CN101994004B - Process for extracting and separating rare-earth elements - Google Patents
Process for extracting and separating rare-earth elements Download PDFInfo
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- CN101994004B CN101994004B CN2009100908805A CN200910090880A CN101994004B CN 101994004 B CN101994004 B CN 101994004B CN 2009100908805 A CN2009100908805 A CN 2009100908805A CN 200910090880 A CN200910090880 A CN 200910090880A CN 101994004 B CN101994004 B CN 101994004B
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Abstract
The invention provides a process for extracting and separating rare-earth elements. In the process, acid organic extracting agents such as P507, P204, C272 and naphthenic acid, aqueous solution of organic acid salt of magnesium and/or calcium, and rare-earth solution are mixed for pre-extraction; rare earth ions are extracted into an organic phase; and the organic phase is clarified to form a rare earth ion loaded organic phase used for extracting and separating mixed rare earth feed liquor. A single rare-earth compound or a concentrate of several rare-earth elements is obtained through multi-stage extraction-washing-back extraction. The aqueous solution of organic acid salt of magnesium and/or calcium is prepared by roasting minerals such as magnesite, limestone, calcite and dolomite and dissolving with organic acid; the contents of impurities such as silicon, iron and aluminium are low; three-phase substances are not generated in the pre-extraction and extraction and separation processes; the purity of rare earth products is not influenced; the organic phase is not subjected to ammonia saponification, and ammonia nitrogen wastewater is not generated; the production cost of the rare earth products is greatly reduced; and a great amount of three-waste treatment cost is saved.
Description
Technical field
The present invention relates to a kind of technology of acid organic extractant extracting and separating rear earth element.Specifically acid organic extractant is mixed in advance with the acylate aqueous solution, the earth solution of magnesium and/or calcium and extract; Rare earth ion is extracted in the organic facies; Through clarification; The load organic extractant that obtains containing rare earth ion is used for the extract and separate of mishmetal feed liquid, belongs to rare earth solvent extraction and separation field.
Background technology
The general solvent extraction that adopts of separation purification of single rare earth element is gone up in industry at present; The most frequently used technology has: saponification P507 (di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), P204 (di-(2-ethylhexyl)phosphoric acid), C272 (two (2; Phosphonic acids) etc. 4,4-tri-methyl-amyl) extractant in hydrochloric acid system the extracting and separating rear earth element ([1] rare earth chemistry collection of thesis, Changchun should be changed institute; Nineteen eighty-two, Science Press; [2] Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), and metallurgical industry publishing house, 2002, P542-547); Medium-gadolinium and rich-europium ion type Rare Earth Mine rare earth full-separating process (CN87101822); Ammonification P507 solvent extraction and separation mixed rare earth craft (CN85102210); Organic phase continuous saponification technique (CN95117989.6); Saponification naphthenate acid system separates purification yittrium oxide (Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), metallurgical industry publishing house, 2002, P582,590).The used extractant of above-mentioned extract and separate all belongs to acid organic extractant, and the extracting power (distribution ratio) of rare earth and water balance acidity are inversely proportional to, and generally extracts a rare earth ion and will replace 3 hydrogen ions and get into waters; Therefore must adopt ammoniacal liquor or NaOH that extractant is carried out saponification earlier, (seeing reaction equation 1) removed in the hydrogen ion displacement, exchange extract and separate (seeing reaction equation 2) with rare earth ion then; This shows, in extraction process,, cause cost to increase not only owing to consume a large amount of ammonia; And to produce a large amount of ammonia nitrogen waste waters; Water resource is caused serious pollution, because ammonia nitrogen waste water concentration is lower, recovery difficult is big; And cost recovery is very high, and enterprise is difficult to accept.How eliminating the pollution of ammonia nitrogen waste water to environment, is a great problem of being badly in need of solution in the present Rare Earth Separation industry.
HA+NH
4 +==NH
4A+H
+-----------reaction equation 1
3NH
4A+RE
3+==REA
3+ 3NH
4 +-----------reaction equation 2
HA represents organic extractant, RE
3+Represent trivalent rare earth ions.
