CN1009332B - Extracting and separating rear earth element from sulfuric acid system - Google Patents
Extracting and separating rear earth element from sulfuric acid system Download PDFInfo
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Abstract
To smelt the infusion that rare earth ore concentrate makes with sulfuric acid strengthening roasting, use in the magnesium oxide and purification, obtain purified rare earth sulfate solution.Be that available P204 kerosin carries out fractionation extraction.The concentration of mishmetal in the feed liquid＜50 grams per liter rare earth oxides, the concentration of extraction agent＜2 mol.Technology of the present invention can make heavy rare earths enriched substance in samarium, europium, the gadolinium etc., and (Eu203 11%, Sm203～50%, the Eu203 rate of recovery～99%, products such as thick Neodymium trichloride (Nd203/RE203＞85%) and lanthanum cerium nitride.Thick ammonification neodymium can be made the raw material of high-performance magnet neodymium iron boron.Technology of the present invention is saved transition, and operations such as extraction agent saponification greatly reduce the cost of product.
Description
The present invention relates to the rare-earth extraction separating process of rare earth metal hydrometallurgy, is the technology of extraction agent fractionation extraction grouping separation of rare earth elements with di-(2-ethylhexyl)phosphoric acid (hereinafter to be referred as P204) in sulfuric acid system specifically.
Bastnasite and bastnasite have sulfuric acid roasting method and sodium carbonate roasting method and caustic soda decomposition method with the decomposition method that mixes the ore deposit of monazite.
It is that the rare earth ore concentrate ore deposit of mixing of monazite (bastnasite or the bastnasite with) is mixed afterwards in rotary kiln continuous roasting (rare earth under 300～800 ℃ temperature with the vitriol oil that sulfuric acid roasting method decomposes rare earth ore concentrate, the first volume, " rare earth " writes group, metallurgical industry press, 1978,190～210 pages), material adds from the kiln tail, move and exsiccation gradually to kiln hood in the decomposition course, the roasting material that kiln hood is discharged is generally 2～5 millimeters bead, diffusing pulp thing can directly be used water extraction behind the chance water.Rare earth ore concentrate and vitriol oil mixing post-heating are to above-mentioned temperature, and elements such as rare earth and thorium generate soluble sulphate, and fluorite is transformed into calcium sulfate and the volatile gases hydrogen fluoride or the silicon fluoride of indissoluble; Mineral such as iron, manganese also decompose to some extent and change into vitriol.Material behind sulfuric acid baking will be used water extraction, owing to contain impurity such as iron, phosphorus, manganese, thorium in the infusion, must purify.Classical purifying method is, adding sodium-chlor and sodium sulfate in infusion makes rare earth be precipitated out with its impurity with the form of rare earth sulfuric acid sodium double salt to separate, the rare earth sulfuric acid sodium double salt that is precipitated out is converted into the oxyhydroxide of rare earth with 20～30% the caustic soda aqueous solution after washing, with hydrochloric acid rare-earth hydroxide is dissolved, form rare-earth chloride solution.
The method of rare earth element grouping has double salt precipitation method and fractional-distillation extraction (" rare earth " writes group for rare earth, the first volume, metallurgical industry press, 1978,534-536 page or leaf), but with extraction process for well.With P244 is extraction agent, is thinner with kerosene, in hydrochloric acid system or nitric acid system, lucium extraction can be divided into light, in, three groups of heavy rare earths.The principle of grouping is certain aqueous phase acidity and a percentage extraction of control.Under different acidity, P204 is different with the complex ability of rare earth element, controls certain acidity and can make it have certain percentage extraction and stripping rate, and rare earth element just can be by predetermined boundary grouping.The boundary and the acidity control scope of grouping are as follows: samarium-neodymium grouping, and washing lotion acidity 0.5～1.2 mol hydrochloric acid, separation factor β Sm/Nd is 5～11; Samarium-gadolinium grouping, washing lotion acidity is 1.5～2.0 mol hydrochloric acid, separation factor β Gd/Sm is 3～3.5; Gadolinium-terbium grouping, washing lotion acidity 2.0 mol hydrochloric acid, separation factor β Tb/Gd is 5～6, the concrete fractionation extraction grouping flow process of its rare earth element is, the concentration of feed liquid is 1～1.2 mol rare earth chloride, and feed acidity is PH4～4.5, the P204 kerosin that consists of 1.0 mol of organic phase, the acidity of washing lotion is 0.8 mol hydrochloric acid, carries out neodymium-samarium grouping.It contains the raffinate of rare earth elements such as lanthanum neodymium, generate rare earth chloride with in the ammonia and back condensing crystal, the organic phase of rare earth elements such as its load gadolinium, dysprosium is carried out the grouping extraction of gadolinium-dysprosium again, the concentration of extraction agent still is 1 mol P204, kerosene is thinner, the acidity of washing lotion is 2.0 mol hydrochloric acid, and the water after the extraction forms middle-weight rare earths carbonate with the yellow soda ash precipitation.The organic phase that the extraction back generates is stripped with 5 mol hydrochloric acid, generates yttrium and heavy rare earths chloride product.
Divide the flow process of group rare-earth to compare with the double salt precipitation method has many good qualities with the P204 fractionation extraction, P204 fractionation extraction method of grouping has been simplified technology, realized the production serialization, exempted double salt precipitation, the heavy physical labor of operations such as alkali conversion, can produce light, in, the heavy rare earths product, enlarged Comprehensive Utilization of Rare, can directly directly be connected mutually again, further separate purification again, and reduced the three wastes with following step fractionation extraction process.Carry out fractionation extraction with P204 in hydrochloric acid system, P204 needs saponification, consumes a large amount of alkali, and the P204 solution loss is increased.
It is the technology (smeltery, Tong County, Beijing City, Beijing College of Iron and Steel Technology, with P204 the continuous extraction of rare earth chloride is separated 1979 in hydrochloric acid system) of extraction agent fractionation extraction grouping separation of rare earth elements in hydrochloric acid system that units such as smeltery, Tong County, Beijing City and Beijing College of Iron and Steel Technology have proposed with P204.
