CN1040889C - Extracting technological method for purifying separating rare earth element - Google Patents

Extracting technological method for purifying separating rare earth element Download PDF

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CN1040889C
CN1040889C CN92113216A CN92113216A CN1040889C CN 1040889 C CN1040889 C CN 1040889C CN 92113216 A CN92113216 A CN 92113216A CN 92113216 A CN92113216 A CN 92113216A CN 1040889 C CN1040889 C CN 1040889C
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rare earth
earth element
liquid
organic phase
extraction
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CN1087388A (en
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孙军
区海峰
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Beijing General Research Institute for Non Ferrous Metals
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Abstract

The present invention relates to method for extracting and separating rare-earth elements in a water solution, which is completed by carrying out solution-solution extraction between a water phase containing rare-earth elements and an organic phase containing bi-(biisobutyl methyl)phosphoric acid [HD(DIBM)P]. Because the method adopts the extraction agent, the extraction capacity is large, the delamination effects are good, and the reverse extraction acidity is low. The quantity for treating rare earth in unit time by using the method of the present invention is large; the present invention has the advantages of high productive efficiency, short productive periodicity and equipment investment saving, the consumption of chemical raw materials, such as acid alkali, etc., is reduced, and the present invention has large economic benefit.

Description

The extracting process of purifying separating rare earth element
The present invention relates to be separated in separating of rare earth element in the aqueous solution or the rare earth element in the aqueous solution and non-rare earth with liquid-liquid extraction.
" rare earth element " used herein is meant lanthanide series rare-earth elements, comprises that the element of ordination number from 57 to 71 and ordination number are that 39 yttrium and ordination number are 21 scandium.Said light rare earths is lanthanum, cerium, praseodymium, neodymium.Middle heavy rare earths is samarium, europium, gadolinium.Heavy rare earths is terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium.
The extraction agent that is used for the rare earth element of the extracting and separating aqueous solution, or the extraction agent that is used for extracting and separating aqueous solution middle-weight rare earths element and non-rare earth lipid acid, naphthenic acid, D2EHPA[are arranged is P204, di-(2-ethylhexyl)phosphoric acid, di (2-ethylhexyl) phosphoric acid], HEP (EHP) [is P507,2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester, 2-ethylhexyl phosphoricacid mono-2-ethylhexyl ester] etc.Lipid acid, naphthenic acid water-soluble big, in use the extraction agent composition can change.For the layering situation of improving its organic phase and water usually needs to add Fatty Alcohol(C12-C14 and C12-C18) or heating again, and produce odour nuisance, contaminate environment, and the operator's of technology Working environment is degenerated.D2EHPA, HEP (EHP) though overcome some shortcoming of lipid acid and naphthenic acid, but D2EHPA is used for heavy rare-earth extraction when separating or the very high acidity of needs during organic phase regeneration, so will consume a large amount of chemical reagent such as soda acid; HEP (EHP) is when heavy rare-earth extraction separates or organic phase when regeneration, and its acidity is than some reduction of D2EHPA, but still very high, also makes troubles to technological operation.
Employed representative extraction agent is the CYANEX272[goods marks in the process of a kind of liquid-liquid extraction separation of rare earth elements that Chinese patent literature CN1004330B describes, two (2,2,4 tri-methyl-amyls) phospho acid, bis (2,4,4-trimethylpentyl) phosphinic acid].When this extraction agent was used for the heavy rare earths separation, its advantage was that separating factor is bigger, and reextraction acidity is low; But its weak point is that layered effect is poor in extraction process, needs to add improving agent (or being additive) to improve its flowability, and another shortcoming is that its loading capacity is low.
Purpose of the present invention just is to work out a kind of method of liquid-liquid extraction purifying separating rare earth element, use a kind of novel extraction agent in the method, the loading capacity of this novel extraction agent is big, layered effect is good again in extraction process, the acidity of stripping is lower than D2EHPA and HEP (EHP), close with CYANEX272 or low slightly, this novel extraction agent has bigger separating factor again and uses this novel extraction agent to make between the rare earth element in liquid-liquid extraction technology to separate when heavy rare earth element separates, especially make between some heavy rare earth element and separate preferably, and rare earth element is separated with non-rare earth, and remove the non-rare earth impurity in the rare earth element.
Employed novel extraction agent is HD (DIBM) P[two (diisobutyl methyl) phosphoric acid among the present invention, bis (2,6-dimethyl-4-heptyl) phosphoric acid, (C9H190) 2PO (OH)].Because the reason of HD (DIBM) P molecular structure, it has higher sterically hindered, in the extracting power that reaches between rare earth element and some non-rare earth between the rare earth element bigger difference is arranged, but be not used for as yet between the rare earth element and the separating of rare earth and some non-rare earth, contriver's experiment shows that this novel extraction agent has advantages such as loading capacity is big.Its extracting power is:
Sc 3+＞Lu 3+＞Yb 3+＞Tm 3+＞Er 3+＞Y 3+＞Ho 3+＞Dy 3+＞Tb 3+＞Gd 3+＞Eu 3+＞Sm 3+＞Nd 3+＞Ce 3+＞La 3+.
Fe 3+＞Ln A+＞Ca 2+Mg 2+＞Na +, NH4 +(Ln 3+Expression trivalent lanthanon and ruthenium ion) and HD (DINM) P and Sc 3+Fe 3+The reextraction acidity of the extract in organic phase is also very low.Hydrogen ion concentration can be with Sc less than mineral acid example hydrochloric acid, sulfuric acid, the nitric acid of 1 mol 3+And Fe 3+Plasma is stripped into aqueous phase, and the reextraction acidity of P507, P204 is greater than the mineral acid of 6 mol hydrogen ion concentrations, for example hydrochloric acid, sulfuric acid, nitric acid.Pka value HD (DIBM) P is 4.75, and D2EHPA is 3.5, and HEP (EHP) is 4.51.