Chinese invention patent application 200710163930.9 discloses a kind of preprocess method and application technology thereof of organic extractant; The carbonated rare earth water sized mixing or size mixing with the alkaline-earth metal mineral of calcic, magnesium, with earth solution obtain the preliminary treatment slurries; At a certain temperature organic extractant is carried out preliminary treatment; Rare earth ion in the slurries is extracted in the organic facies, and the non-saponifiable extraction that the load organic extractant that obtains containing rare earth ion is used for rare earth separates
Chinese invention patent application 200710187954.8 discloses a kind of preprocess method, product and application technology thereof of organic extractant; Organic extractant directly mixed in advance with earth solution and the alkaline earth metal compound powder or the water slurry that contain magnesium and/or calcium extract; The rare earth ion of aqueous phase is extracted into organic facies; The hydrogen in statu nascendi ion that exchanges dissolves alkaline earth metal compound, and the non-saponifiable extraction that the load organic extractant that obtains containing rare earth ion is used for rare earth element separates.
International application for a patent for invention PCT/CN2008/000280 discloses a kind of preprocess method, product and application thereof of organic extractant; It mixes organic extractant and earth solution and the alkaline earth metal compound powder that contains magnesium and/or calcium or water slurry to extract in advance or mix in advance with the carbonated rare earth slurries and extracts; The rare earth ion of aqueous phase is extracted into organic facies; The hydrogen in statu nascendi ion that exchanges is with alkaline earth metal compound or carbonated rare earth dissolving; Keep the extraction system acidity balance, the non-saponifiable extraction that the load organic extractant that obtains containing rare earth ion is used for rare earth element separates.
What above-mentioned three applications for a patent for invention were adopted is the alkaline-earth metal mineral of calcic, magnesium; Or contain the alkaline earth metal compound powder or the water slurry of magnesium and/or calcium, promptly contain magnesium and/or calcium oxide, hydroxide, carbonate powder or water slurry organic facies is carried out preliminary treatment or extraction in advance, because the alkaline-earth metal mineral of calcic, magnesium and oxide thereof, hydroxide product contain impurity such as more silicon, iron, aluminium; Solid-liquid reaction speed is slow and incomplete; Cause to produce the three-phase thing in preliminary treatment or the extraction process, influence extraction process and carry out smoothly, and; Impurity such as iron, aluminium is prone to collection goes in the organic facies, thereby influences product quality.
The present invention carries out roasting-organic acid dissolving method preparation with mineral such as magnesite, lime stone, calcite, dolomites; Or just magnesia, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture adding organic acid dissolve; Obtain the acylate aqueous solution of magnesium and/or calcium; Again through filtering, with Impurity removals such as silicon, iron, aluminium, the pure magnesium bicarbonate that obtains and/or the calcium bicarbonate aqueous solution mix in advance with acid organic extractant, earth solution and extract.This invention is compared with above-mentioned patent and had the following advantages: (1) extracts in advance and extraction separation process does not produce the three-phase thing, do not introduce impurity such as iron, aluminium, do not influence product quality, (2) liquid-liquid reactions, and reaction speed is fast, and rare earth extraction is more complete, and flow is prone to accurately control; (3) directly adopt calcic, magnesium raw ore or specification lower oxide, hydroxide, less demanding to raw materials quality, cost can reduce significantly.
Summary of the invention
The purpose of this invention is to provide a kind of new technology that does not produce ammonia nitrogen waste water, the direct extracting and separating rear earth element of acid organic extractant that production cost is low.
For reaching the purpose of foregoing invention, the present invention adopts following technical scheme:
The present invention has studied the process of the direct extracting and separating rear earth element of a kind of acid organic extractant according to the characteristic of acid organic extractants such as P507, P204, C272, aphthenic acids.Acid organic extractant mixed in advance with the acylate aqueous solution, the earth solution of magnesium and/or calcium extract; Rare earth ion is extracted in the organic facies; Through clarification, obtain containing the load organic phases of difficult collection rare earth ion, when being used for the extracting and separating rear earth element be prone to the collection rare earth ion exchanged; Separate through multitple extraction, difficult collection rare earth ion is separated with easy collection rare earth ion.The fundamental reaction formula is following
RE
a 3++ 3HA==RE
aA
3+ 3H
+-----------reaction equation 3
M (RCOO)
2+ 2H
+==M
2++ 2RCOOH-----------reaction equation 4
Or M (RCOO)
2+ 2HA==MA
2+ 2RCOOH----------reaction equation 5
3MA
2+ 2RE
a 3+==2RE
aA
3+ 3M
2+-----------reaction equation 6
RE
aA
3+ RE
b 3+==RE
bA
3+ RE
a 3+-----------reaction equation 7
M represents magnesium or calcium constituent, RE
aRepresent difficult collection rare earth element, RE
bRepresent the Yi Cui rare earth element.
Magnesium or calcium ion get into water, do not get into extraction separation process basically, and keep extraction process water balance acidity stable, and alkaline earth metal content is low in the rare-earth products.
