CN103045862B - Separation and purification method of trace hafnium in rock - Google Patents

Separation and purification method of trace hafnium in rock Download PDF

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CN103045862B
CN103045862B CN201310001366.6A CN201310001366A CN103045862B CN 103045862 B CN103045862 B CN 103045862B CN 201310001366 A CN201310001366 A CN 201310001366A CN 103045862 B CN103045862 B CN 103045862B
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hcl
purification method
rock
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mixed solution
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CN103045862A (en
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凡金龙
张生栋
丁有钱
杨磊
杨志红
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China Institute of Atomic of Energy
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China Institute of Atomic of Energy
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Abstract

The invention belongs to the technical field of radiochemical separation, and discloses a separation and purification method of a trace hafnium in a rock. The method comprises the following two steps that (1), a rock sample is dissolved and adjusted as an HNO3 medium, the medium serves as an upper P350 column of upper column liquid, and then Hf is washed by an eluting agent HNO3, and desorbed by a desorbent HNO3-HCl; (2), an Hf sample in Step (1) is adjusted as an H2SO4-Cit mixed liquid medium, an organic phase is obtained through extraction with N1923-dimethylbenzene, washed by H2SO4-Cit mixed liquid, and then subjected to reverse extraction by HCl-HF mixed liquid, reverse extraction liquid is placed on a TOA chromatographic column, the column is washed by HCl-HF, and effluent liquid is purified Hf product liquid. The method has the advantages that the separation flow is simple, the Hf recovery rate is greater than 98%, and the decontamination factor is high.

