CN85101874A - P507 extration resin chromatography is separated and extraction HIGH PURITY THULIUM OXIDE and lutecium oxide - Google Patents

Abstract

The invention belongs to the chromatographic separation of element.Can be used for industrial-scale production HIGH PURITY THULIUM OXIDE and lutecium oxide, more with short production cycle than ion exchange method, the purity height, present method is a stationary phase with the P507 extration resin, with hydrochloric acid is moving phase, chromatography separation and Extraction HIGH PURITY THULIUM OXIDE and lutecium oxide from rareearth enriching material fast and efficiently on the post, Tm ₂O ₃Purity＞99.995%, yield 90～98%, Lu ₂O ₃Purity 99.99%, yield 75～85%.

Description

P507 extration resin chromatography is separated and extraction HIGH PURITY THULIUM OXIDE and lutecium oxide

The invention belongs to the chromatographic separation rare earth element, from the enriched substance of thulium and lutetium, extract the novel method of HIGH PURITY THULIUM OXIDE and lutecium oxide.

Solvent extraction and ion exchange method are mainly adopted in the separation of plant-scale rare earth element, and the former selectivity is good, latter's separation efficiency height.And the extraction high-purity rare-earth then biases toward the ion exchange method ion exchange method because the formation and the dissociation reaction speed of complex compound are slow, causes separation cycle long.

The present inventor as far back as 1975 at first with P ₅₀₇(abbreviation of the own ester of 2-ethylhexyl phosphonic acid single 2-ethyl) is used for extraction-chromatography rare-earth separating (Peng Chunlin, Ji Yongyi, Lu Anqiu etc.; Analytical chemistry 8(4) 318(1980); Peng Chunlin, Cui Yongde, Song Qingxiu analytical chemistry 11(7) 489(1983), it merges the high efficiency of solvent-extracted highly selective and ion-exchange chromatography, 15 rare earth elements have been separated quantitatively, in rare earth analysis, obtained using widely, showed favorable industrial application prospect.

In recent years, the domestic P that occurred ₅₀₇Extration resin, it is with P ₅₀₇Extraction agent is aggregated in vinylbenzene, and a kind of novel extraction resin on the skeleton of divinylbenzene is to be the improvement of carrier to silica gel, still is mainly used in rare earth analysis and separates.

The objective of the invention is to adopt P ₅₀₇The extration resin chromatography, from rareearth enriching material efficiently, separation and Extraction high purity rare earth oxides apace.

P set forth in the present invention ₅₀₇The technology of extration resin chromatography separation and Extraction HIGH PURITY THULIUM OXIDE and lutecium oxide is: with-50～200 purpose P ₅₀₇Extration resin (0.55 gram P ₅₀₇/ gram resin) be the ratio of the post footpath of stationary phase chromatographic column and height between 1/15 to 1/40, be moving phase with 0.7～4N hydrochloric acid, be raw material with 70～90% grade person's rareearth enriching materials, the mode (flow velocity 0.2～1ml/cm of employing gradient elution ²Divide) chromatography rare-earth separating on the post, and Er, Tm appear successively, Yb, Lu(are positive sequence), the fraction collection effluent liquid, with oxalate precipitation, and calcination becomes oxide compound after the enrichment.

When adopting present method separation and Extraction thulium and lutetium, the separation factor β of adjacent rare earth ^Tm _Er=3.14, β ^Yb _Tm=2.94, β ^Lu _Yb=1.76, rare earth loaded heavy increase, separation factor descends, and adopts technology of the present invention, advances post with the rareearth enriching material of 70～90% grades, can once obtain purity 〉=99.995%Tm ₂O ₃, yield 90～98% also can obtain purity and be 99.99% Lu ₂O ₃, yield 75～85%.The elution acidity of present method is lower, and lower more than 1～3 times than HDEHP and HEH φ P, separation cycle is short, the top condition of using φ 50mm post was respectively 18～23 hours thulium and lutetium, faster more than 20 times than ion exchange method, using the inventive method has tangible economic benefit, every processing 1Kg80%Tm ₂O ₃Enriched substance can obtain 750 the gram about purity＞99.995%Tm ₂O ₃, amount to 1300 yuan of Renminbi, 176 yuan of Renminbi are amounted in chemical reagent consumption.Every processing 1Kg80%Lu ₂O ₃Enriched substance can obtain 640 gram left and right sides purity and be 99.99% Lu ₂O ₃, amount to 1920 yuan of Renminbi, 244 yuan of Renminbi are amounted in chemical reagent consumption.