The concrete technical scheme of the present invention is following:
The present invention proposes a kind of technology of extracting and separating rear earth element, comprise the steps: at least
(1) with the acylate aqueous solution of blank organic extractant and magnesium and/or calcium, earth solution simultaneously or substep mix in advance and extract; Rare earth ion is extracted in the organic facies; Through clarification, obtain load organic phases and the surplus water of collection, load organic phases middle rare earth content REO is 0.05-0.23mol/L; The surplus aqueous pH values of coming together is 1.5-5, the acylate aqueous solution of said magnesium and/or calcium by magnesium or/and the calcium mineral through roasting-organic acid dissolving method preparation.
The rare earth feed liquid that the load organic phases that (2) will contain rare earth ion is used to contain rare earth element more than 2 kinds or 2 kinds carries out extract and separate, through multitple extraction, washing, back extraction, obtains containing raffinate, washing lotion and the strip liquor product of different rare earth elements; The load organic phases that maybe will contain rare earth ion is directly with hydrochloric acid or nitric acid back extraction; Obtain containing mixed chlorinated rare earth solution or the mixeding acid rare-earth solution of REO 0.1-2mol/L; This solution is produced mixed chlorinated rare earth or mixeding acid rare-earth product through condensing crystallizing, or further extract and separate is produced single rare earth compound product.
Step (1) adopts single-stage or the 2-20 level flows altogether and/or the counter-current extraction mode extracts in advance; The volume ratio of organic extractant and water: organic facies/water=0.1-10; Two phase incorporation times are 3-80 minute, and settling time 5-120 minute, temperature was controlled at 15-90 ℃ in the groove.
The extract and separate of rare earth element described in the step (2) adopts 10-200 level fractional extraction mode to carry out; Back extraction is adopted the 3-20 stage countercurrent or/and reflux type carries out; The volume ratio of organic extractant and water: organic facies/water=0.1-20; Two phase incorporation times are 3-15 minute, and settling time 5-30 minute, temperature was controlled at 15-90 ℃ in the groove.
Rare earth element in said earth solution and the rare earth feed liquid is at least a in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, yttrium, lutetium, yttrium, the scandium;
The said blank organic extractant of step (1) is the organic extractant behind the back extraction rare earth in the extraction separation process; Organic extractant is one or more mixed extractants among acidic phosphorus extractant and the carboxylic acid extractant; As contain one or more mixed extractants in P507, P204, P229, C272, C301, C302, aphthenic acids or the isomeric acid; And to use organic solvent diluting, extractant concentration be 0.5-1.7mol/l.
The raffinate that contains a kind or several kinds difficult collection rare earth element that the said earth solution of step (1) obtains for rare earth extraction segregation section; Or for containing re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixed solution of a kind or several kinds of rare earth elements, its rare earth concentration REO is 0.1-1.5mol/L.The said rare earth feed liquid of step (2) is mixed chloride solution, nitrate solution, sulfate liquor or its mixed solution that contains rare earth element more than 2 kinds or 2 kinds, and its rare earth concentration REO is 0.2-1.8mol/L.
Magnesia and/or calcium oxide content are 0.1-25wt% in the acylate aqueous solution of said magnesium of step (1) and/or calcium, are optimized for 1-15wt%
The acylate aqueous solution of said magnesium of step (1) and/or calcium is prepared through roasting-organic acid dissolving method by at least a mineral in magnesite, lime stone, calcite, dolomite, marble or the asbestos tailings.Mineral were at 700-1000 ℃ of roasting 1-10 hour; Add organic acid and dissolve, solvent and solute weight ratio is 5-1000: 1, and the organic acid consumption is the 100%-200% of theoretical consumption; Reaction temperature is controlled at 0-90 ℃; Reaction time is 0.1-5 hour, through filtering, obtains the acylate aqueous solution of pure magnesium and/or calcium.Optimizing solid weight ratio is 10-100: 1, and reaction temperature is 0-60 ℃, the reaction time is 0.5-2 hour.
Said organic acid is: saturated monocarboxylic acids such as formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid; Dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, decanedioic acid; One or more mixing in sulfanilic acid, phthalic acid, mandelic acid, monoxone, 3 hydroxy propane tricarboxylic acids (citric acid), hydroxysuccinic acid (tartaric acid), 2,3 dihydro base propionic acid (glyceric acid), gluconic acid, 2 hydracrylic acids (lactic acid), acrylic acid, glycolic acid (glycolic), the fumaric acid substituted carboxylic acids such as (rich next acid).
