/0247—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using basic solutions or liquors
    • 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
    • C22B60/026—Obtaining 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
    • 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
    • C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins

Definitions

  • This invention relates to recovering uranium from an aqueous calcium fluoride slurry.
  • U.S. Patent Specification No. 2,965,440 discloses the recovery of uranium from an ore containing iron.
  • the ore is ground to a suitable particle size and is then roasted to produce a uranium-iron complex.
  • the complex can then be magnetically separated from the remainder of the ore.
  • a waste stream is produced which contains uranium, fluoride, ammonium, and nitrate ions.
  • a calcium hydroxide or lime slurry is added which precipitates calcium fluoride.
  • the ammonium diuranate waste stream is processed in an ammonia stripping column, and the calcium fluoride slurry which is produced is sent to a settling lagoon where excess water is decanted and run off.
  • Some of the uranium remains in the calcium fluoride slurry as insoluble calcium uranate. This calcium uranate waste not only creates an expensive disposal problem but also represents a loss of a valuable resource.
  • the present invention provides a method of recovering uranium from an aqueous calcium fluoride slurry containing less than 100 ppm of iron characterized in that a magnetic field of at least 10 Kilogauss is applied to the slurry in a high gradient magnetic separator comprising two magnetic poles between which is a porous ferromagnetic intermediate through which the slurry passes, and separated calcium uranate is removed from the porous ferromagnetic intermediate.
  • This procedure is simple, reasonably inexpensive, does not require large amounts of capital, and can produce a uranium product which can be added directly to already existing uranium processes.
  • a dispersant in line 1 is added to a calcium fluoride slurry in line 2.
  • the slurry passes through ball mill 3 which grinds up any large particles which may be present, then pump 4 forces the slurry into cyclone separator 5 which separates the slurry into large particles which are recycled in line 6 and finer particles which are passed through line 7 and valve 8 to high gradient magnetic separator 9.
  • the magnetic separator comprises an iron box 10 containing poles 11 and 12 of an electromagnet between which is a porous ferromagnetic intermediate 13. As the calcium fluoride slurry passes through the separator, the uranium in the slurry adheres to the porous ferromagnetic intermediate.
  • the remaining slurry goes to detector 14 which provides a signal when the separator has become saturated with uranium so that the uranium now passes through the separator.
  • the slurry then passes through valve 15 to sludge dewaterer 16 which removes some of the water.
  • the remainder of this slurry becomes waste sludge.
  • valves 8 and 15 are turned so that carbonate leach solution in line 17 now passes into the separator, dissolving the uranium which adheres to the porous ferromagnetic intermediate.
  • the carbonate leach solution containing the uranium passes through valve 15 and line 18 to filter 19 which removes any large particles which may be present.
  • nitric acid is used to remove the uranium from the separator and two separators are used to provide a continuous batch operation.
  • the calcium fluoride slurry passes through line 30 through valve 31 in the separator 32 through valve 33 and line 34 to a storage pond. While that is occurring, nitric acid in line 35 passes through valve 36 into separator 37 dissolving uranium on the porous ferromagnetic intermediate of that separator. The dissolved uranium passes through valve 38 and line 39 where it is sent to a solvent extractor.
  • valves 31, 33, 36, and 38 are closed and valves 40, 41, 42, and 43 are opened.
  • the nitric acid now passes through line 35 through valve 40, dissolves the uranium in separator 32, then passes through valve 41 and out line 39.
  • the calcium fluoride slurry now passes through valve 42 into separator 37 through valve 43 and out line 34.
  • the initial calcium fluoride slurry may contain 1 to 10 percent solids, of which at least 95 percent by weight is calcium fluoride, and the rest is water, and from 1 to 1000 ppm uranium, usually in the form of some type of calcium uranate.
  • the uranium in these slurries may be enriched in uranium 235, making it particularly valuable.
  • the invention will work with any liquid slurry of calcium fluoride which contains an insoluble uranium compound. This slurry must have less than 100 parts per million of iron present because the iron is dissolved with the uranium and would contaminate it in the subsequent processes. Such contamination would make it necessary to reprocess the uranium in the form of uranium hexafluoride in order to separate it from the iron. In the absence of iron, however, the product of this invention can be directly fed into the solvent extraction process.
  • a dispersant may be added to the calcium fluoride slurry to aid in breaking up the larger size particles.
  • the dispersants include detergents such as sodium sulfurate of a naphthalene-formaldehyde condensation product, 5 to 8 percent sodium sulfate in a condensed organic acid, and complex polymerized organic salts of sulfuric acids of alkyl-aryl type.
  • the preferred dispersant is a sodium sulfurate of a naphthalene-formaldehyde condensation product sold by Stepan Chemical Company as "Stepantan A". From 0.01 to 0.02 percent by weight of a dispersant may be used if desired.
  • the ball mill or other means of reducing the particle size in the slurry is necessary only if large particles are present.
  • the particles in the slurry should be no larger than about 5 pm.
  • the process of this invention requires the use of a high gradient magnetic separator.
  • a high gradient magnetic separator two poles of a magnet are spaced less than about 7.6 cm (three inches) apart, and the spacing between them is filled with a porous ferromagnetic intermediate.
  • the separator must have a magnetic field of at least 10 kilogauss in order to remove the uranium particles, which are only very weakly magnetic. Generally greater than 75 kilowatts of power are required and the magnet should have a coil diameter of less than 40 centimeters.
  • a separator can typically take up to 2.72 tonnes (3 tons) per hour of solids throughput.
  • the separator traps the calcium uranate, for example, CaU0 4 , particles on the intermediate, which should have a porosity of greater than 50%. If nitric acid is not used the intermediate can be made of steel wool, but if nitric acid is used stainless steel wool is needed as ordinary steel wool is attacked by nitric acid.
  • the calcium fluoride slurry is run through the separator until a detector indicates that the separator has become saturated and uranium is now passing through the separator.
  • a suitable detector can be a Geiger counter or similar device, but a fluorimetor is preferred as they are the most sensitive to uranium.
  • the flow rate through the separator should be less than about 37.9 litres (10 gallons) per minute as higher rates may wash the uranium off the intermediate.
  • the uranium can be removed from the intermediate in the separator by a variety of means. For example, almost any carbonate solution which is from 2 to 5 molar will dissolve the uranium in the separator. While sodium or any other alkali metal carbonate can be used, ammonium carbonate is preferred as it is more compatible with subsequent processes.
  • the preferred method of removing the uranium is to back wash with an aqueous solution of nitric acid.
  • the nitric acid wash should have a pH of greater than about 2 in order to avoid dissolving the calcium fluoride and should have a pH of less than about 3 or it will not dissolve the uranium.
  • the leachate can be sent directly to a solvent extraction system using, for example, di-2-ethylhexyl phosphoric acid-trioctyl phosphine oxide (DEPA-TOPO) in an organic solvent such as kerosene, as is well known in the art.
  • DEPA-TOPO di-2-ethylhexyl phosphoric acid-trioctyl phosphine oxide
  • the uranium can be removed from the carbonate solution on an ion exchange column as is also well known in the art. The uranium can then be removed from the ion exchange column with a solution of nitric acid which is then sent to a solvent extraction process.
  • the extra step of extraction on an ion exchange column is avoided when nitric acid is used to remove the uranium from the separator.
  • An aqueous calcium fluoride solution containing 2 percent solids and 15 parts per million uranium as calcium uranate can be passed through a separator as shown in Figure 1 containing a stainless steel wool intermediate.
  • the separator can have a field of 20 kilogauss, a power of 150 kilowatts, and a coil diameter of 30 centimeters. 1.81 tonnes (two tons) per hour of slurry can be passed through the separator.
  • a fluorimeter indicates that uranium is no longer being detained on the intermediate, the calcium fluoride flow is terminated and the intermediate is washed with a 10% solution of nitric acid.
  • the uranium in the nitric acid is then extracted using the DEPA-TOPO extractant.

