EP3652355A1 - Procédé pour la production de césium à partir de solutions de départ aqueuses - Google Patents

Procédé pour la production de césium à partir de solutions de départ aqueuses

Info

Publication number
EP3652355A1
EP3652355A1 EP18753059.7A EP18753059A EP3652355A1 EP 3652355 A1 EP3652355 A1 EP 3652355A1 EP 18753059 A EP18753059 A EP 18753059A EP 3652355 A1 EP3652355 A1 EP 3652355A1
Authority
EP
European Patent Office
Prior art keywords
salt
amount
range
cesium
ppm
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.)
Withdrawn
Application number
EP18753059.7A
Other languages
German (de)
English (en)
Inventor
Rainer Dietz
Johannes Willems
David Wohlgemuth
Henrike REMPEL
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.)
Albemarle Germany GmbH
Original Assignee
Albemarle Germany GmbH
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 Albemarle Germany GmbH filed Critical Albemarle Germany GmbH
Publication of EP3652355A1 publication Critical patent/EP3652355A1/fr
Withdrawn legal-status Critical Current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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali 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
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition

Definitions

  • the invention relates to a process for cesium recovery from aqueous
  • the object of the invention has been found to provide a process for the economic recovery of cesium, which can continue to ensure compliance with environmental wastewater limits by Cs removal for the discharge of waste water into water and largely tolerated many interfering ions and impurities.
  • the object is achieved by a process for cesium recovery from aqueous starting solutions with cesium ion contents in the range of 50 ppm to 5000 ppm, wherein the cesium ions contained in the aqueous solution with the aid of an at least 1, 1-fold überstöichiometrischen amount of blood lye salt selected from the group consisting of K 4 [Fe (CN) 6 ], Na 4 [Fe (CN) 6 ], Ca 2 [Fe (CN) 6 ] or mixtures thereof solutions in a first stage in the pH range of 2 to 12 are precipitated as a double salt with divalent cations in the temperature range of 10 to 80 ° C, wherein the divalent cations either in the starting solutions in a for
  • water-soluble salt are added at least until reaching the equimolar amount and in a second stage by thermal decomposition back into a
  • the invention features the use of typical "impurities" in aqueous solutions, such as magnesium and calcium, to remove the cesium present by adding yellow blood lye salt as a mixture of various sparingly soluble double salts of the exemplary composition
  • Particularly preferred is a method in which a superstoichiometric amount of blood lye salt-containing solutions in the range of 1, 15 to 1, 5 times amount is used, which shifts the precipitation equilibrium far on the product side.
  • the precipitation of the double salt is carried out in a first stage in the pH range of 4 to 1 1.
  • the process can be advantageously designed by the precipitation of the double salt is carried out with the addition of inorganic filter aids such as diatomaceous earth or diatomaceous earth.
  • a very particularly advantageous variant of the method consists in precipitating the superstoichiometric amount of alkali-blood lye salt remaining in the starting solution by adding a water-soluble iron (III) salt in the pH range from 4 to 7 to the already formed double salt.
  • the excess of blood lye salt used is precipitated by addition of iron (III) salts and separated.
  • the existing Cs 2 Mg [Fe (CN) 6 ] crystals act as "seed crystals" for the blue of Berlin, which is easier to remove by filtration, and surprisingly the Berlin blue binds further cesium from the solution by adsorption, so that the residual solubility of Cs in the solution of 20 ppm (only by precipitation of Cs 2 Mg [Fe (CN) 6 ] and Cs 2 Ca [Fe (CN) 6 ]) can be reduced to about 10 ppm
  • This step not only removes the necessary excess of yellow blood lye salt from the solution, but also achieves further and improved Cs depletion, which increases the Cs yield with optimal utilization of the precipitating reagent used and thus makes it possible to economically produce water To use sources with low cesium levels.
  • the process can be further improved by using iron (III) sulfate in excess of the amount of blood-lye salt remaining in the starting solution of up to 100% by weight.
  • the process is particularly advantageous because the thermal digestion in the second stage is carried out in a calcining step under oxidative conditions at temperatures of 400 ° C. to 800 ° C.
  • the cesium salts contained in the solution are further purified by recrystallization.
  • the precipitation is preferably carried out in a reaction vessel without intermediate filtration at room temperature.
  • the reaction is fast with about 1 hour reaction time and tolerant to other impurities.
  • the filter residue consists of a mixture of various sparingly soluble Cs salts, which contain about 40 to 50 wt .-% of cesium based on the weight after separation of the mother liquor.
  • the wet precipitated salt mixture is converted in a calcining step in air at 600 ° C into insoluble oxides and soluble Cs compounds.
  • cesium constituents and Na / K all other elements form water insoluble hydroxides, oxides or
  • the calcination residue is leached with water and a Cs salt solution is obtained, from which the insoluble constituents are filtered off. By washing or resuspending the residue in water, the Cs yield can be increased to about 90%.
  • the present invention has the following advantages:
  • Na 4 [Fe (CN) 6 ] x 10 H 2 O is added at room temperature as an aqueous solution or as a solid and stirred for 30 minutes. The precipitation occurs spontaneously. Subsequently, Fe 2 (SO 4 ) 3 is added as an aqueous solution or as a solid and stirred for 30 minutes. The further precipitation is spontaneous. It is then filtered through a paper fold filter and the residue is unwashed dried at 100 ° C.
  • Residue of leaching oxides / hydroxides / carbonates of Fe, Ca, Mg, Sr and K.
  • the residue of the thermal decomposition is leached with at least the necessary amount for the complete solution of deionized water and filtered off from insoluble constituents.
  • the aqueous solution contains 1.4 g of Cs (100% of theory).
  • composition of the solution 3.8% by weight CsCl / 1, 7% by weight CsOH / 2.3% by weight NaCl / ⁇ 0.1% by weight KCl