The acylate aqueous solution of said magnesium of step (1) and/or calcium or add organic acid by magnesia, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture and dissolve preparation.Being about to magnesia, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture adding organic acid dissolves; Solvent and solute weight ratio is 5-1000: 1; The organic acid consumption is the 100%-200% of theoretical consumption, and reaction temperature is controlled at 0-90 ℃, and the reaction time is 0.1-5 hour; Through filtering, obtain the acylate aqueous solution of pure magnesium and/or calcium.The optimization solvent and solute weight ratio is 10-100: 1, and reaction temperature is 0-60 ℃, the reaction time is 0.5-2 hour.
The load organic phases middle rare earth content REO that step (1) obtains is 0.1-0.2mol/L, comes together surplus aqueous pH values between 2-4, and wherein content of rare earth REO is less than 0.002mol/L.
Step (1) is the organic acid of extraction generation in advance, returns the preparation of the acylate aqueous solution that is used for magnesium and/or calcium.
Advantage of the present invention is:
The present invention carries out hybrid extraction with the acylate aqueous solution, the earth solution of acid organic extractants such as P507, P204, C272, aphthenic acids and magnesium and/or calcium; Rare earth ion is extracted in the organic facies; Through clarification; The load organic phases that obtains containing rare earth ion is used for the extract and separate of mishmetal feed liquid, and separates through multitple extraction, obtains the enrichment of single rare earth compound or several kinds of rare earths.Through roasting-organic acid dissolving preparation, impurity contents such as silicon, iron, aluminium are low by mineral such as magnesite, lime stone, calcite, dolomites for the acylate aqueous solution of used magnesium and/or calcium, and extraction and extraction separation process do not produce the three-phase thing in advance; Do not influence product purity; And organic facies do not produce ammonia nitrogen waste water without the ammonia saponification, eliminates the pollution of ammonia nitrogen waste water to environment from the source; And reduce the rare-earth products production cost significantly, save a large amount of three wastes disposal costs.
Description of drawings
Fig. 1: acid organic extractant mixes in advance with the acylate aqueous solution, the earth solution of magnesium and/or calcium and extracts, and directly prepares the process schematic representation of mixed rare earth compound then with sour back extraction.
Fig. 2: acid organic extractant mixes in advance with the acylate aqueous solution, the earth solution of magnesium and/or calcium and extracts, and carries out the process schematic representation that multistage fractional extraction separates the single rare earth compound then.
Symbol description among the figure:
The blank organic facies of Y1-; The Y2-load organic phases; The F-rare earth feed liquid; The C-earth solution; The acylate aqueous solution of D-magnesium and/or calcium;
The E1-surplus water that comes together; E2-waste water; W-back extraction acid;
A-raffinate outlet (product 1); B1-strip liquor outlet (product 2); B1 '-washing lotion inlet; B2-washing lotion outlet (product 3)
The specific embodiment
Below with embodiment method of the present invention and application thereof are described further
Embodiment 1
The light calcined magnesia that magnesite was obtained 850-900 ℃ of roasting in 2 hours; Adding glutaric acid dissolves; Solvent and solute weight ratio is 80: 1, and the glutaric acid consumption is 110% of a theoretical consumption, reacts 40 minutes down at 20 ℃; Through clarification filtration, obtain the pure glutaric acid magnesium aqueous solution (MgO:1.2%).
With the flow velocity of the glutaric acid magnesium aqueous solution with 3.73L/min, lanthanum-cerium chloride solution (0.928mol/L) carries out common stream extraction with the flow velocity of 0.8L/min in 1.5mol/L P507 organic facies 6 grades of preparatory extraction tanks of flow velocity adding with 4L/min; Incorporation time 25 minutes; Clarified 20 minutes, and obtained containing the load organic phases of difficult collection rare earth ion lanthanum cerium, its content of rare earth REO is 0.185mol/L; The surplus aqueous pH values of coming together is 2.8, and REO content is less than 0.001mol/L.
Load organic phases directly is used for the LaCe/Pr fractional extraction separates,, obtain 99.9% praseodymium chloride and lanthanum-cerium chloride enrichment through 65 grades of fractional extractions.With extracting the glutaric acid aqueous solution that produces in advance, return the preparation that is used for the glutaric acid magnesium aqueous solution.