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)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (9)

1. Ein Verfahren zur Wiedergewinnung von Uran aus einer wässrigen Kalzium-Fluoridaufschlämmung, die weniger als 100 ppm Eisen enthält, dadurch gekennzeichnet, daß ein Magnetfeld von zumindest 10 Kilogauss in einem Magnetseparator mit hohem Gradienten auf die Aufschlämmung einwirkt, welcher Separator zwei Magnetpole umfaßt, zwischen denen sich ein poröses ferromagnetisches Zwischenglied befindet, durch welches die Aufschlämmung passiert, und daß abgetrenntes Kalzium-Uranat von dem porösen ferromagnetischen Zwischenglied entfernt wird.
2. Ein Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Kalzium-Uranat von dem Separator durch Waschen mit einer wässrigen Lösung von Salpetersäure, die einen pH-Wert zwischen 2 und 3 besitzt, entfernt wird.
3. Ein Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Uran in der wässrigen Lösung der Salpetersäure mittels eines Lösungsmittels extrahiert wird, unter Verwendung von Di-2-Äthylhexyl-Phosphorsäure-Trioctyl-Phosphin-Oxid.
4. Ein Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Kalzium-Uranat von dem Separator durch Auslaugen mit einer wässrigen Karbonatlösung entfernt wird.
5. Ein Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Karbonatlösung 2- bis 5- molariges Ammonium-Karbonat ist.
6. Ein Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß das Uran in der Karbonatlösung auf einer lonenaustauschersäule entfernt wird.
7. Ein Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das Uran auf der lonenaustauschersäule von dieser mit einer wässrigen Lösung von Salpetersäure entfernt wird.
8. Ein Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Magnetpole weniger als 7,6 cm (3 Zoll) voneinander entfernt sind und einen Spulendurchmesser von weniger als 40 cm aufweisen.
9. Ein Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das poröse ferromagnetische Zwischenglied rostfreie Stahlwolle mit einer Porösität von mehr als 50% ist.
EP82302567A 1981-05-22 1982-05-20 Verfahren zur Gewinnung von Uran Expired EP0066419B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26668181A 1981-05-22 1981-05-22
US266681 1981-05-22

Publications (3)