Well-known separation factor β represents two elements, for example the possibility of extracting and separating between two rare earth elements. βRi / Rj = [ Ri ] o / [ Ri ] a [ Rj ] o / [ Rj ] a … … [ 1 ]
R represents rare earth element in the formula, and i, j represent different rare earth elements, [] oThe concentration of expression rare earth element in organic phase, [] aThe expression rare earth element is in the concentration of aqueous phase.When being not equal to 1, the β value represents the separative possibility of Ri and Rj.The β value is easier to collection greater than 1 o'clock explanation Ri than Rj and goes in the organic phase.
Measured the β value with the method that those of ordinary skill in the art knows altogether.At room temperature, in separating funnel, add isopyknic organic phase and water.Organic phase is HD (DIBM) P-kerosin, and the concentration of HD (DIBM) P is 1 mol, and saponification deg (ammonification degree) is 25%.Water is the aqueous chloride solution of mishmetal, and the concentration of mishmetal is 0.5 mol, and the acidity PH=3 of aqueous phase liquid was with separating funnel vibration 15 minutes.Standing demix is measured the concentration of each rare earth element at organic phase and water, calculates corresponding separating factor according to formula [1], and its result is as follows:
βce/La3.4，βpr/Ce1.4，βNd/Prl.03，βSm/Nd3.1，βEu/Sm1.5，βGd/Eu1.3，βTb/Gd4.0，βDy/Tb1.7，βHo/Dy1，4，βY/Ho1.2，βEr/Y1.7，βTm/Er2.5，βYb/Tm2.8，βLu/Yb1.4。
The method of a kind of liquid-liquid extraction purifying separating rare earth element of the present invention, make be present at least a rare earth element in the aqueous solution separate with at least a other rare earth elements in being present in this aqueous solution or make be present in the aqueous solution at least a rare earth element and be present in this aqueous solution at least a non-rare earth separate, this sepn process comprise with contain rare-earth element salt the aqueous solution water and contain two (diisobutyl methyl) phosphoric acid [HD (DIBM) P], bis (2,6-dimethyl-4-heptyl) phosphori acid] organic phase of extraction agent carries out liquid-liquid extraction and separates.
When liquid-liquid extraction, formed by the following aqueous solution with the contacted water of organic phase that contains extraction agent HD (DIBM) P (being the stock liquid of said rare earth element salt brine solution).The aqueous solution that is used as the rare earth element of stock liquid can be the aqueous solution with the xenotime of acid system, alkaline process, ion exchange method processing, baotite, the resulting rare-earth element salt of monazite and ion-exchange absorption type ore deposit.The aqueous solution of used rare-earth element salt can be the aqueous solution of various salts a kind of salt wherein such as rare earth nitrate, rare earth sulfate, rare earth chloride, rare earth perchlorate, but is good with the aqueous solution of rare earth chloride, rare earth nitrate a kind of salt wherein.It also can be the above-mentioned salt that other salts of rare earth element generate after anionresin.If desired, the concentration of the rare earth element of solution can be concentrated to predetermined concentration before use.Usually the concentration of representing the aqueous solution of rare-earth element salt in the liquid-liquid extraction process with the oxide compound of rare earth element.Usually the concentration of the aqueous solution of rare-earth element salt is that 1-500 grams per liter (in the oxide compound of rare earth element) is equivalent to the 0.01-4.5 mol, again in the concentration of the aqueous solution of rare earth element vitriol be 5-40 grams per liter (with the oxide compound of rare earth element) for good, also the concentration in the aqueous solution of rare earth element vitriol is that 20 gram-35 grams per liters (with the oxide compound of rare earth element) are better; The concentration of the aqueous solution of the concentration of the muriatic aqueous solution of rare earth element and rare earth element nitrate is 40-450 grams per liter (in the oxide compound of rare earth element) and is advisable, and is that 40-250 grams per liter (with the oxide compound of rare earth element) is better in its concentration again.The hydrogen ion concentration of the aqueous solution of rare-earth element salt (for example rare earth element vitriol, rare earth element muriate, rare earth element nitrate, rare earth element oxymuriate a kind of salt wherein) is 10 -4Between-3 mol.
When the concentration of extraction agent HD (DIBM) P increases in the organic phase, the extracting power of rare earth element is also increased, but the factor that is separated from each other between the rare earth element does not have significant variation with the variation of extraction agent HD (DIBM) P concentration in the organic phase.So extraction agent two in organic phase (diisobutyl methyl) concentration of phosphoric acid is not an important factor, so extraction agent HD (DIBM) P can be a very wide scope.The concentration of extraction agent HD (DIBM) P is that the 3-100% (V/V) of organic phase volume is the 0.1-3 mol in the organic phase.
Except extraction agent, the organic phase that is used for processing method of the present invention also can contain at least a organic thinner in organic phase.Organic thinner can be aliphatic hydrocarbon such as hexane, pentane, dodecane, kerosene; Halohydrocarbon such as chloroform, tetracol phenixin; The solvent type petroleum cuts of aromatic hydrocarbon such as benzene, toluene, ethylbenzene, dimethylbenzene and perfume oil.