Embodiment 2
Light calcined magnesia and calcium oxide mixture that dolomite was obtained 800-850 ℃ of roasting in 2 hours; Adding formic acid dissolves; Solvent and solute weight ratio is 100: 1, and the formic acid consumption is 120% of a theoretical consumption, reacts 40 minutes down at 20 ℃; Through clarification filtration, obtain the pure magnesium bicarbonate and the calcium bicarbonate aqueous solution (MgO+CaO:0.92%).
With magnesium formate and the calcium formate aqueous solution flow velocity with 6.4L/min, lanthanum-cerium chloride solution (0.665mol/L) is with the flow velocity of 1.5L/min, and 1.3mol/L P204 organic facies adds in 12 grades of preparatory extraction tanks with the flow velocity of 6L/min and extracts; Incorporation time 25 minutes; Through 6 grades of stream, extractions of 6 stage countercurrents altogether, obtain containing the load organic phases of lanthanum cerium, its content of rare earth REO is 0.165mol/L; The surplus aqueous pH values of coming together is 3.5, REO content 0.0011mol/L.
Load organic phases directly is used for the LaCe/PrNd fractional extraction separates,, obtain lanthanum-cerium chloride and praseodymium chloride neodymium through 75 grades of fractional extractions.With extracting the formic acid that produces in advance, return the preparation of the formates aqueous solution that is used for magnesium and/or calcium.
Embodiment 3
With the calcium oxide that lime stone obtained 800-850 ℃ of roasting in 2 hours, add butyric acid and dissolve, solvent and solute weight ratio is 16: 1; The butyric acid consumption is 160% of a theoretical consumption; Reacted 30 minutes down at 70 ℃,, obtain the pure calcium butyrate aqueous solution (CaO:6.25%) through clarification filtration.
With the flow velocity of the calcium butyrate aqueous solution with 1.12L/min, lanthanum nitrate hexahydrate (0.744mol/L) extracts in 1.5mol/L P507 organic facies 8 grades of preparatory extraction tanks of flow velocity adding with 6L/min with the flow velocity of 1.5L/min; Incorporation time 25 minutes; Through 5 grades of stream, extractions of 3 stage countercurrents altogether, obtain containing the load organic phases of difficult collection rare earth ion lanthanum, its content of rare earth REO is 0.185mol/L; The surplus aqueous pH values of coming together is 4.5, REO content 0.0016mol/L.
Load organic phases directly is used for the La/Ce fractional extraction separates,, obtain 99.99% lanthanum nitrate and 99.9% cerous nitrate through 68 grades of fractional extractions.With extracting the butyric acid that produces in advance, return the preparation that is used for the calcium butyrate aqueous solution.
Embodiment 4
The magnesia water is sized mixing, add acetate and dissolve, solvent and solute weight ratio is 8: 1, and the acetate consumption is 180% of a theoretical consumption, reacts 60 minutes down at 30 ℃, through clarification filtration, obtains the pure magnesium acetate aqueous solution (MgO:17.5%).
With the flow velocity of the magnesium acetate aqueous solution with 0.56L/min, lanthanum nitrate hexahydrate (0.744mol/L) extracts in 1.5mol/L P507 organic facies 8 grades of preparatory extraction tanks of flow velocity adding with 6L/min with the flow velocity of 1.5L/min; Incorporation time 25 minutes; Through 5 grades of stream, extractions of 3 stage countercurrents altogether, obtain containing the load organic phases of lanthanum, its content of rare earth REO is 0.186mol/L; The surplus aqueous pH values of coming together is 4.6, REO content 0.0015mol/L.
Load organic phases directly is used for the La/Ce fractional extraction separates,, obtain 99.99% lanthanum nitrate and 99.9% cerous nitrate through 68 grades of fractional extractions.With extracting the acetate that produces in advance, return the preparation that is used for the magnesium acetate aqueous solution.
Embodiment 5
The calcium oxide water is sized mixing, add propionic acid and acrylic acid and dissolve, solvent and solute weight ratio is 80: 1; Propionic acid and acrylic acid consumption are 150% of theoretical consumption; Reacted 30 minutes down at 15 ℃,, obtain the pure propionic acid magnesium and the acrylic acid magnesium aqueous solution (MgO:1.8%) through clarification filtration.
With propionic acid magnesium and the acrylic acid magnesium aqueous solution flow velocity with 2.6L/min, lanthanum-cerium chloride solution (0.928mol/L) is with the flow velocity of 0.8L/min, and 1.5mol/L P507 organic facies adds with the flow velocity of 4L/min carries out common stream extraction in 6 grades of preparatory extraction tanks; Incorporation time 25 minutes; Clarified 20 minutes, and obtained containing the load organic phases of difficult collection rare earth ion lanthanum cerium, its content of rare earth REO is 0.185mol/L; The surplus aqueous pH values of coming together is 3.0, and REO content is less than 0.001mol/L.
