CN85102210B - Process for seperation of mixed rare-earths by ammoniated heh (ehp) - Google Patents
Process for seperation of mixed rare-earths by ammoniated heh (ehp) Download PDFInfo
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Abstract
The grouping and separation of ion-adsorbing rare earth ore mainly comprising light rare earth by aminated P507 through solvent extraction belongs to hydrometallurgical solvent extraction. Simulated string extraction grouping and separation are carried out to the chloride water solution of ion-adsorbing rare earth ore mainly comprising light rare earth in a liquid dividing funnel having 90 to 120 stages by using 20 to 45 % of aminated P507 kerosene as an extractant, washing solution and 0.8 to 5NHC1 of back extraction acids, the extractant has the concentration of 1 to 7M, and the chloride water solution has the concentration of 1 to 2M; three groups of rare earth having light, medium and heavy weight are obtained by Nd-Sm, La-Ge and Tb-Dy grouping separation, the three groups of rare earth are substances respectively enriching in Ce, Pr and Nd, Sm, Eu, Gd, Tb and Dy, and Dy, Ho, Er, Tm, Yb, Lu and Y, and La2O3 having larger than 99.97 % of purity and larger than 99 % of yield is also obtained.
Description
The invention belongs to hydrometallurgical solvent extraction
Someone adopts HEH(EHP to bastnasite-monazite mixing ore deposit) hydrochloric acid system, carry out Nd-Sm, Ce-Pr, the La-Ce grouping separates or light, the full extraction of middle-weight rare earths separates continuously.Its Nd-Sm, the rare earth of going into organic phase that comes together after the La-Ce grouping separates accounts for the 2-6% and 63% of total points from rare earth respectively.Li Deqian etc. exist: " with 2-ethylhexyl phosphonic acids list-2 ethylhexyl ester extracting and separating rear earth element, cerium (IV); the research of scandium and thorium " rare earth collection of thesis, Science Press, mention with part ammonification HEH(EHP in the nineteen eighty-two 20-29 page or leaf) extraction of dividing into groups, and compared the ammonification and the extraction ability of ammonification two extraction agents not, propose in the literary composition to carry out Nd-Sm grouping, the grouping back rare earth of going into organic phase that comes together and account for total points from 73% of rare earth to containing aqueous chloride solution based on the ion adsorption type rare earth ore of heavy rare earths.But use ammonification HEH(EHP) aqueous chloride solution that contains based on the ion adsorption type rare earth ore of light rare earths is carried out Nd-Sm, grouping is not reported.
The present invention carries out same Nd-Sm to the aqueous chloride solution that contains based on the ion adsorption type rare earth ore of light rare earths, the La-Ce grouping, its rare earth that comes together into organic phase accounts for 32-35% and the 45-55% of total points from rare earth respectively, carry out the Tb-Dy grouping simultaneously, in making, heavy rare earths obtains enrichment respectively, the ion adsorption type rare earth ore that contains based on light rare earths is different from bastnasite-monazite mixing ore deposit, solitary stone ore, the rare earth of xenotime etc. is formed, it is very big that their content also differs, therefore at the composition and different requirements of different rare-earth mineral, one and its corresponding reasonably extraction process flow just must be proposed.
The objective of the invention is at the composition that contains based on the ion adsorption type rare earth ore of light rare earths, use ammonification HEH(EHP) solvent extraction carries out Nd-Sm, La-Ce, Tb-Dy grouping separate finally obtain three be respectively, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and the enriched substance of Dy, Ho, Er, Tm, Yb, Lu, Y and purity greater than 99.97% yield greater than 99% La203.
The present invention ammonification HEH(EHP)-kerosene makes extraction agent, the first step grouping is by carrying out between the Nd-Sm, the grouping back only has about 2% at La-Nd raffinate aqueous phase Ce content, second step separated between La-Ce, can obtain like this purity greater than 99.97% yield greater than 99% La203 and Ce, Pr, Nd enriched substance.The 3rd step divided into groups to Sm-Lu, Y in the organic phase of coming together after the Nd-Sm grouping, made content in the ore deposit only obtain enrichment at the Eu that Tb and the content of 0.2-0.5% is 0.2-1.0%, thereby in obtaining, two groups of enriched substance of heavy rare earths.