Abstract

L'invention concerne un procédé pour la production de césium à partir de solutions de départ aqueuses, présentant des teneurs en ions césium dans la plage allant de 50 ppm à 5000 ppm, procédé selon lequel, dans une première étape, les ions césium contenus dans la solution aqueuse sont précipités à l'aide d'une quantité surstoechiométrique d'un facteur d'au moins 1,1 de solutions contenant du prussiate de potasse, dans une plage de valeurs de pH allant de 2 à 12, sous forme de sel double, avec des cations bivalents dans la plage de températures allant de 10 à 80 °C, les cations bivalents étant soit déjà présents dans les solutions de départ en une quantité au moins équimolaire par rapport à la teneur en césium, soit ajoutés sous forme de sel soluble dans l'eau puis, dans une deuxième étape, ils sont de nouveau transformés en une forme soluble dans l'eau par digestion thermique et, dans une troisième étape, ils sont séparés des résidus insolubles.
EP18753059.7A 2017-07-11 2018-07-09 Procédé pour la production de césium à partir de solutions de départ aqueuses Withdrawn EP3652355A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017211796 2017-07-11
PCT/EP2018/068575 WO2019011876A1 (fr) 2017-07-11 2018-07-09 Procédé pour la production de césium à partir de solutions de départ aqueuses

Publications (1)

Publication Number Publication Date
EP3652355A1 true EP3652355A1 (fr) 2020-05-20

Family

ID=63168358

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18753059.7A Withdrawn EP3652355A1 (fr) 2017-07-11 2018-07-09 Procédé pour la production de césium à partir de solutions de départ aqueuses

Country Status (8)

Country Link
US (1) US11155895B2 (fr)
EP (1) EP3652355A1 (fr)
KR (1) KR20200029438A (fr)
CN (1) CN110869524B (fr)
AU (1) AU2018299849A1 (fr)
BR (1) BR112020000290A2 (fr)
CA (1) CA3068780A1 (fr)
WO (1) WO2019011876A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ296292B6 (cs) * 1995-04-06 2006-02-15 Cabot Corporation Zpusob výroby cesné soli
FI111765B (fi) * 1996-06-26 2003-09-15 Fortum Nuclear Services Oy Menetelmä cesiumin erottamiseksi ydinjäteliuoksista sekä menetelmä heksasyanoferraattien valmistamiseksi

Also Published As

Publication number Publication date
CN110869524B (zh) 2022-07-05
AU2018299849A1 (en) 2020-02-06
KR20200029438A (ko) 2020-03-18
CN110869524A (zh) 2020-03-06
WO2019011876A1 (fr) 2019-01-17
US20200208239A1 (en) 2020-07-02
BR112020000290A2 (pt) 2020-07-14
CA3068780A1 (fr) 2019-01-17
US11155895B2 (en) 2021-10-26

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