Description

The separation purification method of trace hafnium in rock
Technical field
The invention belongs to Radiochemical Separation technical field, be specifically related to the separation purification method of trace hafnium in rock.
Background technology
Right 182the analysis and research of Hf occupy critical role in geoscience.Due to 182hf content is extremely low, and the rock sample amount of need analyzing is less than the usage quantity of 1g much larger than trace element analysis in the geological sample of bibliographical information up to 10g().On the other hand, rock sample system is very complicated, not only contains the matrix element (Na, K, Ca, Mg, Ba, Al, Fe, Ti) of a large amount of constants, and also has a lot of trace elementss.Therefore Hf chemical recovery rate is high, decontamination factor is high and removal, need to set up one 182separation and purification process that W disturbs.
From rock sample, the method for separating hafnium mainly contains ion exchange method and chromes, wherein chromes are owing to having the high efficiency of solvent-extracted highly selective and ion-exchange chromatography concurrently, be widely used in the separation between metal ion, the especially very close interionic separation of chemical property.
Yang etc. have carried out the method research of single-column extraction chromatography separated Zr-Hf from high Ti geological sample, set up the method for TNOA/Aliquat336-HCl extraction chromatography system separated Hf, Zr from Al, Fe, the basalt that Ti content is high, thick andesite stone of single-column separation, but this method cannot separated Nb and Ta, and Fe and same Zr, Hf extract reservation jointly, thereby affect the retention rate of Zr, Hf.
Le Fevre etc. has set up LiBO 2alkali fusion dissolves geological sample, U-TEVA resin-HNO 3the separated Zr+Hf of extraction chromatography system single-column, then measures the isotopic method of Hf with MC-ICP-MS.With 3mol/LHNO 3-0.3%H 2o 2upper prop also washes away most of rock matrix element (Al, P, Ti, Cr, Fe, Mo etc.); 0.5mol/L HF desorb Hf+Zr(Th, U are also desorbed), in this method, between Hf and Zr, Th, U, fail to realize completely separated.
Money journey has been studied P 350the method of trace Hf and Zr in the separated rock sample of (extraction) extraction chromatography.The simulated system of the method is comparatively simple, with 6mol/L HNO 3for upper prop liquid retains Zr and Hf, with 6mol/L HCl desorb Hf and separated with Zr, but this method used to free liquid system very complicated, and have certain conditions of streaking.
Utilize AMS to measure 182hf is easily subject to nuclear isobar 182the interference of W, existing a lot of about the Hf report separated with W in the world at present.A kind of simple solvent extraction method of Maji etc. development is separated for Hf and W's, with 0.3mol/L TOA-hexanaphthene at 6mol/L HCl medium (containing a small amount of H 2o 2) in can efficiently extract W and substantially not extract Hf, the separation factor of W and Hf reaches 1.6 * 10 6, separated milligram magnitude Hf and W, and measure with AMS.But when HCl concentration is greater than 2mol/L, extraction there will be third phase, bring to operation and measurement unfavorable.Further experiment shows, in the situation that not adding Hf (IV) with W (VI), still occurs third phase, and along with acid concentration and extractant concentration increase, third phase is more obvious.Fan Jinlong etc. are in < < amine extractant high efficiency separation Hf(IV) with W(VI) method research > > in the separation method of Hf and W is disclosed, but that uses is the liquid-liquid extraction of TOA-dimethylbenzene but not utilizes TOA post, can not directly utilize in actual applications disclosed Parameter Conditions in document to carry out.
Summary of the invention
(1) goal of the invention
According to the existing problem of prior art, the separation purification method of Hf in the rock sample that the invention provides that a kind of separation process is simple, Hf rate of recovery >98%, decontamination factor is high.
(2) technical scheme
In order to solve the existing problem of prior art, technical scheme provided by the invention is as follows:
The isolation and purification method of trace hafnium in rock, the method comprises two portions:
(1) after rock sample is dissolved, be adjusted to HNO 3medium is as P on upper prop liquid 350post, then uses eluent HNO 3washing, finally uses strippant HNO 3-HCl desorb Hf.
(2) Hf sample is adjusted to H 2sO 4-Cit(citric acid) mixed solution medium, uses N 1923-xylene extraction obtains organic phase and uses H 2sO 4the washing of-Cit mixed solution, then uses the back extraction of HCl-HF mixed solution, TOA chromatograph post on strip liquor, and wash pillar with HCl-HF, effluent liquid is the Hf product liquid after purifying.Its preferred version is:
(1) after rock sample is dissolved, be adjusted to 8 ~ 10mol/L HNO 3p on medium 350post, then uses 9 ~ 11mol/L HNO 3as eluent washing, remove major element (as Na, K, Ca, Mg, Ba, Al, Fe, Ti), trace rare earth elements and similar element (as Zr, Th, U), finally use 2.2 ~ 2.5mol/LHNO 3-2.2 ~ 2.5mol/L HCl desorb Hf.
(2) Hf sample is adjusted to 3 ~ 3.5mol/L H 2sO 4-5 ~ 6%(massfraction) Cit mixed solution medium, by 6 ~ 7%(volume fraction) N 1923-xylene extraction obtains organic phase also with 3 ~ 3.5mol/LH 2sO 4-5 ~ 6%Cit mixed solution washing, then use the back extraction of 8 ~ 9mol/L HCl-0.05 ~ 0.1mol/L HF mixed solution, adds 1 ~ 5mg abundance to be greater than 96% in strip liquor 186w, then goes up TOA chromatograph post, and washs pillar with 8 ~ 9mol/L HCl-0.05 ~ 0.1mol/L HF, and effluent liquid is the Hf product liquid after purifying.
