CN1039543C - High-purity rare-earth preparing method by separating beavy metal impurity - Google Patents

High-purity rare-earth preparing method by separating beavy metal impurity Download PDF

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CN1039543C
CN1039543C CN92100069A CN92100069A CN1039543C CN 1039543 C CN1039543 C CN 1039543C CN 92100069 A CN92100069 A CN 92100069A CN 92100069 A CN92100069 A CN 92100069A CN 1039543 C CN1039543 C CN 1039543C
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compound
extraction agent
rare earth
extraction
solution
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CN1063718A (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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Abstract

The present invention relates to a method for separating heavy metal compound impurities from rare earth compounds or mixtures thereof by an extracting method to prepare high purity rare earth. Rare earth is prepared into an aqueous solution with a proper concentration, the aqueous solution is mixed with an extracting agent, oscillation and balance are carried out for 1 to 8 hours at room temperature or so, wherein the extracting agent comprises phosphonotrithioic acid or ester thereof or thiophosphate and 8-hydroxyquinoline alkyl derivatives, and a diluting agent uses aliphatic hydrocarbon or kerosene. The extracting agent is circularly used after back extraction by hydrochloric acid, and the content of the heavy metal impurities in the rare earth purified by the method is less than 0.5 ppm.

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 the method for high-purity rare-earth compound.
Along with high-tech development, more and more higher to the purity requirement of rare earth 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, oxidation one 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 89 1 01083.1) provides a kind of method with precipitator method separating beavy metal from earth solution.
The invention provides a kind ofly with extraction process separating beavy metal compound impurity from rare earth compound or mixture, 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 hard according to the hard parent of hsab theory, the soft principle of soft parent, 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 the rare earth at least, thereby and difficult characteristics with the rare earth ion complexing 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:
To contain the rare earth compound of above-mentioned heavy metal compound impurity or its mixture, to be mixed with concentration be 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:
Extraction agent I comprises: phosphonothionic acid or its ester class, perhaps select group thiophosphate for use, and their general formula is respectively:
Figure C9210006900041
R in the formula 1, R 2, R 3, R 4, R 5, R 6Identical also can be inequality, they can be respectively C 8-20The straight or branched alkyl or their mixture.
Extraction agent II is: the oxine alkyl derivative of general formula (IV), R in the formula 7Be C 8-20Straight or branched alkyl or alkylene or their mixture.
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 rare earth aqueous solution to be purified forever and mixed the vibration balance 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 cotype (I) for use, the R in the formula 1With R 2Be all mutually:
Figure C9210006900052
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 person's extraction agent solution was mixed the vibration balance 8 hours, 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.Extraction agent is selected the compound of general formula (III) for use, R in the formula 5With R 6Be all mutually:
Figure C9210006900061
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 general formula (IV), R in the formula 7For:
Figure C9210006900062
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. the solution of feed liquid 2. extraction agents
3. mixer-settler I 4. back extraction groove I
5. strip liquor 6. spent acid
7. the solution of the extraction agent that the feed liquid behind the extraction agent purifying 8. is 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 14. high-purity rare-earth solution of the another kind of extraction agent of impurity
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 tribute or their mixture, and described method comprises:
(1) preparation feed liquid:
It is 1-3 that rare earth to be purified is made pH, and concentration is the aqueous solution of 0.5-1 mole,
(2) preparation extraction agent:
Select for use dissimilar extraction agent I and II to be dissolved in respectively in thinner aliphatic hydrocarbon or the kerosene, make the solution that concentration is the 0.1-1 mole,
Extraction agent I comprises: phosphonothionic acid or its ester class or select group thiophosphate for use, their general formula is respectively R in the formula 1, R 2, R 3, R 4, R 5, R 6Identical also can be inequality, they can be respectively C 8-20The straight or branched alkyl or their mixture,
Extraction agent II is: oxine alkyl derivative class, and general formula is: R in the formula 7Be C 8-20Straight or branched alkyl or alkylene or their mixture,
Make the solution of feed liquid and above-mentioned arbitrary extraction agent, mix vibration in 15-30 ℃, balance 1-8 hour, compare 1-5, leave standstill phase-splitting after the balance, organic phase is through recycling 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, and water is the high-purity rare-earth compound.
2. according to the method for claim 1, it is characterized in that described rare earth compound is a Lanthanum trichloride, contains the compound of beavy metal impurity cobalt, nickel, copper, 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 general formula (I), R in the formula 1And R 2Be all mutually: 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 again with above-mentioned extracting process and condition extract once high-purity Lanthanum trichloride.
3. according to the method for claim 1 or 2, it is characterized in that used extraction agent is the compound of general formula (III), R in the formula 5And R 6Be all mutually:
Figure C9210006900032
4. according to the method for claim 1 or 2, it is characterized in that, the compound impurity of feed liquid iron content and copper, used extraction agent is the compound of general formula (IV), R in the formula 7For:
Figure C9210006900033
Mixture, aqueous phase is high-purity Lanthanum trichloride.
5. according to claim 1,2 or 4 method, it is characterized in that, contain the compound of beavy metal impurity iron, cobalt, nickel, 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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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
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
FR3071172B1 (en) * 2017-09-18 2019-10-04 IFP Energies Nouvelles PROCESS FOR SEPARATING FURANIC COMPOUNDS, PARTICULARLY 5-HYDROXYMETHYLFURFURAL, FROM DIMETHOXYSULFOXIDE BY LIQUID-LIQUID EXTRACTIONS
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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