Above-mentioned grouping separate obtain three contain light, in, the heavy rare earths enriched substance is next step extracting and separating or ion-exchange, or extraction chromatography separates single rare earth favourable condition is provided.Collection is gone into the rare earth ion of organic phase and the H in the acidic phosphonate in extraction process
+Exchange, aqueous phase acidity is constantly raise, influence further extracting and separating,, just must add alkali to keep aqueous phase acidity in certain limit for maintaining extracting and separating under certain separating factor condition.Ammonification HEH(EHP of the present invention) single port or twoport are imported the alkali mode and change into the extraction agent introducing port and merge into one, so both reduced equipment, be convenient to operation again.Ammonification HEH(EHP) except improving the extracting and separating factor, because ammonium ion has replaced H
+, make the acidity of water can remain on certain level all the time, rare earth ion and ammonium ion exchange, and have improved the operation capacity of organic phase like this, and rare earth ion concentrations at different levels change gently in the extraction section, make that operation is easier to be carried out.For reaching better separation purpose, must use mineral acid to wash acid, the rare earth of unnecessary extracted organic phase is washed, play fractionation, to reach the satisfied separating effect of expection.
The present invention is composed as follows with containing based on the ion adsorption type rare earth ore mixed rare-earth oxide of light rare earths: La35-36; Ce0.1-0.85; Pr5-10; Nd20-30; Sm 3.4-10.4; Eu0.2-1.0; Gd2.45-5.3; Tb0.22-0.5; Dy1.8-3.2; Ho0.1-0.51; Er0.99-1.75; Tm0.11-0.25; Yb0.96-1.8; Lu0.02-0.2; Y12.18-20, make 1-2M aqueous solution of rare earth chloride pH2-4 with dissolving with hydrochloric acid, by extraction, reinforced washing, the 90-120 level separatory funnel simulation tandem that all unit of stripping section are formed is carried out gently, in, the heavy rare earths grouping separates, with ammonification HEH(EHP in a mixing agitated pool), add ammonification HEH(EHP respectively at extraction phase washing section two ends) and washings, reinforced level adds and contains the aqueous solution that mixes rare earths material or contain the organic phase solution that comes together into rare earth, two ends are flowed out the aqueous solution that contains the raffinate rare earth and the organic phase solution that contains rare earth respectively, import next extraction then, a reinforced washing section is as the further extracting and separating of stock liquid, perhaps organic phase solution is imported an end of stripping section, the other end imports strip liquor, two ends are flowed out isolating rare earth aqueous solution and extraction agent HEH(EHP respectively), extraction agent import mixed in the agitated pool to mix mutually with a certain amount of strong aqua obtaining the ammonification HEH(EHP that can continue to use) (its flow process is seen figure).
The present invention uses ammonification HEH(EHP) extraction agent, its general expression:
(R is the 2-ethylhexyl in the formula)
With the not miscible HEH(EHP of water) (the basic ester of 2-ethylhexyl phosphonic acids single 2-ethyl) be thinner with kerosene, at 1-1.7M HEH(EHP) add a certain amount of concentrated ammonia solution in the kerosene, its ammonification degree is HEH(EHP) 20-45%(be ammonification HEH(EHP) account for total HEH(EHP before the ammonification) and percentage composition).Washings is 0.4-1.5N HCl, and strip liquor is 1-1.5N HCl and 4.5-4.8N HCl.
The present invention is with 43% ammonification 1.5M HEH(EHP)-kerosene and 1.5M HEH(EHP) kerosene, be that 0.108M and Tb, Dy aqueous chloride solution extract Tb, the Dy separating factor is measured to concentration, the Tb-Dy separating factor brings up to 2, the results are shown in Table 1.
The present invention is a raw material with the 1.5-1.8M mixed rare earth chlorides aqueous solution, pH2-3, with 34-36% ammonification 1.5M HEH(EHP)-kerosene carries out Nd-Sm grouping, washings 0.4-0.6N HCl, feed liquid, washings, the flow of extraction agent is respectively 0.281/hr, 0.221/hr, 1.081/hr, carry out the multi-stage countercurrent fractionation extraction, get water La-Nd, wherein contain Sm＜0.05%, collection is gone into the Sm-Lu in the organic phase solution, it is stock liquid with the raffinate water that Y contains Nd＜0.05%, with 34-36% ammonification 1.5M HEH(EHP)-kerosene carries out La-Ce and separates purification La, washings is 0.8-1.2N HCl, feed liquid, washings, the flow of extraction agent is respectively 0.361/hr 0.121/hr and 0.91/hr, carry out the multi-stage countercurrent fractionation extraction and get pure La, its purity is greater than 99.97%, yield is greater than 99%, it comes together into the Ce of organic phase, Pr, the rare earth of Nd, with back extraction acid 1-1.5N HCl, carry out the aqueous chloride solution that multi-stage countercurrent back extraction tandem must contain Ce-Nd, its flow that contains rare earth organic phase and back extraction acid is respectively 0.31/hr and 0.061/hr.Coming together into the organic phase solution of Sm-Lu, Y after Nd-Sm grouping) as feeding liquid, with 34-36% ammonification 1.5M HEH(EHP-kerosene and washings 1.3-1.5N HCl carry out Tb-Dy and divide into groups, its feed liquid, washings, extraction agent flow are respectively 0.61/hr0.171/hr and 0.211/hr carries out the multi-stage countercurrent fractionation extraction, get raffinate water Sm-Dy, Tb yield～100% is Dy～6% and contain Dy-Lu, the organic phase solution of Y wherein.The latter carries out multi-stage countercurrent back extraction tandem with back extraction acid 4.5-4.8N HCl, must contain DY-Lu, the aqueous chloride solution of Y, and its flow that contains rare earth organic phase and back extraction acid is respectively 0.181/hr and 0.061/r.