In extraction separation process of the present invention, can contain at least a additive (being improving agent again) in the organic phase but also can not contain additive.In extraction separation process of the present invention, generally do not need to add additive.The additive that is added comprises the higher alcohols isooctyl alcohol for example that C4-C15 is arranged, and higher phenols is cresols for example, and phosphoric acid fat is TBP (tributyl phosphate) for example, sulfoxide etc.The amount that adds additive is to make that additive is the 3-20% (V/V) of organic phase cumulative volume in organic phase
Extraction agent HD (DIBM) P can be directly used in the extraction of rare earth, and loading capacity is lower; If with extraction agent HD (DIBM) P earlier with alkali with its saponification, be used for extracting rare-earth again, will show very big loading capacity.Carry out the used alkali of saponification and include ammoniacal liquor, alkali metal hydroxide for example sodium hydroxide, potassium hydroxide; Alkaline earth metal hydroxides, oxide compound be magnesium hydroxide, magnesium oxide etc. for example.Carry out the saponified process with ammoniacal liquor and can cry ammonification.The saponification deg of used extraction agent HD (DIBM) P is 0-100% in the technological process of liquid-liquid extraction purifying separating rare earth element of the present invention.The saponification deg of extraction agent HD of the present invention (DIBM) P reaches at 100% o'clock, still can be used for the extraction of rare earth, the mole ratio of extraction agent HD (DIBM) P and rare earth is not 6: 1 that resemble P507, the P204 in this moment extract, formed 3: 1, the saturated extraction quantity of mol of extraction agent HD (DIBM) P is 2.5 times of P507,3 times of P204,2 times of lipid acid.Said saponification deg is the ratio of the mol sum of the gram mark of saponified extraction agent HD (DIBM) P and extraction agent HD (DIBM) P, the numerical value of representing with percentage ratio.The saponification deg of extraction agent can be decided according to the needs of technical process.The saponified method is to add to contain the organic phase solution of extraction agent HD (DIBM) P and the above-mentioned alkali of calculated amount (for example ammoniacal liquor, sodium hydroxide) and mix and form in soap tank.
Aqueous phase hydrogen ion (H in extraction process +) concentration be an important factor because it affects the distribution condition of rare earth element in water, organic phase.The ability of organic extractant phase rare earth element is along with aqueous phase acidity (H +Concentration) reduction and increasing.H when aqueous phase +When ionic concn was hanged down, rare earth element can be assigned in the organic phase more; And as aqueous phase H +When ionic concn was high, rare earth element can be allocated in aqueous phase more.In the process of abstraction purification separation of rare earth elements of the present invention, the H of water when extraction +Hydrogen ion concentration when ionic concn makes extraction is 10 -7～1 mol.The hydrionic concentration of aqueous phase can be regulated with alkali or basic salt.Used alkali includes for example bicarbonate of ammonia etc. of sodium hydroxide, ammoniacal liquor, basic salt.But with ammoniacal liquor is good, is good with strong aqua especially.Used ammonia concn can be the ammoniacal liquor of various concentration such as 1-14 mol, the ammoniacal liquor of the most handy 9～10 mol.The amount of adding ammoniacal liquor should be come together according to rare earth element and be calculated into the amount of organic phase.
Temperature during extraction is at 10-50 ℃, being good at 20-40 ℃.
The amount and the selected equipment of rare earth element that should enter organic phase in the saponification deg of the throughput ratio between when extraction organic phase solution, feed liquid, washings and the concentration of extraction agent, extraction agent, the rare earth feed liquid is relevant.Their throughput ratio can be decided by the well-known method of calculation of the those of ordinary skill under this area.
Owing in extraction process, there is undesirable a small amount of rare earth elements to enter organic phase, so after extraction, need to wash organic phase with washings, they are washed aqueous phase from organic phase, washings is a kind of acid, can be hydrochloric acid, nitric acid, sulfuric acid, perchloric acid a kind of acid or the aqueous solution of the salt of the rare earth element in organic phase that should come together for example muriate, rare earth element nitrate, rare earth element vitriol, the aqueous solution of rare earth element perchlorate a kind of salt wherein of rare earth element wherein.Preferably hydrochloric acid, nitric acid a kind of acid wherein of washings.During as washings, under any circumstance their concentration is inessential with hydrochloric acid, nitric acid.Their concentration can be 0.1～10 mol, is preferably 0.2～5 mol.If during as washings, with the rare earth element muriate, the aqueous solution of rare earth element nitrate a kind of salt wherein is good with rare-earth element salt, their concentration be the 1-500 grams per liter (in the oxide compound of rare earth element down with), 25-300 grams per liter preferably.
After extraction and washing operation, it and then is exactly separating and the regeneration of organic phase of water and organic phase.The regeneration of said organic phase be exactly with a kind of acid for example a kind of acid wherein of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid be that strip liquor is stripped into aqueous phase with the rare earth element in the organic phase of supported rare earth, make organic phase regeneration.Preferably hydrochloric acid, nitric acid a kind of acid wherein of strip liquor, strip liquor hydrochloric acid, nitric acid wherein a kind of concentration of acid are the 0.5-10 mol, again with the 1-5 mol for better.
The regenerated organic phase enters soap tank carries out being used further to extraction after the saponification (with the ammoniacal liquor saponification time cry again ammonification), and the organic phase that contains extraction agent is recycled.Rare earth element by back extraction is collected in aqueous phase.
The method according to this invention can make rare earth element separate with non-rare earth by the enriching and purifying rare earth element, can make a kind of salt of rare earth element convert another kind of salt to again, can contain of the separation of two kinds of rare earth elements at least in separating again until whole luciums.For example be used to contain the mixture of n rare earth element, through n-1 above-mentioned technology, can be separately with several mixed rare-earth elements.Above-mentioned technology comprises extraction section, washing section, reextraction section (RS Regenerator Section) and saponification section.If adopt the method for the separation of rare earth elements of multiple exit, isolating number of times can reduce.
