CN85102220A - High purity yttrium obtained by solvent extraction - Google Patents
High purity yttrium obtained by solvent extraction Download PDFInfo
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- CN85102220A CN85102220A CN 85102220 CN85102220A CN85102220A CN 85102220 A CN85102220 A CN 85102220A CN 85102220 CN85102220 CN 85102220 CN 85102220 A CN85102220 A CN 85102220A CN 85102220 A CN85102220 A CN 85102220A
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- yttrium
- rare earth
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Abstract
With liquid-liquid-solution solvent extraction technology, proposition is that extraction agent, naphthenic acid-naphthenic acid ammonium-Fatty Alcohol(C12-C14 and C12-C18)-kerosene are extracted organic phase with the naphthenic acid, is the multistage fractionation extraction process of single stage method high purity, high yield separating yttrium the mixed rare earth chlorides solution of leading from heavy rare earths.Obtain purity＞99.99%, direct yield＞98% of yttrium, and contain Y
2O
3The low yttrium mischmetal of 1.2-1.5%.
Description
The invention belongs to hydrometallurgy Rare Earth Separation technology, the technology of solvent extraction and separation yttrium
Nature yttrium (ordination number 39) and
Series elements (ordination number 57-71) symbiosis, their chemical property is very similar, causes mutual separation difficulty.High-purity yttrium oxide increases day by day in the demand of aspects such as fluorescent luminescent material, laserable material.Current, the hydrometallurgical processes of purification yttrium is mainly used liquid-liquid extraction, and used extraction system is had nothing in common with each other.Japan (Japan special permission 74-54216) is enriched in water (the yttrium grade is increased to 93.1% from 62%) with naphthenic acid with yttrium, and the organic phase middle-weight rare earths contains yttrium 1.5%, extracts pure yttrium with di-(2-ethylhexyl)phosphoric acid from rich yttrium aqueous phase afterwards.In addition, Japan (Japan special permission 79-80222) is extraction agent with di-(2-ethylhexyl)phosphoric acid, from the mixed rare earth chlorides of the thick yttrium that contains La-Lu behind the extraction branch group rare-earth, and back extraction organic phase middle-weight rare earths.Add DTPA in the strip liquor, with naphthenic acid purification by liquid extraction yttrium, obtain purity＞99% of yttrium, yield 58%, Beijing Non-Ferrous Metal Research General Academy's report " is produced phosphor powder class yttrium oxide technical study with siron south, extraction process Congjiang mishmetal " and " with the technology of separating high-purity yttrium in the mishmetal of siron south, the naphthenic acid extraction process Congjiang ", this process using 20% naphthenic acid (～90% ammonification)-15% isooctyl alcohol-kerosene organic phase, from the 0.8M re chloride through 55 grades of extractions, yttrium from 63.9% purify to＞99.99%, the rate of recovery 95.47% of yttrium, carry that yttrium content is 7-8% in the low yttrium rare earth behind the yttrium, contain the concentration C y of yttrium in the outlet raffinate of high-purity yttrium
3+～0.16M.
The objective of the invention is heavy rare earths is that main mixed rare earth chlorides is a raw material, with native annulus alkanoic acid (Naphtnenie Aoid, be designated hereinafter simply as HA) be extraction agent, by one not good liquor-liquid counter-current extraction, from the mishmetal that contains yttrium 50-70% high purity high yield purification yttrium is provided and is suitable for the extraction process condition of industrial production yttrium.Because naphthenic acid has the high efficiency separation yttrium, therefore, is extracted organic phase with naphthenic acid-naphthenic acid ammonium-mixed fatty alcohol-kerosene, without a minute group rare-earth, can directly obtain purity＞99.99% from mixed rare earth chlorides solution, high-purity y of yield＞98%
2O
3The technology of high efficiency separation yttrium provided by the invention is not reported in patent.
Processing condition provided by the invention are as follows:
1. organic phase: (1) extraction agent: naphthenic acid is and the symbiotic pentacyclic monocarboxylic acid that contains of oil, is the petroleum industry by product, cheap, loading capacity is big, nontoxic, its molecular formula is generally write as CH
3(CH
2)
n-
-(CH
2)
m-COOH, acid number are 174, proportion 0.9330(20 ℃), apparent molecular-weight average 300-350, refractive index η
20 D14753
(2) thinner: commercially available kerosene
(3) additive: C
7-9Mixed fatty alcohol (below write a Chinese character in simplified form ROH),
Interpolation ROH can improve the flowability of organic phase.
(4) extracted organic phase is by the %ROH(volume ratio of the M naphthenic acid of (0.65-0.70) M naphthenic acid ammonium-(0.15-0.30)-(15-20))-kerosene forms.