The packet header unit of waiting of metallurgical institute has proposed technical process (the packet header metallurgy institute of the usefulness 2-own ester of ethylhexyl phosphoric acid single 2-ethyl (hereinafter to be referred as P507) separation of rare earth elements, Baotou steel company, the smeltery, packet header, the P507-HC1 system is light, middle-weight rare earths extracts continuous separation technology expanding test report entirely, 1982, October) this technology is to be raw material with the rare earth chloride, its feed concentration is 240～250 grams per liter rare earth chlorides, feed acidity is PH2-3, organic phase consists of 50%P507-50% kerosene (volume ratio), saponification 0.54 mol P507, washing lotion acidity is 1.22～1.28 mol hydrochloric acid, at first carrying out neodymium-samarium grouping, is that extraction agent carries out praseodymium-neodymium successively again with P507, cerium-praseodymium, lanthanum-cerium, samarium-europium, the grouping of gadolinium-terbium separates and obtains Neodymium trioxide, Praseodymium trioxide, cerium oxide, lanthanum trioxide, product such as Samarium trioxide and heavy rare-earth oxide.
It is the processing method of extraction agent extracting and separating rear earth element that the Japanese documentation spy opens that clear 54-93672 also introduced with P507, in order to accelerate the speed of phase-splitting, needs to add phase separation agent, prevents the generation of emulsification and third phase.
With P507 is that the advantage of extraction agent is that reextraction acidity is low, is easy to strip, and separation factor is bigger than P204 between some rare earth element, but the P507 extraction more still needs saponification with the present invention, and the price of P507 is than P204 height.
(Beijing Non-Ferrous Metal Research General Academy, Beijing Non-Ferrous Metal Research General Academy, the vitriol intensified roasting of Baotou rare earth ore concentrate-extraction process is produced rare earth chloride commerical test report, 1979, August) technology of the vitriol intensified roasting of Baotou rare earth ore concentrate has been proposed, improved the temperature of roasting, prolonged roasting time, make the phosphorus in the ore, thorium, impurity such as iron form materials such as sl. sol. phosphoric acid salt, with water extraction calcining matter material, the acidity of infusion is 0.05～0.15 mol sulfuric acid, with in calcium oxide or the lime carbonate and infusion, the iron of trace in the solution, phosphorus, thorium is respectively with ironic hydroxide, tertiary iron phosphate, thorium hydroxide, forms such as thorium phosphate further precipitation are removed, and obtain pure rare earth sulfuric acid solution with separated from impurities, if with P204 or P507 is that extraction agent is connected mutually with the technology of hydrochloric acid system fractionation extraction grouping separation of rare earth elements, just must be by transformation process, it is the muriate of rare earth that rare earth sulfuric acid solution is made the transition.The method of transition is in the sulphuric acid soln of PH4-5, is extraction agent with lipid acid or the naphthenic acid that contains 5 carbon to 9 carbon, and kerosene is that thinner extracts, and is the anti-stripping agent generation rare earth chloride of stripping with the hydrochloric acid of 5 mol again.
Since nineteen eighty-three, high-performance magnet neodymium iron boron came out, the neodymium little for the past purposes found market, in order to reduce the production cost of high-performance magnet neodymium iron boron, just must work out a new production technique that reduces the Neodymium trioxide cost.The purity requirement of the raw material Neodymium trioxide of industrial production high-performance magnet neodymium iron boron is not high, allows to contain a small amount of Pr6011 in the Neodymium trioxide, so it is low to work out cost, the method that quality meets as the Neodymium trioxide of high-performance magnet neodymium iron boron raw material necessitates.
Purpose of the present invention just be to work out one with vitriol intensified roasting rare earth concentrate water logging after the technical process of the fractionation extraction grouping separation of rare earth elements that directly is connected of purification rare earth sulfuric acid solution, save operation transition, make this technology can produce enriched substance and lanthanum, the cerium chloride of rare earth elements such as samarium, europium, gadolinium and can produce the cheap Neodymium trioxide that is applicable to as high-performance magnet neodymium iron boron raw material.Another object of the present invention is to simplify existing technical process, and the consumption of saving industrial chemicals reduces product cost.
J.Alstad once was extraction agent has been measured various single rare earth elements in sulphuric acid soln partition ratio (J.Alstad et al International Solvent extraction conference 1974.1083-1111 page or leaf) with P204.Extracting rare-earth element in sulphuric acid soln, forefathers had once carried out a few thing, also there is the people that single rare earth elements such as cerium, europium, terbium were done extracting and separating research, but because rare earth element solubleness in sulphuric acid soln is less, the purified rare earth sulfate solution of difficult again directly acquisition is that extraction agent carries out the systematic research of fractionation extraction grouping separation of rare earth elements in the vitriolic earth solution for extremely not seeing with P204 as yet so far.
The present invention is a kind of processing method of fractionation extraction grouping separation of mixed rare-earth element, with di-(2-ethylhexyl)phosphoric acid (being called for short P204) is extraction agent, with with the not miscible organic solvent of water be thinner, infusion with vitriol intensified baked rare earth ore concentrate, oxide compound neutralization with alkaline-earth metal, and make purified sulfuric acid rare earth feed liquid, directly carrying out the fractionation extraction grouping in the sulfuric acid rare earth purified solution separates, the acidity of feed liquid is PH4 to 0.315 mol sulfuric acid, the acidity of washing lotion is 0.25～1 mol sulfuric acid, the concentration of mishmetal in the feed liquid＜50 grams per liter rare earth oxides, with the not miscible thinner of water in the concentration of extraction agent di-(2-ethylhexyl)phosphoric acid be＜2 mol, said alkaline earth metal oxide is a magnesium oxide.
With P204 is in the processing method of extraction agent fractionation extraction grouping separation of rare earth elements in sulfuric acid system, the being extracted property of rare earth element increases along with the increase of rare earth element ordination number, that is to say that the big rare earth element of the ordination number rare earth element littler than ordination number preferentially is extracted in the organic phase, when the organic phase that contains rare earth element contacts with washing lotion, the little rare earth element priority enrichment of ordination number is in washing lotion, and the big rare earth element priority enrichment of ordination number is in containing the organic solution of extraction agent, and the rare earth element grouping is separated.Along with the increase of rare earth feed liquid acidity, the percentage extraction of all rare earth elements and partition ratio descend; Its separation factor β descends lentamente with the increase of feed acidity; Along with the decline of P204 concentration in the organic phase, the also corresponding decline of the partition ratio of rare earth element, percentage extraction, but separation factor β value is not subjected to the influence of P204 concentration substantially, therefore controls certain feed acidity and just rare earth element can be divided into groups to separate with washing lotion acidity.