In the technology first three section can be carried out in the column extractor that multistage mixing clarification system or packed column or band stir.Used extraction agent HD (DIBM) P also can be used as the stationary phase of extration resin in technology of the present invention, carries out reversed-phase chromatography.
In fact technological process of the present invention can adopt those of ordinary skill is all known under the present technique field half adverse current, adverse current, methods such as stream, cross-flow altogether.
For rare earth element is separated with non-rare earth, make rare earth element obtain the another kind of salt that a kind of salt that purification enrichment can make rare earth element again converts rare earth element to.Can with extraction agent HD (DIBM) P with above-mentioned thinner for example kerosene it is diluted to required concentration.Carrying out saponification more for example adds ammoniacal liquor and makes extraction agent HD (DIBM) P in the organic phase to needed saponification deg.To extract by needed comparing through extraction agent saponified organic phase and leach liquor as the rare-earth mineral of water, make rare earth element enter organic phase from water, standing demix is told organic phase.With the organic phase of supported rare earth element, wash as washings with deionized water, remove the ion that is clipped in the non-rare earth in the organic phase.Will be through the organic phase of supported rare earth element of washing, as strip liquor, carry out back extraction with the acid of desired concn, make organic phase regeneration, and obtain the aqueous solution as the rare earth element of water.The aqueous solution of resulting rare-earth element salt can be used for the separation of rare earth element, or after further removing the ion of non-rare earth again, evaporation concentration becomes solid rare-earth salts product.
The method according to this invention can make at least two rare earth elements obtain separating, can be with the aqueous solution (being good to contain nitrate of rare earth element or muriate especially) of the salt that contains these rare earth elements as water and contain and carry out liquid-liquid extraction between the organic phase of extraction agent HD (DIBM) P and realize.At first according to concrete experiment condition with extraction agent HD (DIBM) the P saponification in the organic phase to needed saponification deg or do not carry out saponification.To contact with the organic phase that contains extraction agent as the aqueous solution that contains two rare earth elements at least (as feed liquid) of water and extract, some (or some) rare earth element is come together into organic phase, other (or another) rare earth elements are stayed water, make rare earth element obtain separating.With washings the organic phase of the rare earth element that contains some (or some) and a small amount of other (or another) rare earth elements is washed then, a spot of other (or another) rare earth elements are removed from organic phase, enter water.Organic phase, water are separated.Contact with organic phase with strip liquor and to carry out back extraction and make organic phase regeneration.More than provided in the superincumbent narration of operational condition of each operation.
At first several rare earth elements are divided into two groups with method of the present invention, again two groups are handled with aforesaid method respectively, be divided into group n time, make several rare earth elements be divided into one rare earth element at last.In a word, the aqueous solution of the first operation middle-weight rare earths element salt with contain the organic phase of thinner and contact with extraction agent two (diisobutyl methyl) phosphoric acid [HD (DIBM) P], an a kind of rare earth element or group rare earth element with high partition ratio, preferentially enter organic phase, an a kind of rare earth element or a group rare earth element with low partition ratio then are enriched in aqueous phase; In second operation organic phase then optionally with contain hydrochloric acid, nitric acid, sulfuric acid, perchloric acid wherein a kind of acid or the aqueous solution that contains rare earth element muriate, rare earth element nitrate, rare earth element vitriol, rare earth element perchlorate a kind of salt wherein as washings, get less the sort of rare earth element or a group rare earth element or a non-rare earth to remove organic extractant phase; Make organic phase and aqueous phase separation then; In the 3rd operation, contact with organic phase as strip liquor, contain the organic phase of extraction agent with regeneration with containing aqueous acid.
The advantage of the method for liquid-liquid extraction purifying separating rare earth element of the present invention just is to have adopted new extraction agent two (diisobutyl methyl) phosphoric acid [HD (DIBM) P] as extraction agent.Because this new extraction agent loading capacity is big, layered effect is good, and reextraction acidity is low.Some heavy rare earths is had bigger separating factor, and rare earth and some non-rare earth have bigger separating factor, and it is big to make method of the present invention handle the amount of rare earth under identical appointed condition, has saved facility investment and time.Because reextraction acidity is low, can not doping, saved industrial chemicals and additives such as soda acid, and this extraction agent production cost is than P507 with CYANEX272 is low makes technical process of the present invention have bigger economic benefit.
Fig. 1 technical process Fig. 1 Fig. 2 technical process Fig. 2
With following embodiment method of the present invention is further described, will helps the understanding of couple the present invention and advantage thereof, and not as the qualification to protection domain of the present invention, protection scope of the present invention is decided by claims.
Embodiment 1
Comparison with the organic phase solution loading capacity of different extraction agents, in the separating funnel of four series of 50 milliliters, HD (DIBM) the P-kerosin that adds 1 mol respectively, the D2EHPA-kerosin of 1 mol, the HEP of 1 mol (EHP)-kerosin, each 28 milliliters of the CYANEX272-kerosins of 1 mol add the strong aqua (11.9 mol) of different volumes then, vibration is 20 minutes on the Kang Shi vibrator, makes it reach different saponification degs.Few its composition of yttrium mixed chlorinated rare earth solution that respectively adds 12 milliliters (PH3.5) in each separatory leaks is with embodiment 5, and the concentration of few yttrium mixed rare earth solution is 1.041 mol, and vibration is 20 minutes on the Kang Shi vibrator, makes it reach balance.Leave standstill, make water and organic phase layering, the concentration results of measuring organic phase middle-weight rare earths element is as shown in table 1.