Load organic phases directly is used for the LaCe/Pr fractional extraction separates,, obtain 99.9% praseodymium chloride and lanthanum-cerium chloride enrichment through 65 grades of fractional extractions.Propionic acid and acrylic acid with extraction generation in advance return the preparation that is used for the propionic acid magnesium and the acrylic acid magnesium aqueous solution.
Embodiment 6
With the flow velocity of the magnesium citrate aqueous solution (MgO:5%) with 1.4L/min, sulfuric acid LaCePrNd solution (0.25mol/L) extracts in 1.5mol/L P204 organic facies 6 grades of preparatory extraction tanks of flow velocity adding with 6.1L/min with the flow velocity of 4.46L/min; Incorporation time 25 minutes; Through 4 grades of stream, extractions of 2 stage countercurrents altogether, obtain containing the load organic phases of LaCePrNd, its content of rare earth REO is 0.182mol/L; The surplus aqueous pH values of coming together is 4.2, REO content 0.0015mol/L.Load organic phases through 10 stage countercurrent back extractions, obtains LaCePrNd nitrate with the back extraction of 5.5N nitric acid.
With extracting the citric acid that produces in advance, return the preparation that is used for the magnesium citrate aqueous solution.
Embodiment 7
With the flow velocity of the calcium acetate aqueous solution (CaO:1.2%) with 4.6L/min; Mix the flow velocity of rare earth sulfate solution (0.25mol/L), extract in 1.5mol/L P507 organic facies 10 grades of preparatory extraction tanks of flow velocity adding, through 6 grades of stream, extractions of 4 stage countercurrents altogether with 5L/min with 3.6L/min; Obtain containing the load organic phases of LaCePrNd; Its content of rare earth REO is 0.178mol/L, and the surplus aqueous pH values of coming together is 3.2, REO content 0.0012mol/L.Load organic phases through 6 stage countercurrent back extractions, obtains mixed chlorinated rare earth solution with the back extraction of 6N hydrochloric acid, and further extract and separate single rare earth, or process evaporating, concentrating and crystallizing obtains the mixed chlorinated rare earth product.
With extracting the acetate that produces in advance, return the preparation that is used for the calcium acetate aqueous solution.
Embodiment 8
With 9M
3Propionic acid magnesium (MgO:0.5%) and 4M
31.5mol/L the mixed extractant of P507 (80%) and P204 (20%) adds 20M
3Tank diameter in mixed 3 minutes, add 1M then
3Praseodymium chloride solution (REO 0.724mol/L) mixed 15 minutes, and 25 ℃ of reaction temperatures through clarification in 15 minutes, obtain containing the load organic phases of difficult collection rare earth ion praseodymium, and its concentration is 0.180mol/L, and the surplus aqueous pH values of coming together is 3, REO content 0.0011mol/L.
Load organic phases directly is used to contain the extract and separate of praseodymium/neodymium mixed chlorinated rare earth solution, through 96 grades of fractional extractions, obtains 99.9% praseodymium chloride and 99.9% neodymium chloride.
Embodiment 9
With 4 M
31.5mol/L P507 extractant and 0.6M
3Praseodymium chloride solution (REO 1.237mol/L) adds 12M
3Tank diameter in mixed 2 minutes, add 3M then
3Succinic acid magnesium (MgO 1.5%) mixed 30 minutes, and 20 ℃ of reaction temperatures through clarification in 30 minutes, obtain containing the load organic phases of difficult collection rare earth ion praseodymium, and its concentration is 0.185mol/L, and the surplus aqueous pH values of coming together is 2.5, REO content 0.0012mol/L.
Load organic phases directly is used to contain the extract and separate of praseodymium/neodymium mixed chlorinated rare earth solution, through 96 grades of fractional extractions, obtains 99.9% praseodymium chloride and 99.9% neodymium chloride.
Embodiment 10
With 4 M
31.5mol/L P507 extractant, 0.6M
3Terbium chloride solution (REO 1.237mol/L) and 3M
3Magnesium acetate (MgO 1.5%) adds 12M simultaneously
3Reactive tank in mixed 20 minutes, 35 ℃ of reaction temperatures through clarification in 30 minutes, obtain containing the load organic phases of difficult collection rare earth ion terbium, its concentration is 0.185mol/L, the surplus aqueous pH values of coming together is 4, REO content 0.0005mol/L.
