PL227656B1 - Method for preparing solutions of zirconium sulfate(IV) and hafnium(IV) with the solution of oxalate - Google Patents
Method for preparing solutions of zirconium sulfate(IV) and hafnium(IV) with the solution of oxalate Download PDFInfo
- Publication number
- PL227656B1 PL227656B1 PL403863A PL40386313A PL227656B1 PL 227656 B1 PL227656 B1 PL 227656B1 PL 403863 A PL403863 A PL 403863A PL 40386313 A PL40386313 A PL 40386313A PL 227656 B1 PL227656 B1 PL 227656B1
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- PL
- Poland
- Prior art keywords
- hafnium
- oxalate
- zirconium
- solution
- zirconium sulfate
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims description 7
- GVOLZAKHRKGRRM-UHFFFAOYSA-N hafnium(4+) Chemical compound [Hf+4] GVOLZAKHRKGRRM-UHFFFAOYSA-N 0.000 title claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 title description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 5
- -1 oxalate ions Chemical class 0.000 claims description 4
- 229910052845 zircon Inorganic materials 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 229910052735 hafnium Inorganic materials 0.000 description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QXDNWIJGNPKDRX-UHFFFAOYSA-J hafnium(4+);oxalate Chemical class [Hf+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O QXDNWIJGNPKDRX-UHFFFAOYSA-J 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical group OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HNNUVNCHWLBGRE-UHFFFAOYSA-F hafnium(4+) zirconium(4+) tetrasulfate Chemical compound S(=O)(=O)([O-])[O-].[Hf+4].[Zr+4].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] HNNUVNCHWLBGRE-UHFFFAOYSA-F 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical class [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229910001735 zirconium mineral Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Przedmiotem wynalazku jest sposób otrzymywania siarczanowych roztworów cyrkonu(IV) i hafnu(IV) z ich roztworów szczawianowych.The present invention relates to a method of obtaining zirconium (IV) and hafnium (IV) sulfate solutions from their oxalate solutions.
Cyrkon i hafn stanowią parę pierwiastków o bardzo podobnych własnościach chemicznych, stąd bardzo trudną do rozdzielenia. Cyrkon, oczyszczony od towarzyszącego mu hafnu do poziomu <100 ppm (naturalna zawartość Hf w minerałach cyrkonowych to ok. 2%), znajduje szerokie zastosowanie w technice jądrowej. Jedną z nowych efektywnych metod rozdziału cyrkonu od hafnu jest separacja tych pierwiastków na chelatującej żywicy jonowymiennej Diphonix® z 0,5 M roztworu kwasu siarkowego, będąca przedmiotem patentu PL nr 211 353 i publikacji Smolik, M; et al. Separation of zirconium and hafnium using Diphonix® chelating ion-exchange resin Hydrometallurgy 95 (2009) 350353. Znany jest więc sposób rozdzielania hafnu i cyrkonu na chelatującej żywicy jonowymiennej zawierającej geminalnie podstawione grupy kwasu dwufosfonowego oraz odpowiednio uporządkowane grupy sulfonowe i karboksylowe. W procesie tym z kolumny odbierany jest roztwór siarczanu cyrkonu(IV) o zmniejszonej zawartości hafnu, a na kolumnie z jonitem pozostają zaadsorbowane jony cyrkonu(IV) i hafnu(IV) w stosunku [Hf/Zr] większym niż w roztworze wprowadzanym. Jony te są następnie desorbowane z żywicy w znany ze zgłoszenia patentowego P-385844 sposób przy pomocy wodnych roztworów szczawianu amonu łub soli sodowej kwasu etylenodwuaminotetraoctowego. Wymienione ligandy tworzą trwałe związki kompleksowe z hafnem(IV) i cyrkonem(IV) i skutecznie usuwają je z żywicy. Utworzone w ten sposób np. kompleksy szczawianowe cyrkonu(IV) i hafnu(IV) muszą zostać następnie przeprowadzone w formę nadającą się do dalszego rozdzielania metodą wymiany jonowej (np. roztwory siarczanowe).Zirconium and hafnium are a pair of elements with very similar chemical properties, hence very difficult to separate. Zirconium, purified from the accompanying hafnium to the level of <100 ppm (the natural content of Hf in zirconium minerals is approx. 2%), is widely used in nuclear technology. One of the new effective methods of separating zirconium from hafnium is the separation of these elements on the chelating ion-exchange resin Diphonix® from 0.5 M sulfuric acid solution, which is the subject of patent PL No. 211 353 and the publication of Smolik, M; et al. Separation of zirconium and hafnium using Diphonix® chelating ion-exchange resin Hydrometallurgy 95 (2009) 350353. Thus, a method of separating hafnium and zirconium on a chelating ion exchange resin containing geminally substituted diphosphonic acid groups and appropriately ordered sulfone and carboxyl groups is known. In this process, zirconium (IV) sulphate solution with reduced hafnium content is collected from the column, and zirconium (IV) and hafnium (IV) ions remain adsorbed on the ion exchanger column in the ratio [Hf / Zr] greater than in the introduced solution. These ions are then desorbed from the resin in the manner known from the patent application P-385844 with the aid of aqueous solutions of ammonium oxalate or sodium salt of ethylenediaminetetraacetic acid. These ligands form stable complexes with hafnium (IV) and zircon (IV) and effectively remove them from the resin. The zirconium (IV) and hafnium (IV) oxalate complexes formed in this way must then be converted into a form suitable for further ion exchange separation (e.g. sulfate solutions).