The preparation of example 1. high-purity thuliums

Use φ 50mm chromatographic column, post height/1500mm, there is the glass sand filter disc post lower end, and post has constant temperature circulation sleeve pipe outward, and the control column temperature is 50 ℃, takes by weighing 750 gram-50+200 order P ₅₀₇Extration resin, after the dilute hydrochloric acid immersion with 2 times of volumes, the slurry method is adorned post, takes by weighing 3～10% magnetic rare earth oxide (2%Er of chromatographic column total amount ₂O ₃, 80%Tm ₂O ₃17%Yb ₂O ₃, 1%Lu ₂O ₃) with behind 1: 1 dissolving with hydrochloric acid, steam near and do, add the water dissolution of 10 times of amounts, advance post, control flow velocity 1～4 ml/min, again with 0.7～1.5N hydrochloric acid wash-out Ev, 1.5～2.6N hydrochloric acid wash-out Tm and Yb, 2.6～4N salt pickling acid Yb and Lu, the elution of ladder acidity, substep is collected, and uses inductance coupling plasma emissioning spectral analysis, Ho in the working sample ₂O ₃, Y ₂O ₃, Er ₂O ₃, Yb ₂O ₃, Lu ₂O ₃Content, main body solution becomes oxide compound through the oxalate precipitation calcination.Products obtained therefrom Tm ₂O ₃Purity 〉=99.995%, yield 90～98%, obtaining purity simultaneously is 98～99.95%Er ₂O ₃, Yb ₂O ₃, Lu ₂O ₃Yield＞90%.

The preparation of example 2. high-purity lutetiums

Use φ 50mm chromatographic column, the high 1500mm of post, there is the glass sand filter disc post lower end, and post has constant temperature circulation sleeve pipe outward, and controlled temperature is 50 ℃, takes by weighing 1Kg-50+200 order P ₅₀₇Extration resin, after soaking with the dilute hydrochloric acid of 2 times of volumes, slurry method dress post takes by weighing 3～10% rare earth oxide (20%Yb of chromatographic column total amount ₂O ₃, 80%Lu ₂O ₃) with behind 1: 1 dissolving with hydrochloric acid, steam near and do, the water dissolution that adds 10 times of amounts, advance post, control flow velocity 1～4 ml/min is earlier with 1.0～2.6N hydrochloric acid wash-out Yb, continue with 2.6～4.0N hydrochloric acid wash-out Lu, the elution of ladder acidity, fraction collection is with Ho in the inductance coupling plasma emissioning spectral analysis working sample ₂O ₃, Y ₂O ₃, Er ₂O ₃, Tm ₂O ₃, Yb ₂O ₃And Lu ₂O ₃Content, main body solution becomes oxide compound through the oxalate precipitation calcination, products obtained therefrom Lu ₂O ₃Purity be 99.99% yield 75～85%, still can obtain purity＞99.95%Yb ₂O ₃, yield 80%.

Claims (3)

1, the method for a kind of separation and Extraction HIGH PURITY THULIUM OXIDE and lutecium oxide, it is characterised in that: at 50 ℃, with-50+200 order P ₅₀₇Extration resin is a stationary phase, is moving phase with 0.7～4.0N hydrochloric acid, with the enriched substance raw material of thulium and lutetium, and in the mode of ladder acidity elution, chromatographic separation on the post.

2, as the described chromatography separating method of claim 1., its feature also is the ratio of the post footpath of chromatographic column and height between 1: 15 to 1: 40, and the useful load of rare earth is between 3% to 10%.

3, as the described chromatography separating method of claim 1., its feature is that also the speed of moving phase is at 0.2～1.0ml/cm ²Divide