CN1063718A - The method of separating beavy metal impurity system high-purity rare-earth - Google Patents

The method of separating beavy metal impurity system high-purity rare-earth Download PDF

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CN1063718A
CN1063718A CN92100069A CN92100069A CN1063718A CN 1063718 A CN1063718 A CN 1063718A CN 92100069 A CN92100069 A CN 92100069A CN 92100069 A CN92100069 A CN 92100069A CN 1063718 A CN1063718 A CN 1063718A
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compound
extraction agent
extraction
formula
mixture
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CN1039543C (en
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黄春辉
李标国
周永芬
何俊英
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Peking University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A kind of method with extraction process separating beavy metal compound impurity system high-purity rare-earth from rare earth compound or its mixture.Rare earth is made the aqueous solution of suitable concn, about room temperature, mix the vibration balance with extraction agent 1-8 hours.Extraction agent comprises: phosphonothionic acid or its ester class, perhaps group thiophosphate and oxine alkyl derivative class are two types.Thinner is selected aliphatic hydrocarbon or kerosene for use.Extraction agent recycles after with the hydrochloric acid back extraction.Each beavy metal impurity is lower than 0.5ppm in the rare earth behind this method purifying.

Description

The method of separating beavy metal impurity system high-purity rare-earth
The invention belongs to the rare earth compound field, provide a kind of from rare earth compound or its mixture separating beavy metal impurity, prepare high-purity rare method that goes up compound.
Along with high-tech development, more and more higher to rare purity requirement of going up compound, because rare earth compound is when having only its purity to reach quite high level, its many intrinsic performance just can show.For example, used europium sesquioxide, yttrium oxide in the television screen is if the iron that wherein contains, cobalt, nickel, copper compound impurity greater than 3-5ppm, then can influence fluoroscopic brightness.But can removing wherein at present, the method for heavy metal compound impurity is not that complex process is difficult for continuous production exactly.Chinese patent application (Gansu Rare Earth Co., application number 89101083.1) provides a kind of method with precipitator method separating beavy metal from earth solution.
The invention provides and a kind ofly go up separating beavy metal compound impurity compound or its mixture with extraction process from rare, and obtain the method for high-purity rare-earth compound, collection has the extraction agent of impurity to can be recycled after back extraction.Present method equipment is simple, and is easy to operate and can be continuously or automatic production, the product purity height, and beavy metal impurity is lower than 0.5ppm.
The present invention is according to the soft principle of hard, the soft parent of the hard parent of hsab theory, select the organic extractant of sulfur-bearing, nitrogen ligating atom for use, utilize itself and heavy metal ion to be easy to complexing, these ions comprise iron, cobalt, nickel, copper, lead, the mercury plasma that often is present in rare go up at least, thereby and difficult and rare characteristics that go up complexing of metal ion are separated heavy metal compound and obtained highly purified rare earth compound from rare earth compound or its mixture.
The inventive method comprises:
One, prepare the rare earth compound to be purified or the aqueous solution or the weighing liquid of its mixture:
What will contain above-mentioned heavy metal compound impurity rarely goes up compound or its mixture to be mixed with concentration is the 0.5-1.0 mole, and pH is the aqueous solution of 1-3.Described rare earth compound can be forms such as rare earth nitrate, perchlorate or its muriate.Contained impurity comprises iron, cobalt, nickel, copper, lead, mercury plasma or wherein a part of ion at least.
Two, select for use extraction agent to extract: available extraction agent has two types:
The extraction agent I comprises: phosphonothionic acid or its ester class, perhaps select group thiophosphate for use, and their general formula is respectively:
Figure 921000693_IMG6
R in the formula 1, R 2, R 3, R 4, R 5, R 6Identical also can be inequality, they can be respectively the straight or branched alkyl of C8-20 or their mixture.
The extraction agent II is: the oxine alkyl derivative of logical formula IV, R in the formula 7Straight or branched alkyl or alkylene or their mixture for C8-20.
Figure 921000693_IMG7
Above extraction agent I and II are made the solution of 0.1-1.0 mole respectively with thinner aliphatic hydrocarbon or kerosene.According to heavy metal compound kind and the quantity that feed liquid to be purified contains, can select extraction agent I or II extraction 1-4 time for use, perhaps successively respectively extract 1-2 time with different extraction agents respectively.Be about to above-mentioned extraction agent solution and mix the vibration balance with rare earth aqueous solution to be purified 1-8 hour, equilibrium temperature 15-30 ℃, be preferably in 20-25 ℃.The two is compared and can decide according to what of impurity level, between 1-5.Leave standstill phase-splitting after the balance.Organic phase is through recycling with after 1-10 mole hydrochloride back extraction 1-4 time.Water is used and as above method re-extract 1-4 time of last time identical extraction agent solution, and the multiple method can adopt cross-flow or multi-stage countercurrent mode, perhaps use with the solution of preceding once different extraction agent as above method extract 1-4 time.The organic phase of this moment is also with recycling after the aforesaid method back extraction.Water is sublimed rare earth compound or its mixture solution, and wherein beavy metal impurity is lower than 0.5ppm, can obtain the high-purity rare-earth compound with ordinary method.The flow process of the inventive method is seen synoptic diagram.
List following example in order to be illustrated more clearly in the present invention, but these there is not any restriction to scope of the present invention.
Example 1
Prepare 0.5 mole Lanthanum trichloride earth solution, wherein contained beavy metal impurity ion has: Cu ++43.7ppm, Co ++58.0ppm, Ni ++62.5ppm material liquid pH is 2.
Extraction agent is selected the compound of logical formula I, the R in the formula for use 1With R 2Be all mutually:
With octane is that to be mixed with concentration be 0.49 mole extraction agent solution to thinner.At 20-25 ℃, be in a ratio of 1.Feed liquid was mixed the vibration balance 8 hours with extraction agent solution, so cross-flow coextraction twice, organic phase recycles for four times with 6 mole hydrochloride back extractions, and water removes with ordinary method and anhydrates, and gets high-purity Lanthanum trichloride, and its residual impurity ion is respectively: Co ++0.02ppm, Ni ++＜0.06ppm, Cu ++＜0.015ppm.
Example 2
Feed liquid is identical with example 1, and extraction agent is selected the compound of logical formula III, R in the formula for use 5, R 6Be all mutually:
Figure 921000693_IMG9
, extract once vibration balance 7 hours.
The residual impurity ion is respectively in the product: Co ++＜0.075ppm, Ni ++0.1ppm, Cu ++＜0.015ppm.
Example 3
Remove in the feed liquid and contain beavy metal impurity ion Fe +++55.0ppm, Cu ++43.7ppm other is identical with above-mentioned example outward, extraction agent is the compound of logical formula IV, R in the formula 7For:
Figure 921000693_IMG10
Mixture.
The residual impurity ion is respectively in the product: Fe +++0.25ppm, Cu ++＜0.015ppm.
Example 4
Mixture and method with example 1 and 3 feed liquids extract, and are the extraction agent solution of use-case 1 first time, for the second time the extraction agent solution of use-case 3.
The residual impurity ion is respectively in the product: Fe +++0.35ppm, Co ++0.25ppm, Ni ++＜0.06ppm, Cu ++＜0.015ppm.
The schematic flow sheet brief description:
1. feed liquid
2. the solution of extraction agent
3. mixer-settler I
4. back extraction groove I
5. strip liquor
6. spent acid
7. the feed liquid behind the extraction agent purifying
8. the solution of the extraction agent different with last extraction agent
9. mixer-settler II
10. back extraction groove II
11. strip liquor
12. spent acid
13. collection has the solution of the another kind of extraction agent of impurity
14. high-purity rare-earth solution
If only use a kind of extraction agent, can carry out purifying by 3,4 two grooves.

Claims (5)