Sposób wynalazku polega na tym, że jony szczawianowe rozkłada się za pomocą nadtlenodwusiarczanu amonu w ilości co najmniej stechiometrycznej w stosunku do szczawianu, korzystnie w stosunku (molowo) nadtlenodwusiarczan amonu : szczawian 1:1-1,3:1, przy czym reakcję prowadzi się w podwyższonej temperaturze, korzystnie 100-130°C, przez kilka godzin, korzystnie 2-3 godziny.The method of the invention consists in decomposing the oxalate ions with ammonium peroxodisulfate in an amount at least stoichiometric to the oxalate, preferably in a (molar) ratio of ammonium persulfate: oxalate 1: 1-1.3: 1, the reaction being carried out by at elevated temperature, preferably 100-130 ° C, for several hours, preferably 2-3 hours.
Proponowany sposób pozwala przeprowadzić trwałe i trudne do rozłożenia oraz dalszej przeróbki szczawianowe kompleksy cyrkonu(IV) (hafnu(IV)) w ich roztwory siarczanowe, ponieważ zastosowany nadtlenodwusiarczan reaguje z jonami szczawianowymi rozkładając je do dwutlenku węgla opuszczającego środowisko reakcji, a sam przechodzi w siarczan. Zaletą wynalazku jest uzyskanie roztworów siarczanowych cyrkonu(IV) (hafnu(IV)) będących dogodnym substratem do dalszego rozdzielania cyrkonu od hafnu np. wspomnianą metodą wymiany jonowej.The proposed method allows to carry out stable and difficult to decompose and further processing of zirconium (IV) oxalate complexes (hafnium (IV)) into their sulphate solutions, because the used peroxodisulphate reacts with oxalate ions decomposing them into carbon dioxide leaving the reaction medium, and itself transforms into sulphate . The advantage of the invention is to obtain zirconium (IV) (hafnium (IV)) sulfate solutions as a convenient substrate for the further separation of zirconium from hafnium, e.g. by the mentioned ion exchange method.
P r z y k ł a dP r z k ł a d
Do 300 ml wodnego roztworu szczawianowych kompleksów cyrkonu(IV) i hafnu(IV) uzyskanego jako jedna z frakcji z desorpcji tych pierwiastków 0,25 M roztworem szczawianu amonu (skład: 0,25 M C2O4 -; 2,5 g/l Zr, 0,345 g/l Hf) dodano 18,1 g stałego nadtlenodwusiarczanu amonu i ogrzewano przez 3 godziny w temperaturze ok. 120°C. Następnie do roztworu dodano 3,3 ml stężonego kwasu siarkowego i odparowano roztwór do objętości 117 ml w celu uzyskania roztworu cyrkonu(IV) o stężeniu 0,07 M w 0,5 M kwasie siarkowym (całkowite stężenie siarczanów - 1,8 M). Otrzymany roztwór przepuszczono przez 6,5 g żywicy jonowymiennej Diphonix® umieszczonej w szklanej kolumnie o wewnętrznej średnicy 1,1 cm w temperaturze pokojowej. Wyciek odbierano z prędkością 0,4 ml/min. Uzyskano roztwór siarczanu cyrkonu(IV) o obniżonej zawartości hafnu:To 300 ml of an aqueous solution of zirconium (IV) and hafnium (IV) oxalate complexes obtained as one of the fractions from the desorption of these elements with 0.25 M ammonium oxalate solution (composition: 0.25 MC 2 O 4 - ; 2.5 g / l Zr, 0.345 g / l Hf), 18.1 g of solid ammonium peroxodisulfate was added and heated for 3 hours at ca. 120 ° C. Then 3.3 ml of concentrated sulfuric acid was added to the solution and the solution was evaporated to a volume of 117 ml to obtain a 0.07 M solution of zircon (IV) in 0.5 M sulfuric acid (total sulfate concentration 1.8 M). The resulting solution was passed through 6.5 g of Diphonix® ion exchange resin placed in a glass column with an internal diameter of 1.1 cm at room temperature. The leak was collected at a rate of 0.4 ml / min. A zirconium (IV) sulphate solution with a reduced hafnium content was obtained:
a) 1,5 krotnie z wydajnością cyrkonu 70%a) 1.5 times with the efficiency of zirconium 70%
b) 1,7 krotnie z wydajnością cyrkonu 62%b) 1.7 times with the efficiency of zirconium 62%
c) 2,1 krotnie z wydajnością cyrkonu 49%, co odpowiada separacji przeprowadzonej z roztworu siarczanu cyrkonu(IV) o zbliżonych parametrach (stężenie cyrkonu(IV), hafnu(IV) i siarczanów) przygotowanego wprost z siarczanu cyrko-c) 2.1 times with a zirconium yield of 49%, which corresponds to the separation carried out from a solution of zirconium (IV) sulphate with similar parameters (concentration of zircon (IV), hafnium (IV) and sulphates) prepared directly from zirconium sulphate
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL403863A PL227656B1 (en) | 2013-05-13 | 2013-05-13 | Method for preparing solutions of zirconium sulfate(IV) and hafnium(IV) with the solution of oxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL403863A PL227656B1 (en) | 2013-05-13 | 2013-05-13 | Method for preparing solutions of zirconium sulfate(IV) and hafnium(IV) with the solution of oxalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL403863A1 PL403863A1 (en) | 2014-11-24 |
| PL227656B1 true PL227656B1 (en) | 2018-01-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| PL403863A PL227656B1 (en) | 2013-05-13 | 2013-05-13 | Method for preparing solutions of zirconium sulfate(IV) and hafnium(IV) with the solution of oxalate |
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| Country | Link |
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| PL (1) | PL227656B1 (en) |
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- 2013-05-13 PL PL403863A patent/PL227656B1/en unknown
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| Publication number | Publication date |
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| PL403863A1 (en) | 2014-11-24 |
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