Load organic phases directly is used to contain the extract and separate of terbium/dysprosium mixed chlorinated rare earth solution, through 96 grades of fractional extractions, obtains 99.99% terbium chloride and 99.9% dysprosium chloride.
Embodiment 11
With 4M
30.7mol/L aphthenic acids and 3M
3Calcium acetate (CaO 1.5%) adds 12M simultaneously
3Reactive tank in mixed 50 minutes, clarified 20 minutes, with aqueous phase separation, add 0.6M then
3Yttrium chloride solution (REO 1.237mol/L) mixed 15 minutes, and 35 ℃ of reaction temperatures through clarification in 30 minutes, obtain containing the load organic phases of yttrium, and its concentration is 0.185mol/L, and the surplus aqueous pH values of coming together is 4, REO content 0.0005mol/L.
Load organic phases directly is used to contain the extract and separate of yttrium mixed chlorinated rare earth solution, through 96 grades of fractional extractions, obtains yttrium chloride and other rareearth enriching material greater than 99.99%.
Claims (17)
1. the technology of an extracting and separating rear earth element, it is characterized in that: this technology comprises the steps: at least
(1) with the acylate aqueous solution of blank organic extractant and magnesium and/or calcium, earth solution simultaneously or substep mix in advance and extract; Rare earth ion is extracted in the organic facies; Through clarification, obtain load organic phases and the surplus water of collection, load organic phases middle rare earth content REO is 0.05-0.23mol/L; The surplus aqueous pH values of coming together is 1.5-5, the acylate aqueous solution of said magnesium and/or calcium by magnesium or/and the calcium mineral through roasting-organic acid dissolving method preparation;
The rare earth feed liquid that the load organic phases that (2) will contain rare earth ion is used to contain rare earth element more than 2 kinds or 2 kinds carries out extract and separate, through multitple extraction, washing, back extraction, obtains containing raffinate, washing lotion and the strip liquor product of different rare earth elements; The load organic phases that maybe will contain rare earth ion is directly with hydrochloric acid or nitric acid back extraction; Obtain containing REO mixed chlorinated rare earth solution or mixeding acid rare-earth solution O.1-2mol/L; This solution is produced mixed chlorinated rare earth or mixeding acid rare-earth product through condensing crystallizing, or further extract and separate is produced single rare earth compound product.
2. the technology of a kind of extracting and separating rear earth element according to claim 1; It is characterized in that: step (1) adopts single-stage or the 2-20 level flows altogether and/or the counter-current extraction mode extracts in advance; The volume ratio of organic extractant and water: organic facies/water=0.1-10; Two phase incorporation times are 3-80 minute, and settling time 5-120 minute, temperature was controlled at 15-90 ℃ in the groove.
3. the technology of a kind of extracting and separating rear earth element according to claim 1 and 2; It is characterized in that: the extract and separate of rare earth element described in the step (2) adopts 10-200 level fractional extraction mode to carry out; Back extraction adopts the 3-20 stage countercurrent or/and reflux type carries out the volume ratio of organic extractant and water: organic facies/water=0.1-20, and two phase incorporation times are 3-15 minute; Settling time 5-30 minute, temperature was controlled at 15-90 ℃ in the groove.
4. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: the element in said earth solution and the rare earth feed liquid is at least a in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, yttrium, lutetium, yttrium, the scandium.
5. the technology of a kind of extracting and separating rear earth element according to claim 1; It is characterized in that: the raffinate that contains a kind or several kinds difficult collection rare earth element that the said earth solution of step (1) obtains for rare earth extraction segregation section; Or for containing re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixed solution of a kind or several kinds of rare earth elements, its rare earth concentration REO is 0.1-1.5mol/L.
6. the technology of a kind of extracting and separating rear earth element according to claim 1; It is characterized in that: the said rare earth feed liquid of step (2) is mixed chloride solution, nitrate solution, sulfate liquor or its mixed solution that contains rare earth element more than 2 kinds or 2 kinds, and its rare earth concentration REO is 0.2-1.8mol/L.
7. the technology of a kind of extracting and separating rear earth element according to claim 1; It is characterized in that: the said blank organic extractant of step (1) is the organic extractant behind the back extraction rare earth in the extraction separation process; Organic extractant is one or more mixed extractants among acidic phosphorus extractant and the carboxylic acid extractant; And use organic solvent diluting, extractant concentration is for O.5-1.7mol/l.
