CN101781706A - Process for separating rare-earth element by extraction - Google Patents
Process for separating rare-earth element by extraction Download PDFInfo
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- CN101781706A CN101781706A CN200910118985A CN200910118985A CN101781706A CN 101781706 A CN101781706 A CN 101781706A CN 200910118985 A CN200910118985 A CN 200910118985A CN 200910118985 A CN200910118985 A CN 200910118985A CN 101781706 A CN101781706 A CN 101781706A
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Abstract
The invention mixes and pre-extracts the mixed solution of acidic organic extractants such as P507, P204, C272, and naphthenic acid with magnesium bicarbonate and / or calcium bicarbonate solution and rare-earth solution. The rare-earth ions are extracted into the organic phase, then the loaded organic phase containing rare-earth ions are obtained through clarification, and can be used for the extract separation of the mixed rare-earth feed liquid. After a plurality of different levels of extraction, washing, stripping, single rare-earth compounds or rare-earth elements-containing enrichments can be obtained. The magnesium bicarbonate and/or calcium bicarbonate solution are prepared by roasting, digesting, carbonizing magnesite, limestone, calcite, dolomite and similar minerals, so that the content of impurities, such as silicon, iron, aluminum is lower. Ternary phase sediment is not produced in the pre-extraction and extraction separation process, so that the purity of the rare-earth products are not affected. The organic phase does not need ammonia saponification and does not produce ammonia-nitrogen wastewater. By adopting the invention, the production cost of rare-earth products is greatly lowered and the cost for three waste disposal is also greatly 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 and Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution, earth solution are mixed in advance and extract, rare earth ion is extracted in the organic phase, through clarification, the load organic extractant that obtains containing rare earth ion is used for the extracting and separating of mishmetal feed liquid, belongs to rare earth solvent extraction and separation field.
Background technology
The separation of present industrial single rare earth element is purified and is generally adopted solvent extration, 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 (2,4, the phosphonic acids 4-tri-methyl-amyl)) extraction agent extracting and separating rear earth element ([1] rare earth chemistry collection of thesis in hydrochloric acid system such as, institute should be changed in Changchun, nineteen eighty-two, Science Press; [2] Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), and metallurgical industry press, 2002, P542-547); Medium-gadolinium and rich-europium ion type rare-earth mineral rare earth complete-separation 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 yttrium oxide (Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), metallurgical industry press, 2002, P582,590).The used extraction agent of above-mentioned extracting and separating all belongs to acid organic extractant, extracting power (partition ratio) to rare earth is inversely proportional to water balance acidity, rare earth ion of general extraction will be replaced 3 hydrogen ions and be entered water, therefore must adopt ammoniacal liquor or sodium hydroxide that extraction agent is carried out saponification earlier, (seeing reaction formula 1) removed in the hydrogen ion displacement, exchange extracting and separating (seeing reaction formula 2) with rare earth ion then, this shows, in extraction process not only owing to consume a large amount of ammonia, cause cost to increase, and to produce a large amount of ammonia nitrogen waste waters, water resources 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 that the industrial urgent need of present Rare Earth Separation solves.
HA+NH
4 +==NH
4A+H
+-----------reaction formula 1
3NH
4A+RE
3+==REA
3+ 3NH
4 +-----------reaction formula 2
HA represents organic extractant, RE
3+Represent trivalent rare earth ions.