Because in the sulphuric acid soln of rare earth element, with P204 extraction agent when extracting, neodymium-samarium separation factor β value is bigger, and grouping separation between neodymium-samarium easily is separated into good so at first carry out fractionation extraction between neodymium-samarium.
The concentrate that mixes the ore deposit of bastnasite or bastnasite and monazite, the Baotou rare earth ore concentrate of China for example in the infusion that makes with sulfuric acid strengthening roasting, still contains a spot of impurity element and sulfuric acid freely.The concentration that generally contains rare earth oxide 30～50 grams per liters, phosphorus 0.1～0.5 grams per liter, iron 1.0～2.0 grams per liters, thorium 0.01～0.1 grams per liter, free acid in the infusion is 0.05～0.15 mol sulfuric acid, impurity elements such as phosphorus, iron, thorium must be removed from solution, oxyhydroxide with basic metal or ammonium is made neutralizing agent, certainly will produce the rare earth sulfuric acid double salt precipitation, be directed at the loss of rare earth element.Use calcium oxide or Paris white to purify rare earth sulfate solution, can avoid the generation of rare earth sulfuric acid double salt as neutralizing agent.But owing to generated calcium sulfate, the quantity of slag increases the absorption rare earth ion decreases the rate of recovery of rare earth element, so be the best with magnesium oxide as neutralizing agent.The acidity of the rare earth sulfuric acid infusion that sulfuric acid strengthening roasting makes generally is controlled at 0.05～0.15 mol.Vitriolic acidity is higher than 0.15 mol, and the magnesium oxide consumption increases, and vitriolic acidity is lower than 0.05 mol, causes the rare earth element leaching yield to reduce.Purify and generally at room temperature to carry out, make the PH after the neutralization reach 3.5～5.If solution PH＜3.5 after purifying, iron, thorium separate not exclusively, and PH＞5 a rare earth element loss increases.Contain rare earth oxide 30～50 grams per liters, thorium＜0.001 grams per liter, iron 0.01～0.02 grams per liter, phosphorus 0.0005～0.0020 grams per liter in the solution after the purification, heavy rare-earth oxide accounts for about 2% of total rare earth (TRE) oxide amount, and the content of Eu2O3 is about 0.2% of total rare earth (TRE) oxide amount.Separate so at first carry out neodymium-samarium, will in, heavy rare-earth extraction separates.Rare earth sulfate solution after purifying promptly can be used as neodymium-isolating feed liquid of samarium extraction grouping.
Because the rare earth element chemical property is very similar, be difficult with the method for the single-stage extraction separation of rare earth elements that divides into groups, generally adopt fractional-distillation extraction.The fractionation extraction system is made up of n stage countercurrent extraction section and m stage countercurrent washing section, (document that has is with the independent integral part of charging level as the fractionation extraction system as the charging level for the n level of counter-current extraction section, be not included in the counter-current extraction section), the organic phase solution that contains extraction agent, enter the fractionation extraction system from the first step of counter-current extraction section, discharge from the m level of countercurrent washing section, washing lotion enters the fractionation extraction system from the m level of countercurrent washing section, discharge from the first step of counter-current extraction section with the water that raffinate forms, the feed liquid that contains rare earth element enters the fractionation extraction system from the n level of counter-current extraction section.
Single-stage extraction and all available separating funnel of small-sized tandem fractionation extraction test carry out, and the known mixing of the also available person of an ordinary skill in the technical field of expanding test-clarification formula extractor carries out.When extracting, control certain comparing, vibration regular hour, for example 5～6 minutes with separating funnel.If when extracting, then control the stream ratio between organic phase, feed liquid, the washing lotion with mixing-clarification formula extractor.Temperature when no matter being single-stage extraction or fractionation extraction is advisable between 18 °～35 ℃.
Because extraction agent P204 viscosity is big, must use organic solvent diluting in order to dilute extraction agent.The necessary dissolution extraction agent of thinner, and don't water-soluble.The organic solution that forms after the agent of thinner dissolution extraction is organic phase.When this organic phase and the water that the contains rare earth element certain hour that vibrates together, can be divided into two-phase again after static.Effectively thinner is alkyl hydrocarbon polymer or the aromatic base hydrocarbon polymer that high flash point is arranged.They can be halogenated hydrocarbon, higher alcohols, ether, ester or their mixture, but are good with kerosene.Concentration＜2 mol the P204s of extraction agent in thinner, but with 0.5～1.5 mol P204 for well.
For the fractionation extraction grouping of carrying out neodymium-samarium separates, its condition is to contain 30～46 grams per liter rare earth oxides in the feed liquid, its acidity is PH4～0.15 mol sulfuric acid, organic phase is the kerosin that contains 0.5～1.5 mol P204, washing lotion acidity is 0.4～0.6 mol sulfuric acid, the stream ratio of organic phase, feed liquid, washing lotion is 1: 4～7: 0.3～0.4,3～8 grades of counter-current extraction sections, and the countercurrent washing section is good for 7～12 grades.What of the progression of counter-current extraction section and countercurrent washing section are mainly by the separation factor β of the compositions of feed liquid, rare earth element with require the purity of product to decide.Feed liquid middle-weight rare earths oxide content is greater than 46 grams per liters, near the solubleness of rare earth element in sulphuric acid soln, the rare earth compound crystalline deposit appears easily, rare earth oxide content increases later extraction equipment less than 30 grams per liters, throughput reduces, so be good with 30～46 grams per liter rare earth oxides.