8. the technology of a kind of extracting and separating rear earth element according to claim 7; It is characterized in that: said organic extractant is one or more mixed extractants that contain in P507, P204, P229, C272, C301, C302, aphthenic acids or the isomeric acid; And to use organic solvent diluting, extractant concentration be 0.5-1.7mol/l.
9. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: magnesia and/or calcium oxide content are for O.1-25wt% in the acylate aqueous solution of said magnesium of step (1) and/or calcium.
10. the technology of a kind of extracting and separating rear earth element according to claim 9 is characterized in that: magnesia and/or calcium oxide content are 1-15wt% in the acylate aqueous solution of said magnesium and/or calcium.
11. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: the acylate aqueous solution of said magnesium of step (1) and/or calcium is prepared through roasting-organic acid dissolving method by at least a mineral in magnesite, lime stone, calcite, dolomite, marble or the asbestos tailings.
12. the technology of a kind of extracting and separating rear earth element according to claim 11, wherein the acylate water solution preparation method of magnesium and/or calcium is: said mineral added organic acid again and dissolve at 700-1000 ℃ of roasting 1-10 hour; Solvent and solute weight ratio is 5-1000: 1; The organic acid consumption is the 100%-200% of theoretical consumption, and reaction temperature is controlled at 0-90 ℃, and the reaction time is 0.1-5 hour; Through filtering, obtain the acylate aqueous solution of pure magnesium and/or calcium.
13. the technology of a kind of extracting and separating rear earth element according to claim 12; Wherein used organic acid is in the acylate water solution preparation method of magnesium and/or calcium: formic acid, acetate, propionic acid, butyric acid, valeric acid, the monocarboxylic acid that caproic acid is saturated; Malonic acid, succinic acid, glutaric acid, adipic acid, decanedioic acid dicarboxylic acids; One or more mixing in sulfanilic acid, phthalic acid, mandelic acid, monoxone, 3 hydroxy propane tricarboxylic acids, hydroxysuccinic acid, 2,3 dihydro base propionic acid, gluconic acid, 2 hydracrylic acids, acrylic acid, glycolic acid, the fumaric acid substituted carboxylic acid.
14. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: this technology comprises the steps: at least
(1) with the acylate aqueous solution of blank organic extractant and magnesium and/or calcium, earth solution simultaneously or substep mixes in advance and extracts, rare earth ion is extracted in the organic facies, through clarifying; Obtain load organic phases and the surplus water of collection; Load organic phases middle rare earth content REO is 0.05-0.23mol/L, and the surplus water pH that comes together is 1.5-5, and the acylate water solution preparation method of said magnesium and/or calcium is following: magnesia, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture are added organic acid dissolve; Solvent and solute weight ratio is 5-1000: 1; Organic acid content is the 100%-200% of theoretical consumption, and reaction temperature is controlled at O-90 ℃, and the reaction time is 0.1-5 hour; Through filtering, obtain the acylate aqueous solution of pure magnesium and/or calcium;
The load organic phases that (2) will contain rare earth ion is used to contain the extract and separate of re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixed solution middle rare earth element of rare earth element more than 2 kinds or 2 kinds; Adopt multitple extraction, washing, back extraction, obtain single rare earth solution or contain the enrichment of 2 kinds of rare earth elements at least; The load organic phases that maybe will contain rare earth ion is directly with hydrochloric acid or nitric acid back extraction; Obtain containing mixed chlorinated rare earth solution or the mixeding acid rare-earth solution of REO 0.1-2mol/L; This solution is produced mixed chlorinated rare earth or mixeding acid rare-earth product through condensing crystallizing, or further extract and separate single rare earth compound.
15. technology according to claim 12 or 14 described a kind of extracting and separating rear earth elements; Wherein the acylate water solution preparation method of magnesium and/or calcium is: said solvent and solute weight ratio is 10-100: 1; O.5-2 hour the organic acid consumption is the 100%-200% of theoretical consumption, and reaction temperature is controlled at O-60 ℃, and the reaction time is for; Through filtering, obtain the acylate aqueous solution of pure magnesium and/or calcium.
16. the technology of a kind of extracting and separating rear earth element according to claim 1; It is characterized in that: the load organic phases middle rare earth content REO that step (1) obtains is for O.1-0.2mol/L; Come together surplus aqueous pH values between 2-4, and wherein content of rare earth REO is less than 0.002mol/L.
17. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: step (1) is the organic acid of extraction generation in advance, returns the preparation of the acylate aqueous solution that is used for magnesium and/or calcium.
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