1, a kind of from rare earth compound or its mixture the method for separating beavy metal compound impurity system high-purity rare-earth compound, it is characterized in that using extraction process, described heavy metal comprises at least: the compound of iron, cobalt, nickel, copper, lead or mercury or the mixture in them, and described method comprises:
(1) preparation feed liquid:
It is 1-3 that rare earth to be purified is made pH, the aqueous solution of 0.5-1 mole,
(2) preparation extraction agent:
Select dissimilar extraction agent I and II to be dissolved in respectively to make in thinner aliphatic hydrocarbon or the kerosene solution that concentration is the 0.1-1 mole for use,
The extraction agent I comprises: phosphonothionic acid or its ester class or select group thiophosphate for use, and their general formula is respectively:
Figure 921000693_IMG1
R in the formula 1, R 2, R 3, R 4, R 5, R 6Identical also can be inequality, they can be respectively the straight or branched alkyl of C8-20 or their mixture.
The extraction agent II is: oxine alkyl derivative class, and general formula is:
R in the formula 7Straight or branched alkyl or alkylene or their mixture for C8-20.
Make the solution of feed liquid and above-mentioned arbitrary extraction agent, mix in 15-30 ℃ and vibrate, starting time is 1-8 hour, compares 1-5, leaves standstill phase-splitting after the balance, and organic phase recycles for 1-4 time with the back extraction of 4-10 mole hydrochloride,
Water adopts cross-flow or reflux type to use and the solution extraction of identical or different extraction agent last time 1-4 time, and organic phase recycles after the back extraction as mentioned above, water be high-purity rare on compound.
2,, it is characterized in that described rare earth compound is a Lanthanum trichloride, contains the compound of beavy metal impurity cobalt, nickel, copper according to the method for claim 1, material liquid pH is 2, and 0.5 mole of concentration is in a ratio of 1, thinner is an octane, and extraction agent is the compound of logical formula I, R in the formula 1And R 2Be all mutually:
Figure 921000693_IMG3
At 20-25 ℃, feed liquid is mixed vibration balance 8 hours with extraction agent solution, and organic phase recycles for twice with 6 mole hydrochloride back extractions, water go up for another example method extract once high-purity Lanthanum trichloride.
According to the method for claim 1 and 2, it is characterized in that 3, used extraction agent is the compound of logical formula III, R in the formula 5And R 6Be all mutually:
Figure 921000693_IMG4
4, according to the method for claim 1 and 2, it is characterized in that, the compound impurity of feed liquid iron content and copper, used extraction agent is the compound of logical formula IV, the R in the formula 7For:
Figure 921000693_IMG5
Mixture.Aqueous phase is high-purity Lanthanum trichloride.
5, according to claim 1,2 and 4 method, it is characterized in that, contain the compound of beavy metal impurity iron, cobalt, nickel and copper in the feed liquid, use claim 2 and 4 used extraction agent solution respectively to extract 1-2 time respectively.
CN92100069A 1992-01-14 1992-01-14 High-purity rare-earth preparing method by separating beavy metal impurity Expired - Fee Related CN1039543C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102808194A (en) * 2012-07-04 2012-12-05 嘉兴科菲冶金科技股份有限公司 Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine
CN103060842A (en) * 2012-12-26 2013-04-24 浙江华友钴业股份有限公司 Method for preparing electrodeposited cobalt under large flow
CN108085493A (en) * 2017-11-29 2018-05-29 中铝广西国盛稀土开发有限公司 A kind of method that impurity in rare earth chloride liquid is removed using batch process
CN111526931A (en) * 2017-09-18 2020-08-11 Ifp 新能源公司 Process for separating furans, in particular 5-hydroxymethylfurfural, from dimethyl sulfoxide by liquid-liquid extraction

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102808194A (en) * 2012-07-04 2012-12-05 嘉兴科菲冶金科技股份有限公司 Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine
CN102808194B (en) * 2012-07-04 2015-04-29 浙江科菲科技股份有限公司 Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine
CN103060842A (en) * 2012-12-26 2013-04-24 浙江华友钴业股份有限公司 Method for preparing electrodeposited cobalt under large flow
CN103060842B (en) * 2012-12-26 2016-06-08 浙江华友钴业股份有限公司 A kind of method preparing electrodeposited cobalt under big flow
CN111526931A (en) * 2017-09-18 2020-08-11 Ifp 新能源公司 Process for separating furans, in particular 5-hydroxymethylfurfural, from dimethyl sulfoxide by liquid-liquid extraction
CN111526931B (en) * 2017-09-18 2022-04-12 Ifp 新能源公司 Process for separating furans, in particular 5-hydroxymethylfurfural, from dimethyl sulfoxide by liquid-liquid extraction
CN108085493A (en) * 2017-11-29 2018-05-29 中铝广西国盛稀土开发有限公司 A kind of method that impurity in rare earth chloride liquid is removed using batch process
CN108085493B (en) * 2017-11-29 2019-10-25 中铝广西国盛稀土开发有限公司 A method of impurity in rare earth chloride liquid is removed using batch process

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