The concentration of extraction agent P204 in kerosene increases the organic phase viscosity of formation greater than 1.5 mol, and the phase-splitting difficulty less than 0.5 mol P204, reduces throughput.Washing lotion acidity surpasses 0.6 mol sulfuric acid, and the crystal of the vitriol of rare earth element is separated out, and washing lotion acidity is less than 0.4 mol sulfuric acid, and washing effect is not good.Under above-mentioned good operational condition, the neodymium that all can obtain-samarium grouping separating effect.The organic phase of discharging from countercurrent washing section last step contains samarium, europium, the gadolinium etc., the enriched substance of heavy rare earth element, organic phase middle-weight rare earths oxide content 3～6 grams per liters, outlet aqueous phase rare earth oxide is 25～43 grams per liters, and the concentration of its free acid is 0.08～0.13 mol sulfuric acid.This outlet water is called the sulfuric acid raffinate of rare earth elements such as containing lanthanum, cerium, praseodymium, neodymium.With 5～6 mol hydrochloric acid is anti-stripping agent, to contain in samarium, europium, the gadolinium etc., the organic phase of heavy rare earth element strips, its enriched substance, the organic phase that contains P204 is returned and is recycled.In samarium, europium, the gadolinium etc., contain Eu2O3 11.0～12.2% in the heavy rare earth element enriched substance, Sm2O3 44.0～52.0%, and Gd2O3 about 20%, and the Eu2O3 rate of recovery is 99%, the Sm2O3 rate of recovery＞92% contains Nd2O3＜0.1%.
Preferably with the above-mentioned sulfuric acid raffinate that contains oxide compound 25～43 grams per liters of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, adjust its acidity to PH0.7～4, as carrying out praseodymium-neodymium isolating feed liquid of dividing into groups, the concentration of washing lotion is 0.4～0.56 mol sulfuric acid, contain 1.0～1.5 mol P204 in the organic phase, kerosene is thinner, and the stream ratio of organic phase, feed liquid, washing lotion is 2.0～2.2: 1: 0.7～0.9; The counter-current extraction section is 13～21 grades, and the countercurrent washing section is 7～24 grades, and the grouping of carrying out the fractionation extraction of praseodymium-neodymium separates.The water of discharging from the extraction section first step is the sulfuric acid raffinate that contains rare earth elements such as lanthanum, cerium, and the organic phase that contains neodymium of discharging from the washing section last step is that strip liquor is stripped with the hydrochloric acid of 5-6 mol, and hydrochloric acid soln that must thick neodymium.The organic phase that contains P204 is returned and is recycled.The rate of recovery of Nd2O3 is 93～99%, contains Nd2O3 85～90% among product Nd2O3 that obtains or the NdCl3, La2O3＜0.1%, and CeO2 0.58～3.3%, Pr6O11 5.10-11.35%, Sm2O3＜2.1%.Because Nd2O3/RE2O3 is that 85～90%(RE2O3 is a mixed rare-earth oxide in the required Neodymium trioxide of high-performance magnet NdFeB material, down together), so product of the present invention can be used as the raw material of high-performance magnet neodymium iron boron fully.
Contain the available double salt precipitation method of sulfuric acid raffinate (containing 17～28 grams per liter rare earth oxides) or the oxalate precipitation method or the carbonate precipitation method processing of rare earth elements such as lanthanum, cerium from the water of above-mentioned extraction section first step discharge.But preferably above-mentioned sulfuric acid raffinate is regulated its PH to 1～5, carry out counter-current extraction.Contain 1.0～1.5 mol P204 in the organic phase kerosene, organic phase, water, (feed liquid) be in a ratio of 1～3: 1, the progression of counter-current extraction is 4～8 grades, best 5～6 grades, can get preferable result.The percentage extraction of rare earth element such as lanthanum, cerium＞95%.The organic phase of gained is that anti-stripping agent is stripped with 5～6 mol hydrochloric acid or with 5～6 mol nitric acid, and the sulfuric acid raffinate discards.Contain RE2O3 200 grams per liters in the rare earth element chloride solns such as gained lanthanum, cerium, contain La2O3 33.25～37.74% among the RE2O3, CeO2 57.83～60.67%, Pr6O11 1.70～4.93%, Nd2O3 0.80～4.40%, and this mixed rare-earth oxide can be used as the raw material of producing cerium dioxide polishing powder and norium product.
In order to improve the handiness of operational path of the present invention, according to above-mentioned theory, take the similar main technologic parameters of above-mentioned each operation stage, can at first carry out the fractionation extraction grouping between cerium-praseodymium separates, water is the sulfuric acid raffinate that contains rare earth elements such as lanthanum, cerium, regulates the PH of its raffinate, with the kerosene organic extractant solution that contains P204, raffinate discards, and organic phase is stripped with hydrochloric acid or nitric acid and generated rare earth chloride or nitrate.The organic phase that cerium-praseodymium grouping back generates contains rare earth elements such as praseodymium, neodymium, samarium, europium, and with the reextraction of 5～6 mol hydrochloric acid, the kerosene organic phase that contains P204 is returned and recycled.Regulate anti-stripping agent to required pH value, with the kerosene that contains P204 is organic phase, is that washing lotion is carried out neodymium-samarium fractionation extraction grouping and separated with hydrochloric acid, water gets thick NdC13, in load samarium, europium, the gadolinium etc., the organic phase of heavy rare earth element with hydrochloric acid strip its enriched substance.
The present invention's isolating fractionation extraction of also can at first between praseodymium-neodymium, dividing into groups, water can get the muriate of lanthanum, cerium, praseodymium, organic phase obtain neodymium, samarium, europium, gadolinium in, heavy rare earth element, carry out neodymium-samarium grouping at last again and separate, thick Nd2O3 and Sm, Eu, Gd enriched substance.But generally at first be separated at neodymium-samarium.