The concentration of table 1 organic phase middle-weight rare earths element
The volume of ammoniacal liquor (milliliter) 0 0.464 0.932 1.4 1.86 2.32
Saponification deg % 0 20 40 60 80 100
The concentration mol of organic phase middle-weight rare earths element during with HD (DIBM) P 0.006 0.083 0.13 0.22 0.29 0.33
Annotate: the slow boundary material of saponification deg 〉=80% layering is many
The concentration mol of organic phase middle-weight rare earths element during D2EHPA 0.15 Emulsification is not stratified
The concentration mol of organic phase middle-weight rare earths element during HEP (EHP) 0.11 0.13 0.16 Emulsification is not stratified
The concentration mol of organic phase middle-weight rare earths element during CYANEX272 0.054 0.09 Layering is bad Emulsification
As can be seen from Table 1, along with the saponification deg increase of (can claim the ammonification degree herein), the ability of organic extractant phase rare earth increases, but D2EHPA is not stratified when saponification deg 20% is above, emulsification.Emulsification takes place when HEP (EHP) saponification deg 60%, and CYANEX272 layering when saponification deg 20% is above is bad.And extraction agent HD (DIBM) P that uses in the method for the present invention is at saponification deg＞emulsion does not take place more than 60% yet, and other extracting power of energy force rate of its organic extractant phase rare earth element is much bigger.
Embodiment 2
To different extraction agents, the comparison of the organic phase reextraction degree of supported rare earth.HD (DIBN) the P-kerosin that in 25 milliliters of taper separating funnels, adds 1 mol of load heavy rare earths, 1 mol D2EHPA-kerosin, each 15 milliliters of 1 mol HEP (EHP)-kerosins, the concentration of its heavy rare earths is 0.15 mol, the composition of heavy rare earths (percentage ratio of weight %) is:
Y 2O 3 6.2，Er 2O 3 0.16，Tm 2O 3 7.97，Yb 2O 3 76.9，Lu 2O 3 8.81。7.5 milliliters of hydrochloric acid solns that in each separating funnel, add 0.521 mol more respectively, vibration is 15 minutes on the Kang Shi vibrator, makes it reach balance, behind the standing demix of stripping, separates organic phase and water, and it the results are shown in Table 2.
The different extraction agent load organic oppositing back-extractions of table 2 are got the comparison of degree
Load organic phases Strip liquor
Acidity The rare earth concentration mol Back extraction ratio %
HD(DIBM)P D2 EHPA HEP(EHP) PH2.5 0.511N 0.464N 0.17 0.0033 0.019 5.7 1.1 6.3
The organic phase HD of load heavy rare earths (DIBM) P strips manyly than D2EHPA, HEP (EHP) easily as can be known from Table 2.The remaining acidity of anti-stripping agent is very low to be PH2.5, and rare earth concentration is 56 times of D2EHPA very up to 0.17 mol, 8 times of HEP (EHP).
Embodiment 3
With the vitriol intensified roasting infusion of baotite is aqueous phase liquid, wherein rare earth element is come together carry out purification enrichment in the organic phase, removes non-rare earth impurity, and the vitriol of rare earth element is made the transition into the muriate or the nitrate of rare earth element of rare earth element.
Concentration as the vitriol intensified roasting infusion of the baotite of aqueous phase liquid middle-weight rare earths is 0.2 mol (35 grams per liters are in the oxide compound of rare earth element), and PH is 4, and iron is 0.02 grams per liter (in iron), and calcium magnesium resultant is 2 grams per liters (in calcium, magnesium resultants).Phosphorus is 0.002 grams per liter (in phosphorus).
Pure HD (DIBM) P (3 mol) is diluted to 0.8 mol with kerosene, with V ammoniacal liquor: the ratio of V organic phase=1.16: 20, strong aqua (13 mol) is joined among 0.8 mol HD (BIBM) P, stir the organic phase solution that 20 minutes (160 commentaries on classics/per minute) obtains saponification deg 95%, 0.8 mol (27%V/V).
Add 23.9 milliliters and 20 milliliters organic phase solutions that contain extraction agent HD (DIBM) P0.8 mol saponification deg 95% of the vitriol intensified roasting infusion of baotite in 50 milliliters separating funnel, vibration is 8 minutes on the Kang Shi vibrator, reaches balance.Left standstill 3 minutes, and made organic phase and water layering.The pH value of water is 5.5.The rare earth extraction rate is 99%.With the raffinate venting, stay the supported rare earth organic phase in the separating funnel, be 4/1 with organic phase/water, add deionized water (as washings) vibration 2 minutes, remove the non-rare earth ionic impurity that is clipped in the organic phase.With washings deionized water discharging, repeated washing once adds 2.5 milliliters of the hydrochloric acid (or 6 mol nitric acid) of 6 mol in the organic phase of the rare earth of load again, strips 15 minutes.Left standstill 5 minutes, and obtained anti-stripping agent, its concentrations of rare-earth is 1.6 mol (269 grams per liters are in the oxide compounds of rare earth element).Acidity 0.3 mol.Back extraction ratio is 97%.Calcium, magnesium more than 80% are removed, and the phosphorus more than 70% is removed.Overwhelming majority sulfate radical is removed.
Embodiment 4
Remove lanthanum sesquioxide and calcium oxide impurity in the yttrium oxide.When from lucium, extracting pure yttrium oxide (＞99.99%) with naphthenic acid, often because of contain a spot of lanthanum sesquioxide in the product yttrium oxide and calcium oxide defective.For this reason, in present production, adopt P507 extraction yttrium and remove calcium, lanthanum.But the acidity that P507 strips is too high.The yttrium trichloride aqueous solution after the reextraction contains the free acid of 1-2 mol, and yttrium trichloride is transformed into before the yttrium oxalate, add the ammoniacal liquor neutralization, because a large amount of existence of ammonium chloride cause the oxalate precipitation rate of loss of yttrium to increase.With the method for extraction agent of the present invention, because the free acid content of YCL3 solution that back extraction obtains is low, save with ammonia neutral step, reduced the consumption of soda acid, improved the precipitate recovery rate of yttrium.