Publication Number Publication Date
EP0066419A2 EP0066419A2 (de) 1982-12-08
EP0066419A3 EP0066419A3 (en) 1983-11-02
EP0066419B1 true EP0066419B1 (de) 1986-09-03

Family

ID=23015572

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82302567A Expired EP0066419B1 (de) 1981-05-22 1982-05-20 Verfahren zur Gewinnung von Uran

Country Status (7)

Country Link
EP (1) EP0066419B1 (de)
JP (1) JPS5930651B2 (de)
KR (1) KR900000397B1 (de)
DE (1) DE3272997D1 (de)
ES (1) ES512466A0 (de)
YU (1) YU106082A (de)
ZA (1) ZA822690B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4726895A (en) * 1986-03-28 1988-02-23 Edward Martinez Process for concentration of gold and uranium magnetically
KR101322083B1 (ko) * 2007-05-30 2013-10-25 주식회사 케이씨씨 납석으로부터 철분 제거 방법
CN110614088B (zh) * 2017-03-09 2022-08-02 中国工程物理研究院核物理与化学研究所 一种具备抗菌性能的海水提铀吸附剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2965440A (en) * 1957-01-11 1960-12-20 Tripp Res Corp Method of beneficiating uranium ores by forming ferromagnetic uranium values and magnetically separating same
US3394997A (en) * 1965-04-12 1968-07-30 Gen Electric Method of preparing uranium diuranate
US3676337A (en) * 1970-07-09 1972-07-11 Massachusetts Inst Technology Process for magnetic separation
GB1555670A (en) * 1977-12-12 1979-11-14 Atomic Energy Authority Uk Magnetic separation of particles from liquids in a process for reprocessing nuclear fuel

Also Published As

Publication number Publication date
KR830010211A (ko) 1983-12-26
ES8403976A1 (es) 1984-04-01
YU106082A (en) 1985-03-20
ES512466A0 (es) 1984-04-01
EP0066419A3 (en) 1983-11-02
KR900000397B1 (ko) 1990-01-25
EP0066419A2 (de) 1982-12-08
JPS5930651B2 (ja) 1984-07-28
DE3272997D1 (en) 1986-10-09
JPS57200224A (en) 1982-12-08
ZA822690B (en) 1983-06-29

Similar Documents

Publication Publication Date Title
KR930002530B1 (ko) 희토류 광석의 처리 방법
US7282187B1 (en) Recovery of metal values
US4886648A (en) Process for the recovery of germanium from solutions that contain it
US5531970A (en) Metal and fluorine values recovery from mineral ore treatment
CN111876598B (zh) 一种共萃取分离铀铌的方法
CN111020242A (zh) 一种从独居石精矿中冶炼分离铀、钍和稀土的工艺方法
US4241027A (en) Reductive stripping process for the recovery of either or both uranium and vanadium
JPH02236236A (ja) 金属の回収方法
Hirato et al. Concentration of uranyl sulfate solution by an emulsion-type liquid membrane process
EP0066419B1 (de) Verfahren zur Gewinnung von Uran
US5273725A (en) Metal and fluorine values recovery from mineral ore treatment
CN111087114A (zh) 钽铌生产废水的处理方法
CA1279197C (en) Cobalt recovery method
EP0729437A4 (de)
US4231866A (en) Recovery of organic and aqueous phases from solvent extraction emulsions
GB1596730A (en) Crud handling circuit
RU2612107C2 (ru) Способ извлечения скандия из скандийсодержащего продуктивного раствора
JPH01249624A (ja) 希土類元素とコバルトを含有する残留物の処理方法
US5077020A (en) Metal recovery process using waterglass
CN211350122U (zh) 钽铌生产废水的处理装置
JP3159220B2 (ja) 使用済核燃料からのウラン、プルトニウム及びネプツニウムの回収方法
RU2200992C2 (ru) Способ переработки урансодержащих твердых и/или жидких отходов
JPH01249623A (ja) 希土類元素とコバルトを含有する残留物の処理方法
US3198599A (en) Recovery of uranium and/or vanadium values from ores containing the same
CN114686708A (zh) 一种中和沉淀渣极低放化的方法

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 CH DE FR GB IT LI SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): BE CH DE FR GB IT LI SE

17P Request for examination filed

Effective date: 19840308

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI SE

REF Corresponds to:

Ref document number: 3272997

Country of ref document: DE

Date of ref document: 19861009

ET Fr: translation filed
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: FR

Payment date: 19890321

Year of fee payment: 8

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

Ref country code: SE

Payment date: 19890328

Year of fee payment: 8

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

Ref country code: GB

Effective date: 19890520

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

Ref country code: LI

Effective date: 19890531

Ref country code: CH

Effective date: 19890531

Ref country code: BE

Effective date: 19890531

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

Ref country code: DE

Payment date: 19890630

Year of fee payment: 8

GBPC Gb: european patent ceased through non-payment of renewal fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: SE

Effective date: 19900521

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

Ref country code: FR

Effective date: 19910131

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

Ref country code: DE

Effective date: 19910201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 82302567.1

Effective date: 19910115