Advantage of the present invention is: first, the technology of the present invention technical process that to be the purification rare earth sulfuric acid solution produced of sulfuric acid strengthening roasting directly be connected with the technology of fractionation extraction grouping separation of rare earth elements, save lipid acid (or naphthenic acid) operation transition, need not change extraction system.Because the concentration of the rare earth element in the feed liquid is up to the rare earth oxide about 50 grams per liters, extraction agent P204 does not need to carry out saponifying process more rambunctious.Second, though the concentration of rare earth sulfate solution middle-weight rare earths element is low, extraction equipment is increased, the organic phase input amount that contains extraction agent P204 is many slightly, but owing to reduced transition, operations such as extraction agent saponification, having saved lipid acid (or naphthenic acid) neutralizes with a large amount of chemical materialss such as alkali, and in acidic solution, extract, reduced the solution loss of extraction agent P204, P204 is than P507 low price, the price of P507 approximately is 4 times of P204 price, so use the present invention from concentrate to producing samarium, europium, heavy rare earth element enriched substance or three kinds of products such as pr-nd enriched product and lanthanum cerium chloride in the gadoliniums etc., the expense of the chemical materials that is consumed only are about 2/3 of other technical process chemical materials expenses.The cost of thick Neodymium trichloride is 1/3～1/4 of other flow processs only, so greatly reduce the price of product.The thick neodymium compound of being produced can be used as the raw material of high-performance magnet neodymium iron boron, thereby has reduced the price of high-performance magnet neodymium iron boron; The muriate of lanthanum cerium can be made the raw material of products such as polishing powder and norium; Samarium, europium, gadolinium enriched substance can be used as the raw material that extracts samarium, europium, gadolinium.The 3rd, in the extraction process owing to there is not the interference of silicon, fluorine, phosphorus and micro-flocculation agent, emulsification does not take place, guaranteed normally carrying out of extraction process.The 4th, in sulfuric acid system, use P204 as extraction agent, kerosene is that thinner carries out fractionation extraction grouping separation of rare earth elements, when PH1～4 than the separation factor β height between some rare earth element in hydrochloric acid system, for example, separation factor β sm/Nd is 8.34～11.98 in sulfuric acid system, and β Nd/pr is 1.34, and separation factor β sm/Nd is 5～11 in hydrochloric acid system, and β Nd/pr is 1.29.The 5th, the rare earth sulfate solution of vitriol intensified roasting water logging is used in the magnesium oxide and purification, prevents to generate double salt of rare earth precipitation and calcium sulfate slag, and compare with the rate of recovery 2% that has improved the scavenging process middle-weight rare earths in calcium oxide or the Paris white with purification, the quantity of slag has reduced by one times.
The analysis of rare earth element is carried out with X fluorescent spectrometry, emission spectrometry, non-rare earth spectrophotometry, the total amount of rare earth gravimetric determination in the solution.
Figure one fractionation extraction system synoptic diagram.
Figure two process flow diagrams.
Below the present invention will be described in more detail with embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
The purification of rare earth sulfate solution.
The rare earth sulfate solution (infusion of the sinter of producing by sulfuric acid strengthening roasting) that will contain impurity and free acid, place steel basin slowly to add magnesia powder (industrial magnesium oxide in room temperature, contain magnesium oxide 96%, magnesium ore deposit, Dashiqiao) impurity is removed in neutralization, the last pH value of control solution is 4～4.5, kept 20 minutes, and filtered and promptly to get purified rare earth sulfate solution, the results are shown in Table one, table two.
Table one. the composition of the rare earth sulfuric acid solution before and after purifying
Composition grams per liter RE2O3 grams per liter Th grams per liter Fe grams per liter P grams per liter acidity mol
Purify preceding 45.0 0.1 1.5 0.2 0.07
Purify back 45.0＜0.001 0.01 0.0015 PH4
Table two. purify the shared per-cent of various rare earth elements in the rare earth sulfuric acid solution of back
Rare-earth elements La 2O3 CeO2 Pr6O11 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Y2O3 other
Title
% 27.53 49.70 5.13 15.44 1.20 0.23 0.33 0.20 0.1
Embodiment 2
Feed acidity is to the influence of extraction.
Its experiment condition is: organic phase is 1 mol P204(Shanghai Chemical Plant) No. 260 solvent oil (a kind of kerosene; factory of shanghai refinery) solution; feed liquid is the vitriolic earth solution; containing rare earth oxide is 37.26 grams per liters; be in a ratio of organic phase: water (feed liquid)=1: 1, extracted 5 minutes, the temperature during extraction is 25 ℃; extract with separating funnel, the result is shown in table three, the table four.
Table three, feed acidity is to the influence of extraction
The feed liquid balance has balance RE2O3 RE2O3 partition ratio D
Initial machine phase water distributes extraction La Ce Pr Nd Sm
Acidity RE2O3 ratio
RE2O3 H2SO4 D
Mol grams per liter grams per liter mol % (single rare earth element)
PH4 14.69 22.91 0.125 0.638 39.21 0.19 0.61 0.95 1.24 14.85
0.050 11.98 26.82 0.150 0.447 30.87 0.13 0.41 0.60 0.81 7.94
0.125 8.47 29.90 0.205 0.283 22.07 0.08 0.25 0.36 0.49 4.09
0.205 6.13 33.79 0.260 0.181 15.36 0.051 0.15 0.22 0.29 2.52
0.270 4.45 34.15 0.310 0.130 11.53 0.034 0.11 0.15 0.20 1.75
0.315 3.78 35.31 0.350 0.107 9.67 0.028 0.08 0.12 0.16 1.33
Table four, feed acidity is to the influence of separation factor β
The feed liquid balance has balance RE2O3 RE2O3 separation factor β
Initial machine phase water distributes extraction
Acidity RE2O3 ratio
RE2O3 H2SO4 Ce/Pr/Nd/Sm/
Mol grams per liter grams per liter mol D % La Ce Pr Nd
PH4 14.69 22.91 0.125 0.638 39.21 3.21 1.56 1.31 11.98
0.050 11.98 26.82 0.150 0.447 30.87 3.15 1.47 1.35 9.8
0.125 8.47 29.90 0.205 0.283 22.07 3.12 1.44 1.36 8.35
0.205 6.13 33.79 0.260 0.181 15.36 2.94 1.47 1.34 8.68
0.270 4.45 34.15 0.310 0.130 11.53 3.11 1.35 1.35 8.75
0.315 3.78 35.31 0.350 0.107 9.67 2.49 1.43 1.34 8.34
＊3.09 ＊1.43 ＊1.34 ＊9.5
* represents average mark from factor beta in the table
From table three, four as can be seen along with the increase of feed acidity, the percentage extraction of rare earth element and partition ratio D all descend, separation factor β increases and decline lentamente with the acidity of feed liquid, when the initial acidity of feed liquid was increased to 0.315 mol sulfuric acid by PH4, β Sm/Nd was reduced to 8.34 by 11.98.
Embodiment 3
Organic phase concentration is to the influence of extraction.
Its experiment condition is that feed liquid is the pure earth solution of vitriolic, contains rare earth oxide 39.84 grams per liters, PH4, No. 260 solvent oil is a thinner, compare with the extraction time with embodiment 2, the results are shown in Table five, six.