2. material solution: after decomposing with dense HCl based on the mixed rare-earth oxide of heavy rare earths, regulate rare earth concentration to 0.8-1M.
3. washing lotion: 2-2.5NHCl
4. by 1-(4), 2 and 3 form extraction system
5. above-mentioned extraction system is carried out fractionation extraction in 60 milliliters of separating funnels.Because the partition ratio of yttrium less than other rare earth ion, is pressed the extraction constant difference of HA to each rare earth ion in extraction process, the rare earth ion that is carried on rare earth in the organic phase and aqueous phase exchanges the result of extraction.Non-yttrium rare earth progressively is enriched in the organic phase.Yttrium is then stayed water and is constantly obtained purifying, through 50-60 level liquid-liquid fractionation extraction, and the purity of yttrium＞99.99%, direct yield＞98% contains y in the low yttrium rare earth behind the separating yttrium
2O
31.2-1.5%.
Advantage of the present invention
1. be that the separating effect of extraction agent extracting rare-earth ion pair yttrium is remarkable with the native annulus alkanoic acid, the partition ratio minimum of yttrium in the extraction system, its extraction position is positioned at
Therefore only after the system, do not need the rare earth grouping with a simple extraction system, can be light, single stage method purification yttrium the mishmetal of heavy rare earths from containing, reach the purpose of the high yield of high purity (＞99.99%) (＞98%) recovery yttrium.
2. adopt HA-NH
4A(naphthenic acid ammonium salt)-and ROH-kerosene is the advantage of extracted organic phase: (1) enters in the preceding extracted organic phase of extraction system and allocates finite concentration NH into according to the requirement of processing condition
4The method of A, the organic middle-weight rare earths concentration of may command also keeps ph value of aqueous phase stable.(2) add in the extracted organic phase that a certain amount of ROH has improved the flowability of organic phase more effectively and the separating effect that do not influence yttrium.
3. yttrium content 1.2-1.5% in the low yttrium rare earth of Huo Deing can directly be used as and separate the single rare earth raw material.
4. the rare earth back extraction in the organic phase is more or less freely, as with 3 mol HCl or HNO
3/ 1 mol rare earth ion, excessive 0.2 normal sour back extraction once can guarantee back extraction ratio＞98% of rare earth.
5. the method for regeneration organic phase is simple, handles 1-2 time as usefulness～3NHCl, uses H
2O is washed till scrub raffinate PH＞4, and organic phase promptly can be recycled.
6.HA be natural compounds, cheap, can reduce high-purity y significantly
2O
3Production cost.
7. extraction system provided by the invention also is applicable to and contains y
2O
3The purification of yttrium in＞50% the mishmetal.(mishmetal comprises Y and ordination number 57-71 element).
Embodiment provided by the invention is as follows
With 0.8-0.9MHA and NH
4A is an extraction agent, from Y
2O
3The high yield of single stage method (＞98%) obtains high-purity Y of purity＞99.99% in the enriched substance based on heavy rare earths of content 63% (containing light rare earths 6-7%)
2O
3
1. extracted organic phase: (15-20) HA concentration is organic phase 1 volume of 0.85M in the %ROH-kerosene (volume ratio), adds 12N NH
4The OH0.056 volume makes HA and NH in the organic phase
4The reaction of OH equivalent, generation consists of: 0.18MHA-0.67M NH
4A-(15-20) %ROH(volume ratio)-extracted organic phase of kerosene.
2. material solution: HCl decomposition mixed rare-earth oxide is a rare-earth chloride solution, Y in the rare earth
2O
3Content sees Table 1 for 63%(rare earths material composition).The adjusting rare earth concentration is 1M, PH3-4.
3. washing lotion: 2NHCl
Table 1 raw material rare earth component percentage composition
RE
XO
Y（L
a-E
u） Cd Tb Dy Ho Er Tm Yb Lu Y
（%） ～1 59 3 16 25 6.0 0.7 23 0.05 63
4. extract through 50 grades of fractionation in 60 milliliters of separating funnels by 1,2,3 extraction system of forming.The 1st grade of outlet raffinate water and the 50th grade of outlet organic phase are once, then add 25 volume extracted organic phase from the 1st grade, add 3.9 volume stock liquids and add 7.0 volume 2NHCl washing lotions from 40 grades from the 50th grade, afterwards＞15 ℃ of Xia Zhen Swing 5 minutes, leave standstill phase-splitting, so repeatable operation to system reaches stable state.The yttrium of the 1st grade of outlet in the raffinate shows purity＞99.99% of yttrium with the non-yttrium rare earth impurities of analysis of emission spectrography (seeing Table 2), and the concentration that yield＞98% exports yttrium in the raffinate is 0.2-0.3M, than the outlet of the coloured institute in Beijing magnificent liquid concentration height that comes together.The supported rare earth organic phase middle-weight rare earths concentration of the 50th grade of outlet is 0.03-0.05M, Y in the rare earth
2O
3Content sees Table 3 for (1.40-1.42) %().