Chinese invention patent application 200710163930.9 discloses a kind of pretreatment process and utilisation technology thereof of organic extractant, the carbonated rare earth water sized mixing or size mixing and obtain the pre-treatment slurries with the alkaline-earth metal mineral of calcic, magnesium, with earth solution, at a certain temperature organic extractant is carried out pre-treatment, rare earth ion in the slurries is extracted in the organic phase, 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 pretreatment process, product and utilisation technology thereof of organic extractant, organic extractant directly mixed in advance with earth solution and the alkaline earth metal compound powder that contains magnesium and/or calcium or water slurry extract, the rare earth ion of aqueous phase is extracted into organic phase, 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 pretreatment process of organic extractant, product and application thereof, it is with organic extractant and earth solution and contain the alkaline earth metal compound powder of magnesium and/or calcium or water slurry mixes in advance and extracts, or mix in advance with the carbonated rare earth slurries and to extract, the rare earth ion of aqueous phase is extracted into organic phase, the hydrogen in statu nascendi ion that exchanges is with alkaline earth metal compound or carbonated rare earth dissolving, keep 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 calcic, the alkaline-earth metal mineral of 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, oxyhydroxide, carbonate powder or water slurry carry out pre-treatment or pre-extraction to organic phase, because calcic, the alkaline-earth metal mineral and the oxide compound thereof of magnesium, hydroxide product contains more silicon, iron, impurity such as aluminium, solid-liquid reaction speed is slow and incomplete, cause and produce the three-phase thing in pre-treatment or the extraction process, influencing extraction process carries out smoothly, and, iron, impurity such as aluminium easily collection are gone in the organic phase, thereby influence quality product.
The present invention calcines mineral such as magnesite, Wingdale, calcite, rhombspar-digest-carbonization, or magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture water sized mixing, feed carbon dioxide and carry out carbonization, obtain the Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution, again after filtration, with Impurity removals such as silicon, iron, aluminium, the pure Magnesium hydrogen carbonate that obtains and/or the Calcium hydrogen carbonate 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 quality product, (2) liquid-liquid reactions, speed of response is fast, and rare earth extraction is more complete, and flow is accurately control easily; (3) directly adopt calcic, magnesium raw ore or specification lower oxide compound, oxyhydroxide, 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 novel process 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.
The present invention has studied the processing method 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, naphthenic acid.Acid organic extractant and Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution, earth solution mixed in advance extract, rare earth ion is extracted in the organic phase, 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 with easy collection rare earth ion exchanged, separate through multi-stage solvent extraction, difficult collection rare earth ion is separated with easy collection rare earth ion.The primitive reaction formula is as follows
RE
a 3++ 3HA==RE
aA
3+ 3H
+-----------reaction formula 3
M (HCO
3)
2+ 2H
+==M
2++ 2CO
2+ 2H
2O-----------reaction formula 4
Or M (HCO
3)
2+ 2HA==MA
2+ 2CO
2+ 2H
2O-----------reaction formula 5
3MA
2+ 2RE
a 3+==2RE
aA
3+ 3M
2+-----------reaction formula 6
RE
aA
3+ RE
b 3+==RE
bA
3+ RE
a 3+-----------reaction formula 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 enter water, do not enter 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 as follows:
The present invention proposes a kind of technology of extracting and separating rear earth element, comprise the steps: at least
(1) with blank organic extractant and Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution, earth solution simultaneously or substep mix in advance and extract, rare earth ion is extracted in the organic phase, through clarification, obtain load organic phases and raffinate water, load organic phases middle-weight rare earths content REO is 0.05-0.23mol/L, the raffinate aqueous pH values is 1.5-5, the described Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution by magnesium or/and the calcium mineral prepare through a roasting-digestion carbonization method.
(2) load organic phases that will the contain rare earth ion rare earth feed liquid that is used to contain rare earth element more than 2 kinds or 2 kinds carries out extracting and separating, through multi-stage solvent 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 crystal, or further extracting and separating 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 phase/water=0.1-10, the two-phase mixing time is 3-80 minute, and settling time 5-120 minute, temperature was controlled at 15-90 ℃ in the groove.
The extracting and separating of rare earth element described in the step (2) adopts 10-200 level fractionation 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 phase/water=0.1-20, the two-phase mixing time is 3-15 minute, settling time 5-30 minute, temperature was controlled at 15-90 ℃ in the groove.