Table five. P204 concentration is to the influence of extraction in the organic phase
Organic balanced have a balance RE2O3 RE2O3 partition ratio D
Xiang Zhongji phase water distributes extraction La Ce Pr Nd Sm
P204 RE2O3 RE2O3 H2SO4 ratio
Mol grams per liter grams per liter mol D % (single rare earth element)
1.00 14.61 22.91 0.115 0.638 39.21 0.19 0.61 0.95 1.24 14.85
0.74 12.27 27.95 0.090 0.437 30.51 0.12 0.40 0.60 0.83 10.43
0.52 9.16 31.86 0.070 0.288 22.33 0.069 0.24 0.38 0.55 6.68
Table six. P204 concentration is to the influence of separation factor β in the organic phase
Organic balanced have a balance RE2O3 RE2O3 separation factor β
Xiang Zhongji phase water distributes extraction
P204 RE2O3 RE2O3 H2SO4 ratio Ce/ Pr/ Nd/ Sm/
Mol grams per liter grams per liter mol D % La Ce Pr Nd
1.00 14.61 22.91 0.115 0.638 39.21 3.21 1.56 1.31 11.98
0.74 12.27 27.95 0.090 0.437 30.51 3.34 1.50 1.38 12.55
0.52 9.16 31.86 0.070 0.288 22.33 3.53 1.57 1.44 12.14
From table five, six as can be seen along with the decline of P204 concentration the organic phase, the also corresponding decline of partition ratio, percentage extraction, but separation factor is not subjected to the influence of P204 concentration substantially, and in order to improve the concentration of organic phase middle-weight rare earths element, the extraction agent P204 that adopts higher concentration is for well.
Embodiment 4
With the rare earth sulfuric acid solution after purifying as the fractionation extraction of the neodymium-samarium isolating feed liquid of dividing into groups, its concentrations of rare-earth is 45.38 grams per liters, feed acidity is 0.06 mol sulfuric acid, organic phase is No. 260 solvent oil solution of 1.0 mol P204, washing lotion acidity is 0.572 mol sulfuric acid, 4 grades of extraction sections, 7 grades of washing sections, totally 11 grades.The stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters:
66 milliliters: 5.5 milliliters, organic phase and water duration of contact are 6 minutes, 27 ℃ of extraction temperature, the shared per-cent of each rare earth element is La2O3 27.53 in the feed liquid, CeO2 49.70, Pr6O11 5.13, Nd2O3 15.44, and Sm2O3 1.20, and Eu2O3 0.23, Gd2O3 0.33, and Y2O3 0.20.Export the water of discharge the sulfuric acid raffinate that contains lanthanum, cerium, praseodymium, neodymium from counter-current extraction section first step water, its rare earth concentration is 41.33 grams per liter rare earth oxides, the concentration of free acid is 0.114 mol sulfuric acid, and the organic phase middle-weight rare earths concentration of discharging from the 7th grade of organic phase relief outlet of countercurrent washing section is 3.82 grams per liter rare earth oxides.The rate of recovery of Eu2O3 is 99.15% in the organic phase, organic phase is the enriched substance of heavy rare earth element in samarium, europium, the gadolinium etc., it consists of La2O3＜0.1%, CeO2＜0.1%, Pr6O11＜0.1%, Nd2O3＜0.1%, Sm2O3 49.33%, Eu2O3 11.92%, and Gd2O3 20.19%, and Y2O3 11.05%, water consist of La2O3 27.53%, CeO2 49.70%, and Pr6O11 5.13%, and Nd2O3 15.44%, Sm2O3 1.20%, Eu2O3 0.23%, and Gd2O3 0.37%, and Y2O3 0.20%.
Is that anti-stripping agent is stripped with the organic phase of load samarium, europium, gadolinium enriched substance with 5 mol hydrochloric acid, and water gets the muriate enriched substance of the rare earth element of samarium, europium, gadolinium etc., and No. 260 solvent oil organic phases that contain P204 are returned and recycled.
Embodiment 5
Its experiment condition is substantially with embodiment 4, and the concentration of only different is feed liquid middle-weight rare earths is 30.17 grams per liter rare earth oxides, and the acidity of feed liquid is 0.05 mol sulfuric acid; The stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters: 99 milliliters: 5.5 milliliters, extraction temperature is 23 ℃.The aqueous phase rare earth concentration of discharging from the water outlet is 27.89 grams per liter rare earth oxides.The concentration of its free acid is 0.089 mol sulfuric acid, and the organic phase middle-weight rare earths concentration that the organic phase outlet is discharged is 3.92 grams per liter rare earth oxides.Consist of Nd2O3＜0.1% in the organic phase, Sm2O3 51.23%, and Eu2O3 11.55%; The composition La2O3 28.21% of water, CeO2 50.80%, and Pr6O11 5.23%, and Nd2O3 16.35%, Sm2O3＜0.1%, the rate of recovery of Eu2O3 is 100.12%, the Nd2O3 rate of recovery is 99%.
Embodiment 6
Its experiment condition is substantially with embodiment 5, and the concentration of only different is feed liquid middle-weight rare earths is 35.26
Grams per liter rare earth oxide, the acidity of feed liquid are 0.06 mol sulfuric acid; The stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters: 84 milliliters: 5.5 milliliters, extraction temperature is 28 ℃.The aqueous phase rare-earth oxidation substrate concentration of discharging from the water outlet is 32.34 grams per liters.The concentration of free acid is 0.096 mol sulfuric acid, and the concentration of the organic phase middle-weight rare earths that the organic phase outlet is discharged is 4.05 grams per liter rare earth oxides.Consist of Nd2O3＜0.1% in the organic phase, Sm2O3 51.75%, and Eu2O3 11.32%; Water consist of La2O3 28.06%, CeO2 50.7%, Pr6O11 5.32%, Nd2O3 16.56%, Sm2O3＜0.1%, the rate of recovery of Eu2O3 is 99.3%.