The pure y of table 2
2O
3In non-yttrium rare-earth spectrum analyze
RE
xO
y（PPm）
RE La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er
1 2.2 ＜10 ＜10 ＜3 ＜1 ＜0.5 ＜3 ＜10 44 5.0 31
2 2.0 ＜10 ＜10 ＜3 ＜1 ＜0.5 ＜3 ＜10 2.6 ＜3 15
y
2O
3（%）
RE Tm Yb Lu Y
1 3.8 4.7 ＜10 ＞99.99
2 1.2 0.7 ＜10 ＞99.99
Low yttrium rare earth component in the table 3 outlet organic phase
(X-line fluorescence spectra method)
RExOy La Ce Pr Nd Sm Gd Tb Dy He
（%）
1 0.82 / / 0.91 0.68 15.4 7.6 429 7.8
2 0.74 / / 0.82 0.69 15.2 7.8 42.7 81
RE
xO
yEr Tm Yb Lu Y
1 15.2 1.6 4.6 0.2 1.42
2 15.3 1.6 4.6 0.2 1.40
5. the back extraction of rare earth: with 3NHCl is strip liquor, O/A=20-30, rare earth back extraction ratio～100% of single-stage back extraction, anti-fluid rare earth concentration～1M
6. organic phase is regenerated and is recycled; Organic phase 3NHCl after the back extraction, O/A=4 handle twice back and use the deionized water wash organic phase to scrub raffinate PH＞4, add NH
4OH makes among the HA and generates 0.67MNH
4A can use repeatedly
7.3 the outlet water oxalic acid precipitation of item, calcination makes high-purity y
2O
3
Claims (7)
1, be the technology that extraction system is carried out liquid-liquid purification by liquid extraction yttrium with the native annulus alkanoic acid, it is characterized in that in order to heavy rare earths be main mixed rare earth chlorides be feed liquid (rare earth concentration 1M, PH3-4), with (0.65-0.70) MNH
4A-(0.15-0.30) MHA-(15-20) %ROH (volume ratio) kerosene is formed extracted organic phase, with 2-2.5NHCl is washing lotion, through 40 grades of extraction sections, the fractionation extraction of 10 grades of washing sections, with the grade of yttrium from 60-65% purify to＞99.99%, the yield of flash liberation yttrium＞98%.
2, technology as claimed in claim 1, wherein the mixed rare earth chlorides feed liquid is to decompose mixed rare-earth oxide with HCl to make y in the feed liquid
2O
3Content 60-65%.
3, technology as claimed in claim 1, y in the rare earth
2O
3Content＞50% promptly can be used for the purification of yttrium.
4, technology as claimed in claim 1, wherein NH
4A uses NH
4Among the OH and the 0.65-0.70MHA neutralization reaction generate.
5, technology as claimed in claim 1 is characterized in that adding extracted organic phase from the 40th grade of adding rare earth chloride liquid from the 1st grade, adds washing from the 50th grade.
6, as claimed in claim, the raffinate water of first step outlet contains high-purity yttrium, is the low yttrium mischmetal that contains yttrium 1.4-1.42% in the organic phase of the 50th grade of outlet.
7, technology as claimed in claim 1 after counter-current extraction contacts balance at every turn, adds 25 volume extracted organic phase from the first step, from 40 grades of adding 3.9 volume rare earth chloride feed liquids, adds 7.0 volume HCl washing lotions from 50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102220A CN85102220B (en) | 1985-04-01 | 1985-04-01 | High purity yttrium obtained by solvent extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102220A CN85102220B (en) | 1985-04-01 | 1985-04-01 | High purity yttrium obtained by solvent extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85102220B CN85102220B (en) | 1987-01-14 |
| CN85102220A true CN85102220A (en) | 1987-01-17 |
Family
ID=4792345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85102220A Expired CN85102220B (en) | 1985-04-01 | 1985-04-01 | High purity yttrium obtained by solvent extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85102220B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543476A (en) * | 2015-12-24 | 2016-05-04 | 广西师范大学 | Mixed extraction agents used for separating Y and method for extracting and separating Y from rare earth feed liquid |
-
1985
- 1985-04-01 CN CN85102220A patent/CN85102220B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543476A (en) * | 2015-12-24 | 2016-05-04 | 广西师范大学 | Mixed extraction agents used for separating Y and method for extracting and separating Y from rare earth feed liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85102220B (en) | 1987-01-14 |
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