Described P 350post, TOA chromatograph post are by P 350extraction agent, TOA extraction agent are adsorbed on acidproof, corrosion resistant solid-state balustrade.
(3) beneficial effect
Adopt the beneficial effect that technical scheme provided by the invention has to be: (1) whole sepn process is simple, without medium, transform, simple to operate.At separation phase, only need single-column operation, the interference that just can remove major element and trace elements.(2) good separating effect.The rock sample amount of analyzing in the present invention is up to 10g, and separating difficulty is large.Adopt P 350post carries out separation to Hf, and accurately to control nitration mixture desorption condition be that concentration is 2.2 ~ 2.5mol/LHNO 3-2.2 ~ 2.5mol/L HCl, makes the separation phase Hf rate of recovery up to 98% and the decontamination factor of major element, trace rare earth elements and similar element is greater than to 10 3.(3) purification effect is good, and in the present invention, the magnitude difference of Hf and W is up to 3 magnitudes, and purifying acquires a certain degree of difficulty.Adopt primary amine N 1923organically combine by HCl medium with the amine extractant such as tertiary amine TOA, both without extra media conversion operations, can obtain again more efficient Hf-W separated.N wherein 1923extraction agent not only can be removed monovalence, divalence, trivalent rare earth etc. and be further purified Hf compared with lower valency element, TOA extraction chromatography high efficiency separation Hf-W under 8 ~ 9mol/L HCl-0.05 ~ 0.1mol/LHF system, with TOA multistep extraction process, compare, the method operation is easier, uses vessel few.In addition, before upper TOA chromatograph post step, added 96% 186w, as isotopic dilution agent, further improves the decontamination factor of W.In the finished product that obtain, the Hf rate of recovery is greater than 98%, and the decontamination factor of W is greater than to 10 6.
Accompanying drawing explanation
Fig. 1: elution curve figure in Hf sepn process;
Fig. 2: Zr, Hf separation factor under the strippant condition of different concns.
Embodiment
Below in conjunction with embodiment and Figure of description, the present invention is further elaborated:
Operation steps of the present invention is as follows:
(1) dissolve rock sample, dress post and pre-equilibration
Accurately take 10g rock sample in 50mL polytetrafluoroethylene beaker, use acid by its dissolving.In order to verify the effect of the method, in lysate, accurately add tracer agent: activity is 1000Bq 175hf; 0.6mgK; 1mg Ca; 0.9mg Mg; 0.4mg Al; 1mg Fe; 0.5mg Ti; 0.9mg La; 0.9mg Eu; 0.9mg Lu.Upper prop liquid is long-pending: 6mL; Free column volume: 3.5mL; Flow velocity: 0.3mL/L.Lysate is adjusted to 8 ~ 10mol/L HNO 3the P that after medium, upper pre-equilibration is crossed 350chromatograph post, makes the whole upper props of sample.
(2) separation of Hf
With 40mL9 ~ 11mol/L HNO 3washing pillar, removes the major element (as Na, K, Ca, Mg, Ba, Al, Fe, Ti), trace rare earth elements and the similar element (as Zr, Th, U) that by chromatograph post, are not retained, HNO 3medium and washing composition HNO 3the tracer agent elution curve figure of concentration while being 10mol/L as Fig. 1, in the present invention, the content of tracer agent is measured with mass spectrum, 175the content of Hf is to measure with HpGe.
In the sepn process of Hf, because Zr is very similar to the chemical property of Hf, both separation factors are more conducive to more greatly the separation of Hf, and Fig. 2 is Zr, Hf separation factor under different strippant concentration.As can be seen from Figure, when strippant is 2.2 ~ 2.5mol/L HNO 3during-2.2 ~ 2.5mol/L HCl, separation factor is maximum.With after strippant desorb, collect effluent liquid, obtain Hf in rock.
(3) purifying of Hf
By after Hf sample effluent liquid evaporate to dryness, be adjusted to 3 ~ 3.5mol/L H 2sO 4-5 ~ 6%Cit mixed solution medium is also transferred in 60mL separating funnel, with 10mL5 ~ 7%N 1923-xylene extraction obtains organic phase also with 3 ~ 3.5mol/LH 2sO 4the washing of-5 ~ 6%Cit mixed solution, then uses the back extraction of 8 ~ 9mol/L HCl-0.05 ~ 0.1mol/LHF mixed solution, 0.5mol/L TOA chromatograph post on strip liquor, and wash pillar with 8 ~ 9mol/L HCl-0.05 ~ 0.1mol/LHF, effluent liquid is the Hf product liquid after purifying.
Described P 350post, TOA chromatograph post are by P 350extraction agent, TOA extraction agent are adsorbed on acidproof, corrosion resistant solid-state balustrade.
Embodiment 1
Identical with aforesaid operations method, different is Parameter Conditions, and its Parameter Conditions and effect are as table 1.
The Parameter Conditions that table 1 is different and effect
Embodiment 2
Identical with aforesaid operations method, different is Parameter Conditions, and its Parameter Conditions and effect are as table 2.
The Parameter Conditions that table 2 is different and effect
Embodiment 3
Identical with aforesaid operations method, different is Parameter Conditions, and its Parameter Conditions and effect are as table 3.
The Parameter Conditions that table 3 is different and effect
Embodiment 4
Different from aforesaid operations method, in step (3) on strip liquor before TOA post, in strip liquor, add 1 ~ 5mg abundance be 97% concentrated 186w(wherein 182w only has several piks) as isotopic dilution agent, other Parameter Conditions is with embodiment 3, and its result is as following table:
Table 4 adds isotopic dilution agent 186the purification effect of W