Embodiment 7
Its experiment condition is substantially with embodiment 6, and the concentration of only different is feed liquid middle-weight rare earths is 40.56 grams per liter rare earth oxides, and the stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters: 75 milliliters: 5.5 milliliters, extraction temperature is 21 ℃.The aqueous phase concentrations of rare-earth of discharging from the water outlet is 37.16 grams per liter rare earth oxides.The concentration of free acid is 0.104 mol sulfuric acid; The organic phase middle-weight rare earths concentration that the organic phase outlet is discharged is 4.10 grams per liter rare earth oxides.Organic phase consist of Nd2O3＜0.1%, Sm2O3 51.31%, Eu2O3 11.54%; Water consists of La2O3 28.03%, and CeO2 50.96%, and Pr6O11 5.30%, and Nd2O3 16.31%, Sm2O3＜0.1%.
Embodiment 8
Its experiment condition is substantially with embodiment 4, and the concentration of only different is feed liquid middle-weight rare earths is 45.00 grams per liter rare earth oxides, and washing lotion acidity is 0.556 mol sulfuric acid; The stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters: 100 milliliters: 4.8 milliliters, the aqueous phase rare earth concentration of discharging from the water outlet is 42.60 grams per liter rare earth oxides.The concentration of its free acid is 0.091 mol sulfuric acid, and the organic phase middle-weight rare earths concentration that the organic phase outlet is discharged is 5.90 grams per liter rare earth oxides.Organic phase consist of Nd2O3 0.27%, Sm2O3 48.16%, Eu2O3 12.10%; Water consists of La2O3 27.90%, and CeO2 50.45%, and Pr6O11 5.31%, and Nd2O3 16.52%, and Sm2O3 0.10%.
Embodiment 9
Its experiment condition is substantially with embodiment 4, and the concentration of only different is feed liquid middle-weight rare earths is 45.00 gram liter rare earth oxides, and the acidity of washing lotion is 0.556 mol sulfuric acid; The stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters: 100 milliliters: 5.0 milliliters, the aqueous phase rare earth concentration of discharging from the water outlet is 42.07 grams per liter rare earth oxides, and the concentration of its free acid is 0.09 mol sulfuric acid; The organic phase middle-weight rare earths concentration that the organic phase outlet is discharged is 5.92 grams per liter rare earth oxides.Organic phase consists of Nd2O3＜0.1%, and Sm2O3 49.51%, and Eu2O3 11.95%; Water consists of La2O3 28.08%, and CeO2 50.62%, and Pr6O11 5.27%, and Nd2O3 16.52%, and Sm2O3 0.11%.
Embodiment 10
Water with neodymium-samarium fractionation extraction discharge, the sulfuric acid raffinate that promptly contains lanthanum, cerium, praseodymium, neodymium is as praseodymium-neodymium isolating feed liquid of dividing into groups, to PH4, its rare earth concentration is 40.55 grams per liter rare earth oxides with this feed adjustment, and wherein the shared per-cent of each rare earth element is as follows:
La2O3 27.02, and CeO2 51.42, and Pr6O11 5.45, and Nd2O3 16.62, and Sm2O3 0.14, Eu2O3＜0.1, other＜0.1.
Adopt following condition to carry out the fractionation extraction separation and produce thick Nd2O3, organic phase is No. 260 solvent oil organic solutions of 1 mol P204, and washing lotion acidity is 0.56 mol sulfuric acid, 13 grades of extraction sections, 7 grades of washing sections.The stream ratio of organic phase, feed liquid and washing lotion is 20 milliliters: 10 milliliters: 6.5 milliliters.The time that organic phase contacts with water is 6 minutes.Extraction temperature is 25 ℃.The water of discharging is the sulfuric acid raffinate that contains lanthanum, cerium, and its rare earth concentration is 20.71 grams per liter rare earth oxides, and the concentration of its free acid is 0.27 mol sulfuric acid.Water consists of La2O3 35.16%, and CeO2 59.78%, and Pr6O11 3.39%, and Nd2O3 2.20%.From the organic phase that the 7th grade of organic phase relief outlet of countercurrent washing section discharged, it consists of La2O3＜0.1%, and CeO2 3.22%, and Pr6O11 9.29%, and Nd2O3 86.73%, and Sm2O3 1.60%.The organic phase of the thick neodymium of load is stripped with 5 mol hydrochloric acid, get the muriate of thick neodymium, organic phase is returned and is recycled.
Embodiment 11
Its experiment condition is substantially with embodiment 10, and only different is organic phase, feed liquid and washing lotion
Stream is than being 20 milliliters: 10 milliliters: 7.0 milliliters.The rare earth concentration of discharging water is 20.27 grams per liter rare earth oxides, and the concentration of free acid is 0.26 mol sulfuric acid, and water consists of La2O3 33.25%, and CeO2 57.83%, and Pr6O11 4.93%, and Nd2O3 4.40%; Organic phase consists of La2O3＜0.1%, and CeO2 1.22%, and Pr6O11 5.17%, and Nd2O3 92.35%, and Sm2O3 2.06%.
Embodiment 12
Its experiment condition is substantially with embodiment 10, and only different is that feed acidity is PH1.3,17 grades of extraction sections, 14 grades of washing sections.The stream ratio of organic phase, feed liquid and washing lotion is 15 milliliters: 10 milliliters: 4.5 milliliters.Discharging the water rare earth concentration is 23.24 grams per liter rare earth oxides, and the concentration of its free acid is 0.28 mol sulfuric acid.Water consists of La2O3 36.81%, and CeO2 59.84%, and Pr6O11 2.25%, and Nd2O3 1.34%; Organic phase consists of La2O3＜0.1%, and CeO2 3.11%, and Pr6O11 12.8%, and Nd2O3 82.97%, and Sm2O3 1.60%.
Embodiment 13
Its experiment condition is substantially with embodiment 10, and the concentration of only different is feed liquid middle-weight rare earths is 39.43 grams per liter rare earth oxides, and its feed acidity is PH3.5, and washing lotion acidity is 0.481 mol sulfuric acid.19 grades of extraction sections, 22 grades of washing sections.The stream ratio of organic phase, feed liquid and washing lotion is 20 milliliters: 10 milliliters: 8.3 milliliters.Discharging the water rare earth concentration is 17.03 grams per liter rare earth oxides, and the concentration of its free acid is 0.281 mol sulfuric acid.Water is formed La2O3 37.69%, and CeO2 60.63%, and Pr6O11 1.73%, and Nd2O3 0.80%; Organic phase is formed La2O3＜0.1%, and CeO2 0.79%, and Pr6O11 10.57%, and Nd2O3 87.62%, and Sm2O3 1.75%, the Nd2O3 rate of recovery 96.6%.