Make the stock liquid of water with yttrium trichloride, the concentration of yttrium is 0.2 mol, PH=4, calcic 1.3% in trioxygen-containingization two lanthanums 0.1%, three yttrium oxide in the yttrium oxide.Organic phase solution is for containing HD (DIBM) the P-kerosin (joining method with embodiment 3) of 0.5 mol (16%V/V), and saponification deg 90% is a washings with chemical pure 0.2 mol hydrochloric acid, is anti-stripping agent with the hydrochloric acid of chemical pure 3 mol.Adopt the water charging, adopt the fractionation counter-current extraction to separate.Progression: 3 grades of extraction sections, 14 grades of washing sections, 3 grades of stripping sections.Stream is than being V saponification organic phase: V feed liquid: V washings: V strip liquor=1.32: 1: 0.15: 0.2.Extraction is 8 minutes with back-extraction time.The clarification time of repose is 6 minutes.Temperature is 26 ℃.The concentration that obtains the strip liquor yttrium trichloride is 0.9 mol hydrogen ion concentration, 0.2 mol.Y 2O 3La in the product 2O 3Content is 90ppm, Ca＜7ppm, Y 2O 3〉=99.99%.Recovery of extraction is 99%.
Embodiment 5
The acidity that is used for isolating rare-earth chloride solution is PH=3, rare earth concentration 1.5 mol (266.9 grams per liters are in rare earth oxide), its composition (weight percentage %) is:
La 2O 3， CeO 2， Pr 6O 11， Nd 2O 3， Sm 2O 3， Eu 2Oa， Gd 2O 3，
6.29 ＜0.5 2.71 10.93 7.97 ＜0.1 14.29
Tb 4O 7， Dy 2O 3，Ho 2O 3 Y 2O 3 Er 2O 3 Tm 2O 3 Yb 2O 3 Lu 2O 3
3.04 18.79 4.47 4.09 12.52 0.90 11.21 2.19
The rare earth grouping separates to be carried out in two steps, at first separates from Gd/Tb, carries out Er/Tm then and separates, and obtains La-Gd, Tb-Er, Tm-Lu three group rare-earth enriched substance.Process flow sheet is seen Fig. 1.
The separation of Gd/Tb comprises extraction section a1, washing section b1, and the section of stripping c1, saponification device d1, extraction section a1 are 10 grades, and washing section b1 is 9 grades, and the section of stripping c1 is that 5 grades of d1 are soap tank.
Organic phase solution wherein contains the TBP (tributyl phosphate) of 15% (V/V) for containing the kerosin of extraction agent HD (DIBM) P1 mol, and saponification deg is 50%.The saponified method is that the ammoniacal liquor that adds 10 mol by pipe 4 ' in soap tank d1 carries out saponification.
Hydrochloric acid soln with 2 mol is a washings, is strip liquor with the hydrochloric acid of 3 mol.Feed liquid enters the 10th grade of extraction section a1 by pipe 1 ', enters the 1st grade of extraction section a1 through the organic phase of saponification by pipe 5 ', and washings enters the 9th grade of washing section b1 by managing 2 ', and strip liquor enters the 5th grade of organic phase RS Regenerator Section c1 by managing 3 '.Organic phase and water adverse current.
Stream is than being V saponification organic phase: V feed liquid: V washings: V strip liquor=6.3: 0.67: 0.8: 0.59.Outlet water in extraction back is the La-Gd enriched substance from managing 6 ' discharge, and rare earth concentration is 0.215 mol (31.8 grams per liters is in the oxide compound of rare earth element), its composition (weight percentage, %) as follows:
La 2O 3， CeO 2， Pr 8O 11， Nd 2O 3， Sm 2O 3， Eu 2O 3， Gd 2O 3， Tb 4O 7
15.1 0.9 6.5 26.2 19.1 ＜0.1 31.5 ＜0.05
Extraction liquid after the extraction (load organic phases) washs through washing section, anti-stripping agent (water) after the section of stripping is stripped flows out from managing 7 ', be the Tb-Lu enriched substance, its rare earth concentration is 1 mol (182.8 grams per liters, oxide compound in rare earth element), its composition (weight percentage %) is:
Gd 2O 3， Tb 4O 7， Dy 2O 3， Ho 2O 3 Y 2O 3 Er 2O 3 Tm 2O 3 Yb 2O 3 Lu 2O 3
1.95 5.2 32.2 7.7 7.0 21.4 1.5 19.2 3.7
Second step was carried out the separation of Er/Tm, comprised extraction section a2, washing section b2, and the section of stripping C2, saponification device d2, wherein extraction section a2 is 17 grades, and washing section b2 is 16 grades, and the section of stripping c2 is 5 grades of d2: soap tank.
The concentration of extraction agent and the saponification deg of extraction agent in the organic phase solution that uses, same when ammonia concn separates with Gd/Tb.Hydrochloric acid with 3 mol is washings, is anti-stripping agent with the hydrochloric acid of 4.5 mol.Be the isolating feed liquid of Er/Tm from managing the anti-stripping agent of discharging 7 '.Ammoniacal liquor, through saponified organic phase, feed liquid, washings, anti-stripping agent successively by 10 ', 11 ', 7 ', 8 ', 9 ' pipe enters (see figure 1) in the corresponding apparatus.Organic phase and water adverse current.