The present invention can obtain implementing in factory.
Accompanying drawing 1 explanation of the present invention: (1) ammonification HEH(EHP)-kerosin; (2) concentrated ammonia solution; (3) HEH(EHP after the back extraction)-kerosene; (4) (4) ' washings and strip liquor; (5) contain the aqueous chloride solution that mixes rare earth; (6) the La-Nd aqueous solution of raffinate; (7) contain La purity＞99.97%, the aqueous solution of yield＞99%; (8) contain Ce, Pr, Nd organic phase solution; (9) contain the aqueous solution of Ce-Nd; (10) contain the organic phase solution of Sm-Lu, Y; (11) contain the aqueous solution (Tb yield＞90) of Sm-Dy; (12) contain Dy-Lu, the Y organic phase solution; (13) contain Dy-Lu, the aqueous solution of Y.
Realize that example of the present invention is as follows, present embodiment is that main ion adsorptive type rare earth ore deposit is a separate object with the light rare earths.
Example 1 is with the aqueous chloride solution pH2-3 of 1.5-1.8M mishmetal, 0.281/hr; Washings 0.4-0.6N HCl, 0.221/hr; With 34-36.8% ammonification 1.5M HEH(EHP)-kerosene 1.0811/hr; At 22 stage countercurrent fractionation cascade extractions, get raffinate water La-Nd, contain Sm＜0.05%, collection is gone into the Sm-Lu in the organic phase solution, and Y wherein contains Nd＜0.05%.
Example 2 contains rare earth oxide with 0.5-0.7M and consists of La45%Ce2%; Pr12%, after the aqueous solution of rare earth chloride of Nd41% or the Nd-Sm grouping, the raffinate aqueous phase solution that contains La-Nd is as feeding liquid, 0.361/hr; Washings is 0.8-1.2NHCl0.121/hr; With 34-36% ammonification 1.5M HEH(EHP)-kerosene, 0.91/hr is at 25 stage countercurrent fractionation cascade extractions, pure La, its purity greater than 99.97% yield greater than 99%.
Example 3 is gone into Sm-Lu with the collection that obtains after example 2 groupings, and the organic phase solution of Y is as feeding liquid, and concentration is 0.15-0.17M, 0.61/hr, washings 1.3-1.5N HCl, 0.171/hr; With 34-36% ammonification 1.5M HEH(EHP)-kerosene 0.211/hr; At 35 stage countercurrent fractionation cascade extractions, raffinate water SM-Dy, Tb yield～100%, wherein Dy is 6% and contains Dy-Lu, the organic phase solution of Y.
Example 4, containing Dy-Lu, the organic phase solution of Y, concentration is 0.06-0.1M, 0.181/hr, back extraction acid 4.5-4.8N HCl, 0.061/hr, in 6 stage countercurrent back extraction tandems, 0.18-0.3M contain Dy-Lu, the aqueous solution of Y.
Example 5, to contain the organic phase solution of Ce, Pr, Nd, concentration is 0.9-0.15M 0.31/hr; Back extraction acid 1-1.5N HCl0.061/hr in 6 stage countercurrent back extraction tandems, gets the aqueous solution that 0.45-0.75M contains Ce-Nd.
Claims (4)
1, a kind of HEH(EHP) with the part ammonification-kerosene is the technology of extraction agent rare-earth separating, it is characterized in that raw material is concentration 1.5-1.8M, pH2-3 contains the aqueous chloride solution that light rare earths is main ion adsorption type rare earth ore, carrying out the Nd-Sm grouping is to make washings with 0.4-0.6N HCl, and stream is than being extracted organic phase: feed liquid: washings=1: 0.28: 0.22; Carry out La-Ce grouping and be feed liquid with the raffinate water of Nd-Sm grouping, its concentration is 0.5-0.7M, make washings with 0.8-1.2N HCl, its stream is than being extracted organic phase: feed liquid: washings=0.9: 0.36: 0.12, gained contain the organic phase of Ce, Pr, Nd and carry out back extraction again; Carrying out the Tb-Dy grouping is to make feed liquid with the organic phase after the Nd-Sm grouping, concentration is 0.15-0.17M, makes washings with 1.3-1.5N HCl, and stream is than being extracted organic phase: organic feed liquid: washings=0.21: 0.6: 0.17, gained contains Dy-Lu, and the organic phase of y is carried out back extraction again.