Described rare earth element is at least a in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, yttrium, lutetium, yttrium, the scandium;
The described 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, naphthenic acid 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 difficult collection rare earth elements that the described 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 mixing solutions of a kind or several rare earth elements, its rare earth concentration REO is 0.1-1.5mol/L.The described rare earth feed liquid of step (2) is mixed chloride solution, nitrate solution, sulfate liquor or its mixing solutions that contains rare earth element more than 2 kinds or 2 kinds, and its rare earth concentration REO is 0.2-1.8mol/L.
Magnesium oxide and/or calcium oxide content are 0.1-18wt% in the described Magnesium hydrogen carbonate of step (1) and/or the Calcium hydrogen carbonate aqueous solution, are optimized for 1-8wt%
The described Magnesium hydrogen carbonate of step (1) and/or the Calcium hydrogen carbonate aqueous solution are prepared through roasting-digestion-carbonization method by at least a mineral in magnesite, Wingdale, calcite, rhombspar, marble or the asbestos tailings.Mineral were at 700-1000 ℃ of roasting 1-10 hour, size mixing through digestion and water again, solvent and solute weight ratio is 5-1000: 1, feed carbon dioxide then and carry out carbonization, temperature of reaction is controlled at 0-90 ℃, reaction times is 0.1-5 hour, after filtration, obtains the purified Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution.Optimizing solid weight ratio is 10-100: 1, and temperature of reaction is 0-60 ℃, the reaction times is 0.5-2 hour.
The described Magnesium hydrogen carbonate of step (1) and/or the Calcium hydrogen carbonate aqueous solution or by the preparation of magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture water slurry and carbon dioxide reaction.Being about to magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture water sizes mixing, solvent and solute weight ratio is 5-1000: 1, feed carbon dioxide then and carry out carbonization, temperature of reaction is controlled at 0-90 ℃, reaction times is 0.1-5 hour, after filtration, obtain the purified Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution.The optimization solvent and solute weight ratio is 10-100: 1, and temperature of reaction is 0-60 ℃, the reaction times is 0.5-2 hour.
The load organic phases middle-weight rare earths content REO that step (1) obtains is 0.1-0.2mol/L, and the raffinate aqueous pH values is between 2-4, and wherein content of rare earth REO is less than 0.002mol/L.
The carbon dioxide that step (1) hybrid extraction produces returns the preparation that is used for the Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution through collecting.
Advantage of the present invention is:
The present invention carries out hybrid extraction with acid organic extractants such as P507, P204, C272, naphthenic acid and Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution, earth solution, rare earth ion is extracted in the organic phase, through clarification, the load organic phases that obtains containing rare earth ion is used for the extracting and separating of mishmetal feed liquid, and, obtain the enriched substance of single rare earth compound or several rare earths through the multi-stage solvent extraction separation.The used Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution are prepared through roasting-digestion-carbonization method by mineral such as magnesite, Wingdale, calcite, rhombspars, foreign matter contents such as silicon, iron, aluminium are low, pre-extraction and extraction separation process do not produce the three-phase thing, do not influence product purity, and organic phase 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 processing costss.
Description of drawings:
Accompanying drawing is the synoptic diagram of the processing method of a kind of extracting and separating rear earth element disclosed by the invention.
Fig. 1: acid organic extractant or/and Calcium hydrogen carbonate, earth solution mix in advance and extract, directly prepares the process schematic representation of mixed rare earth compound with Magnesium hydrogen carbonate then with sour back extraction.
Fig. 2: acid organic extractant or/and Calcium hydrogen carbonate, earth solution mix in advance and extract, carries out the process schematic representation that multistage fractionation extraction separates the single rare earth compound with Magnesium hydrogen carbonate then.
Nomenclature among the figure:
The blank organic phase of Y1-; The Y2-load organic phases; The F-rare earth feed liquid; The C-earth solution; The D-Magnesium hydrogen carbonate is or/and Calcium hydrogen carbonate;
E1-raffinate water; 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)
Embodiment
Below with embodiment method of the present invention and application thereof are described further.Protection domain of the present invention is not subjected to the restriction of these embodiment, and protection domain of the present invention is determined by claims.