Claims (9)

1. the separation purification method of trace hafnium in rock, the method comprises separated and two stages of purifying, it is characterized in that, the method comprises following two steps:
(1) after rock sample is dissolved, be adjusted to HNO 3medium is as P on upper prop liquid 350post, then uses eluent HNO 3washing, finally uses strippant HNO 3-HCl desorb Hf;
(2) the Hf sample in step (1) is adjusted to H 2sO 4-Cit mixed solution medium, uses N 1923-xylene extraction obtains organic phase, organic phase H 2sO 4the washing of-Cit mixed solution, then uses the back extraction of HCl-HF mixed solution, TOA chromatograph post on strip liquor, and wash pillar with HCl-HF, and effluent liquid is the Hf product liquid after purifying, strip liquor adds 1～5mg before upper TOA chromatograph post 186the agent of W isotopic dilution, 186the abundance of W is greater than 96%.
2. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, HNO in described step (1) 3the concentration of medium is 8～10mol/L.
3. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, the eluent HNO in described step (1) 3concentration be 9～11mol/L.
4. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, in described step (1), strippant is 2.2～2.5mol/L HNO 3-2.2～2.5mol/L HCl.
5. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, described step is adjusted to 3～3.5mol/L H by Hf sample in (2) 2sO 4-5～6%Cit mixed solution medium.
6. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, N in described step (2) 1923the volume fraction of-dimethylbenzene is 6～7%.
7. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, H in described step (2) 2sO 4the washing of-Cit mixed solution is with 3～3.5mol/L H 2sO 4the washing of-5～6%Cit mixed solution.
8. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, described step (2) is middle with the back extraction of 8～9mol/L HCl-0.05～0.1mol/L HF mixed solution.
9. the separation purification method of trace hafnium in rock according to claim 1, is characterized in that, in described step (2), with 8～9mol/L HCl-0.05～0.1mol/L HF, washs pillar.
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CN103337265B (en) * 2013-06-21 2016-01-20 中国原子能科学研究院 For the Chemical Decomposition flow process of spent fuel element burnup analysis
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Citations (1)

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CN101209858A (en) * 2006-12-28 2008-07-02 北京有色金属研究总院 Method for separating zirconium hafnium by tributyl phosphate extraction chromatography method

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Publication number Priority date Publication date Assignee Title
CN101209858A (en) * 2006-12-28 2008-07-02 北京有色金属研究总院 Method for separating zirconium hafnium by tributyl phosphate extraction chromatography method

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* Cited by examiner, † Cited by third party
Title
凡金龙，等."胺类萃取剂高效分离Hf(Ⅳ)与W(Ⅵ)的方法研究".《核化学与放射化学》.2010,第32卷(第4期),204-205.
凡金龙,等."胺类萃取剂高效分离Hf(Ⅳ)与W(Ⅵ)的方法研究".《核化学与放射化学》.2010,第32卷(第4期),204-205. *

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