Stream is than being V saponification organic phase: V feed liquid: V washings: V strip liquor=7.56: 1: 1.5: 0.16.
Outlet water in extraction back is discharged from managing 12 ', is the Tb-Er enriched substance, and its concentrations of rare-earth is 0.34 mol (61.6 grams per liters is in the oxide compound of rare earth element), the composition of its rare earth (weight percentage %) is:
Gd 2O 3，Tb 4O 7， Dy 2O 3， Ho 2O 3 Y 2O 3 Er 2O 3 Tm 2O 3
2.58 6.89 42.7 10.2 9.28 28.4 ＜0.1
Extraction liquid after the extraction (load organic phases) washs through washing section, anti-stripping agent (water) after the section of stripping is stripped flows out from managing 13 ', be the Tm-Lu enriched substance, its rare earth concentration is 1.5 mol (295.7 grams per liters, oxide compound in rare earth element), its rare earth composition (weight percentage %) is:
Er 2O 3 Tm 2O 3 Yb 2O 3 Lu 2O 3
＜0.1 6.15 78.7 15.2
After entering the d2 saponification, the regeneration organic phase recycles.
Embodiment 6
The acidity that is used for the chloride soln of rare-earth separating is 0.5 mol, and rare earth concentration is 1.5 mol (295.7 grams per liters are in the oxide compounds of rare earth element), its composition (weight percentage, %):
Tm 2O 3 Yb 2O 3 Lu 2O 3
6.15 78.7 15.2
Divide to separate for two steps and carry out, at first separate, carry out Tm/Yb again and separate, and obtain TmCl from Yb/Lu 3, YbCl 3, LuCl 3Three single rare earth compounds.
The Yb/Lu sepn process comprises extraction section a3, washing section b3, and the section of stripping c3, saponification device d3, wherein extraction section a3 is 27 grades, and washing section b3 is 19 grades, and the section of stripping c3 is 5 grades, and d3 is a soap tank.Organic phase solution is the kerosin of 0.7 mol HD (DIBM) P, and saponification deg is 40%." ammoniacal liquor that adds 10 mol carries out saponification by pipe 4 in soap tank d3.Hydrochloric acid soln with 3 mol is a washings, is anti-stripping agent with the hydrochloric acid of 1N.
Feed liquid is by pipe 1 " enter the 27th grade of extraction section a3, the organic phase of saponification is by pipe 5 " enters the 1st grade of extraction section a3, and washings is by pipe 2 " enter the 19th grade of washing section b3, anti-stripping agent is by managing 3 " enters the 5th grade of reextraction section c3.Organic phase and water adverse current.The stream ratio is the organic phase of V saponification: V feed liquid: V washings: V strip liquor=4.66: 0.66: 3.21: 0.155.
Outlet water after the extraction is from managing 6 " discharges, is the Tm-Yb enriched substance.Concentrations of rare-earth is 0.24 mol (47.5 grams per liters is in the oxide compound of rare earth element), its composition (weight percentage, %):
Tm 2O 3 Yb 2O 3 Lu 2O 3
7.25 92.7 ＜0.5
Extraction liquid after the extraction (load organic phases) washs through washing section, anti-stripping agent (water) after the section of stripping is stripped is from managing 7 " flow out, rare earth concentration is 0.3 mol (59.7 grams per liters is in the oxide compound of rare earth element); its rare earth composition (weight percentage %) is:
Lu 2O 399% (Tm+Yb) 2O 3＜1% Lu 2O 3The rate of recovery be 97%.
The regeneration organic phase is got back to d3 and is carried out saponification and recycle.
Carry out the separation of Tm/Yb again, comprise extraction section a4, washing section b4, the section of stripping c4, saponification device d4, wherein extraction section a4 is 8 grades, and washing section b4 is 14 grades, and the section of stripping c4 is 5 grades, and d4 is a soap tank.
Used organic phase solution is the kerosin that contains extraction agent HD (DIBM) P of 0.7 mol, and saponification deg is 30%.With 10 mol ammoniacal liquor saponification, be washings with the hydrochloric acid soln of 2 mol, the hydrochloric acid soln of 3 mol is an anti-stripping agent." the Tm-Yb enriched substance of discharging is and carries out isolating aqueous phase liquid from managing 6.
Ammoniacal liquor, saponification organic phase, feed liquid, washings, strip liquor are successively by 10 ", 11 ", 6 ", 8 ", 9 " pipe enters (process flow sheet is seen Fig. 2) in the corresponding apparatus.Organic phase and water adverse current.
Stream is than being V saponification organic phase: V feed liquid: V washings: V strip liquor=26.7: 4.2: 0.98: 0.31.
Outlet water in extraction back is from managing 12 " discharge, its concentrations of rare-earth is 0.0283 mol (5.4 grams per liters is in the oxide compound of rare earth element), the composition of its rare earth (weight percentage %) is:
Tm 2O 2 99％，(Yb+LU) 2O 3 ＜1％
Extraction liquid after the extraction (load organic phases) washs through washing section, anti-stripping agent (water) after the section of stripping is stripped is from managing 13 " flow out, its rare earth concentration is 1 mol (197.0 grams per liters is in the oxide compound of rare earth element); its rare earth composition (weight percentage %) is:
Tm 2O 3 Yb 2O 3 Lu 2O 3
0.1％ 99％ 0.6％
After entering the d4 saponification, the regeneration organic phase recycles.
Embodiment 7
The composition of rare earth chloride liquid is (weight percentage, %) Sc 2O 216.1, (Lu+Yb) 2O 383.9 the PH of feed liquid is 1.8, the concentration of rare earth feed liquid is 0.0943 mol.Organic phase is HD (DIBM) the P-kerosin of 0.11 mol.