Embodiment 14
Its experiment condition is substantially with embodiment 10, the concentration of only different is feed liquid middle-weight rare earths is 39.43 grams per liter rare earth oxides, the acidity of its feed liquid is PH3.5, washing lotion acidity is 0.512 mol sulfuric acid, 19 grades of extraction sections, 22 grades of washing sections, the stream ratio of organic phase, feed liquid and washing lotion is 20 milliliters: 9.0 milliliters: 7.5 milliliters.Discharging the water rare earth concentration is 17.82 grams per liter rare earth oxides, and the concentration of its free acid is 0.303 mol.Aqueous sulfuric acid phase is formed La2O3 37.74%,
CeO2 60.67%, and Pr6O11 1.70%, and Nd2O3 0.82%; Organic phase is formed La2O3＜0.1%, and CeO2 0.80%, and Pr6O11 11.34%, and Nd2O3 86.80%, and Sm2O3 1.85%, and the Nd2O3 rate of recovery is 96.5%.
Embodiment 15,16,17,18,19,20,21,22
The sulfuric acid raffinate that contains the lanthanum cerium that praseodymium-neodymium is separated is regulated its PH to 4～5, with P204 is extraction agent, No. 260 solvent oils are thinner, carry out the extraction of 6 stage countercurrents, rare earth elements such as lanthanum, cerium are come together into organic phase, strip with 5 mol hydrochloric acid or 5 mol nitric acid then, generate rare earth chloride or rare earth nitrate.Its result as shown in Table 7.
Table seven. the extraction of lanthanum, cerium
The feed liquid organic phase is compared the outlet water and is exported organic RE2O3
Numbering RE2O3 P204 organic phase: water H2SO4 RE2O3 phase RE2O3 percentage extraction
Grams per liter mol (feed liquid) mol grams per liter grams per liter %
1 18.15 1.0 2∶1 0.18 0.53 8.81 97.1
2 18.15 1.5 1.2∶1 0.19 0.41 14.68 97.7
3 21.42 1.0 2∶1 0.20 0.92 10.25 97.7
4 21.42 1.0 2.5∶1 0.21 0.49 8.37 97.7
5 21.42 1.5 1.4∶1 0.21 0.07 15.25 99.7
6 25.33 1.5 1.4∶1 0.25 0.84 17.49 96.7
7 25.33 1.5 1.7∶1 0.26 0.51 14.60 98.0
8 27.47 1.5 1.7∶1 0.27 0.84 16.66 96.9
Claims (2)
1, a kind of processing method of fractionation extraction grouping separation of mixed rare-earth element, infusion with vitriol intensified baked rare earth ore concentrate, with in the alkaline earth metal oxide and purify, make purified rare earth sulfate solution as stock liquid, with di-(2-ethylhexyl)phosphoric acid (being called for short P204) is extraction agent, kerosene is thinner, and feature of the present invention is:
Said alkaline earth metal oxide is a magnesium oxide, the acidity of feed liquid is PH3 to 0.315 mol sulfuric acid, the concentration of mishmetal in the feed liquid＜50 grams per liter rare earth oxides, extraction agent di-(2-ethylhexyl)phosphoric acid concentration＜2 mol, at first carrying out the fractionation extraction grouping between neodymium-samarium separates, its organic phase, feed liquid, the stream ratio of washing lotion is 1: 4-7: 0.3-0.4, the acidity of washing lotion is the 0.25-1.0 mol, the extraction back forms contains lanthanum, cerium, praseodymium, sulfuric acid raffinate such as neodymium and contain samarium, europium, the organic phase of heavy rare earth element in the gadolinium etc.
2) with the said sulfuric acid raffinate that contains the mixed rare-earth oxide 25-43 grams per liter of lanthanum, cerium, praseodymium, neodymium etc., regulate its acidity to PH0.7-4, feed liquid as praseodymium-neodymium fractionation extraction, contain 1.0-1.5 mol P204 in the organic phase, the concentration of washing lotion is 0.4-0.56 mol sulfuric acid, the stream of organic phase, feed liquid, washing lotion is than being 2.0-2.2: 1: 0.7-0.9 forms the organic phase that contains the sulfuric acid raffinate of rare earth elements such as lanthanum, cerium and contain neodymium
3) the sulfuric acid raffinate that will contain rare earth oxide 17-28 grams per liters such as lanthanum, cerium is a feed liquid, regulate its PH to 1-5, contain the P2041.0-1.5 mol in the organic phase, organic phase: water (feed liquid) is 1-3: 1 carries out counter-current extraction, makes lanthanum, cerium mischmetal oxide compound.
2, according to the processing method of a kind of fractionation extraction grouping separation of mixed rare-earth element of claim 1, it is characterized in that, when carrying out between neodymium-samarium the fractionation grouping and separating, contain 30-46 grams per liter rare earth oxide in the feed liquid, the acidity of feed liquid is PH4-0.15 mol sulfuric acid, contain 0.5-1.5 mol P204 in the organic phase, washing lotion acidity is 0.4-0.6 mol sulfuric acid.
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| CN1047614C (en) * | 1993-12-22 | 1999-12-22 | 辛辛那提米勒克郎公司 | Aqueous functional fluid having improved resistance to micro-organisms |
| CN100348748C (en) * | 2004-12-15 | 2007-11-14 | 北京有色金属研究总院 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
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| CN1047614C (en) * | 1993-12-22 | 1999-12-22 | 辛辛那提米勒克郎公司 | Aqueous functional fluid having improved resistance to micro-organisms |
| CN100348748C (en) * | 2004-12-15 | 2007-11-14 | 北京有色金属研究总院 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
| WO2009021389A1 (en) * | 2007-08-10 | 2009-02-19 | Grirem Advanced Materials Co., Ltd. | A PROCESS OF SMELTING MONAZITE RARE EARTH ORE RICH IN Fe |
| AU2008286599B2 (en) * | 2007-08-10 | 2010-11-18 | Grirem Advanced Materials Co., Ltd. | A metallurgical process for iron-rich monazite rare earth ore or concentrate |
| US11447397B1 (en) | 2021-03-19 | 2022-09-20 | Lynas Rare Earths Limited | Materials, methods and techniques for generating rare earth carbonates |
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