2, as the described extracting and separating rear earth technology of claim 1, it is characterized in that HEH(EHP) with kerosene as thinner, before entering extraction section, in agitated pool, mix earlier with a certain amount of ammonia soln the 1-1.7M HEH(EHP of 20-45% ammonification degree) the kerosene extraction organic phase.
3, as the described extracting and separating rear earth technology of claim 1, it is characterized in that gained is contained the organic phase of Ce, Pr, Nd, make strip liquor with 1-1.5N HCl, stream is than for organic phase: back extraction acid=5: 1 must contain the aqueous chloride solution of Ce, Pr, Nd through the multi-stage countercurrent back extraction.
4, as the described extracting and separating rear earth technology of claim 1, it is characterized in that gained is contained Dy-Lu, the organic phase of y, with 4.5-4.8N HCl, stream is than for organic phase: back extraction acid=3: 1 must contain Dy-Lu, the aqueous chloride solution of y through the multi-stage countercurrent back extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102210A CN85102210B (en) | 1985-04-01 | 1985-04-01 | Process for seperation of mixed rare-earths by ammoniated heh (ehp) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102210A CN85102210B (en) | 1985-04-01 | 1985-04-01 | Process for seperation of mixed rare-earths by ammoniated heh (ehp) |
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| Publication Number | Publication Date |
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| CN85102210A CN85102210A (en) | 1986-09-17 |
| CN85102210B true CN85102210B (en) | 1986-12-24 |
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| CN85102210A Expired CN85102210B (en) | 1985-04-01 | 1985-04-01 | Process for seperation of mixed rare-earths by ammoniated heh (ehp) |
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| CN102071316B (en) * | 2010-11-25 | 2012-08-22 | 广东富远稀土新材料股份有限公司 | Three-component separation method of multi-component rare earth |
| CN102618736B (en) | 2012-03-31 | 2013-09-04 | 中国科学院长春应用化学研究所 | Extraction separation method of rare-earth element |
| CN103074505B (en) * | 2013-02-04 | 2014-07-23 | 广东珠江稀土有限公司 | Process for continuously extracting and separating rare earth |
| CN103466679B (en) * | 2013-09-10 | 2015-06-24 | 中铝稀土（常熟）有限公司 | Preparation method of high-purity yttrium oxide |
| CN103526055B (en) * | 2013-10-09 | 2014-12-03 | 南昌航空大学 | Process for grouping quasi-fractionated extraction of neodymium/samarium through bastnaesite |
| CN104195335B (en) * | 2014-09-19 | 2017-02-15 | 厦门稀土材料研究所 | Extraction separation method for heavy rare earth elements |
| CN105256157B (en) * | 2015-11-18 | 2017-09-26 | 江西农业大学 | Pre-separation is extracted to light rare earth ore deposit and the method for middle ruthenium ion Rare Earth Mine combined separation |
| CN105543507B (en) * | 2015-12-19 | 2017-09-01 | 江西农业大学 | The method that light rare earth ore deposit and low ruthenium ion Rare Earth Mine extract combined separation with pre-separation |
| CN105886800B (en) * | 2016-05-06 | 2017-12-12 | 南昌航空大学 | A kind of technical grade samarium raw material prepares the extraction separating method of 5N samariums |
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| CN106244807B (en) * | 2016-07-29 | 2018-08-28 | 乐山东承新材料有限公司 | A method of the recovery purifying rare earth from ion adsorption type rare earth ore waste water |
| CN107385212A (en) * | 2017-07-07 | 2017-11-24 | 金川集团股份有限公司 | A kind of method of the P204 extractions organic removing ammonia of Ni |
| CN108220596B (en) * | 2018-02-08 | 2020-08-25 | 赣州齐畅新材料有限公司 | Praseodymium-neodymium extraction, enrichment and separation method |
| CN108728656B (en) * | 2018-07-06 | 2020-07-14 | 赣州嘉通新材料有限公司 | Separation and recovery method of rare earth-containing waste |
| CN112981144B (en) * | 2021-02-09 | 2022-10-18 | 内蒙古包钢和发稀土有限公司 | Method for extracting rare earth and use of aqueous solution containing ammonia |
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- 1985-04-01 CN CN85102210A patent/CN85102210B/en not_active Expired
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