In 20 milliliters separating funnel, above-mentioned feed liquid and organic phase are mixed vibration 10 minutes by comparing organic phase/water=2/1, obtaining load organic phases, to contain concentrations of rare-earth be 0.011 mol, and the percentage extraction of scandium is 41%, and the percentage extraction of Yb+Lu is 11%.Hydrochloric acid back extraction load organic phases with 1 mol is in a ratio of organic phase/water=1/1, vibrates 10 minutes.Back extraction ratio is 97% for the first time, and back extraction ratio is 100% for the second time, merges the secondary strip liquor, and its rare earth consists of (weight percentage, %) Sc 2O 346, (Lu+Yb) 2O 354%.

Claims (17)

1. the method for a liquid-liquid extraction purifying separating rare earth element, make be present at least a rare earth element in the aqueous solution separate with at least a other rare earth element in being present in this aqueous solution or make be present in the aqueous solution at least a rare earth element and be present in this aqueous solution at least a non-rare earth separate, it is characterized in that this sepn process comprises that the water that will contain the aqueous solution of rare-earth element salt carries out liquid-liquid extraction with the organic phase that contains two (diisobutyl methyl) phosphoric acid extraction agent and separates.
2. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that the aqueous solution of said rare-earth element salt is rare earth nitrate, rare earth sulfate, rare earth chloride, the rare earth perchlorate is a kind of aqueous solution of salt wherein.
3. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that the concentration of the aqueous solution of rare-earth element salt is the 1-500 grams per liter,, be equivalent to the 0.01-4.5 mol in the oxide compound of rare earth element.
4. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 3, it is characterized in that the hydrionic concentration of the aqueous solution of rare-earth element salt is 10 -4～3 mol.
5. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that contain at least a organic thinner in the organic phase, organic thinner is aliphatic hydrocarbon, kerosene, halohydrocarbon, aromatic hydrocarbon, the solvent type petroleum cuts of perfume oil.
6. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that extraction agent two in the organic phase (diisobutyl methyl) concentration of phosphoric acid is the 3-100% of organic phase volume, percent by volume is equivalent to the 0.1M-3 mol.
7. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that contain a kind of additive in the organic phase at least, additive is higher alcohols, higher phenols, phosphoric acid ester, the sulfoxide of C4-C15.
8. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that the hydrogen ion concentration after the water hydrogen ion concentration makes extraction when extraction is 10 -7～1 mol.
9. the method for a kind of liquid-liquid extraction purifying separating rare earth element according to Claim 8 is characterized in that, the hydrionic concentration of aqueous phase is regulated with alkali or basic salt.
10. according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that the temperature of extraction is 10 °-50 ℃.
11. the method according to a kind of liquid-liquid extraction purifying separating rare earth element of claim 1 is characterized in that, is that washings washs organic phase with a kind of acid wherein of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid after extraction.
12. method according to a kind of liquid-liquid extraction purifying separating rare earth element of claim 1, it is characterized in that, be that washings washs organic phase with the aqueous solution that should be extracted into rare earth chloride in the organic phase, rare earth nitrate, rare earth sulfate, rare earth perchlorate a kind of salt wherein after extraction.
13, according to the method for a kind of liquid-liquid extraction purifying separating rare earth element of claim 11, it is characterized in that when washing as washings with a kind of acid wherein of hydrochloric acid, nitric acid, the concentration of hydrochloric acid, nitric acid is 0.1～10 mol.
14. method according to a kind of liquid-liquid extraction purifying separating rare earth element of claim 12, it is characterized in that with rare earth chloride, rare earth nitrate is when wherein a kind of aqueous solution of salt is washings washing organic phase, its concentration is the 1-500 grams per liter, in the oxide compound of rare earth element.
15. the method according to a kind of liquid-liquid extraction purifying separating rare earth element of claim 11 is characterized in that, after extracting and washing, is strip liquor with a kind of acid, and the rare earth element in the organic phase of supported rare earth is stripped into aqueous phase, makes organic phase regeneration.
16. the method according to claim 15 a liquid-liquid extraction purifying separating rare earth element is characterized in that, when being strip liquor with wherein a kind of acid of hydrochloric acid, nitric acid, its concentration is 0.5～10 mol.
17. method according to any a kind of liquid-liquid extraction purifying separating rare earth element of claim 1 to 16, it is characterized in that, the aqueous solution of the first operation middle-weight rare earths element salt with contain thinner and contact with extraction agent two (diisobutyl methyl) phosphoric acid organic phase, an a kind of rare earth element or group rare earth element with high partition ratio, preferentially enter organic phase, have an a kind of rare earth element of lower partition ratio or a group rare earth element or non-rare earth and then be enriched in aqueous phase; In second operation organic phase then optionally with contain hydrochloric acid, nitric acid, sulfuric acid, perchloric acid wherein a kind of acid or the aqueous solution that contains rare earth element muriate, rare earth element nitrate, rare earth element vitriol, rare earth element perchlorate a kind of salt wherein as washings, get less the sort of rare earth element, non-rare earth to remove organic extractant phase, or a group rare earth element, make organic phase and aqueous phase separation then; In the 3rd operation, contact with organic phase as strip liquor, contain the organic phase of extraction agent with regeneration with containing aqueous acid.
CN92113216A 1992-11-25 1992-11-25 Extracting technological method for purifying separating rare earth element Expired - Fee Related CN1040889C (en)

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CN104878202B (en) * 2014-02-28 2017-04-26 中国石油化工股份有限公司 Method for extracting rare earth from rare earth-containing sludge
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