Embodiment 1
The light calcined magnesia that magnesite was obtained 850-900 ℃ of roasting in 2 hours, adding 3-5 water doubly digested 30 minutes down at 80 ℃, water is sized mixing then, solvent and solute weight ratio is 80: 1, feed carbon dioxide (concentration is 30%) then, reacted 40 minutes down at 20 ℃,, obtain the purified Magnesium hydrogen carbonate aqueous solution (Mg0:1.2%) through clarification filtration.
With the flow velocity of the Magnesium hydrogen carbonate aqueous solution with 3.73L/min, lanthanum-cerium chloride solution (0.928mol/L) is with the flow velocity of 0.8L/min, 1.5mol/L carry out common stream extraction in P507 organic phase 6 grades of pre-extraction tanks of flow velocity adding with 4L/min, mixing time 25 minutes, clarified 20 minutes, and obtained containing the load organic phases of difficult collection rare earth ion lanthanum cerium, its rare upward content REO is 0.185mol/L, the raffinate aqueous pH values is 2.8, and REO content is less than 0.001mol/L.
Load organic phases is directly used in the LaCe/Pr fractionation extraction separates,, obtain 99.9% praseodymium chloride and lanthanum-cerium chloride enriched substance through 65 grades of fractionation extractions.Return the preparation that is used for the Magnesium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 2
Light calcined magnesia and calcium oxide mixture that rhombspar was obtained 800-850 ℃ of roasting in 2 hours, size mixing through digestion back water, solvent and solute weight ratio is 100: 1, feed carbon dioxide (concentration is 40%) then, reacted 40 minutes down at 20 ℃, through clarification filtration, obtain the purified Magnesium hydrogen carbonate and the Calcium hydrogen carbonate aqueous solution (MgO+CaO:0.92%).
With Magnesium hydrogen carbonate and the Calcium hydrogen carbonate aqueous solution flow velocity with 6.4L/min, lanthanum-cerium chloride solution (0.665mol/L) is with the flow velocity of 1.5L/min, 1.3mol/L extract in P204 organic phase 12 grades of pre-extraction tanks of flow velocity adding with 6L/min, mixing 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 raffinate aqueous pH values is 3.5, REO content 0.0011mol/L.
Load organic phases is directly used in the LaCe/PrNd fractionation extraction separates,, obtain lanthanum-cerium chloride and praseodymium chloride neodymium through 75 grades of fractionation extractions.Return the preparation that is used for the Magnesium hydrogen carbonate and the Calcium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 3
With the calcium oxide that Wingdale obtained 800-850 ℃ of roasting in 2 hours, water digestion is sized mixing, and solvent and solute weight ratio is 16: 1, feed carbon dioxide (concentration is 60%) then, reacted 30 minutes down at 70 ℃,, obtain the purified Calcium hydrogen carbonate aqueous solution (CaO:6.25%) through clarification filtration.
With the flow velocity of the Calcium hydrogen carbonate aqueous solution with 1.12L/min, lanthanum nitrate hexahydrate (0.744mol/L) is with the flow velocity of 1.5L/min, 1.5mol/L extract in P507 organic phase 8 grades of pre-extraction tanks of flow velocity adding with 6L/min, mixing 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 raffinate aqueous pH values is 4.5, REO content 0.0016mol/L.
Load organic phases is directly used in the La/Ce fractionation extraction separates,, obtain 99.99% lanthanum nitrate and 99.9% cerous nitrate through 68 grades of fractionation extractions.Return the preparation that is used for the Calcium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 4
The calcium oxide water is sized mixing, thin up then, solvent and solute weight ratio is 8: 1, feeds carbon dioxide (concentration is 90%) then, 30 ℃ of reactions 60 minutes down, through clarification filtration, obtains the purified Calcium hydrogen carbonate aqueous solution (CaO:12.5%).
With the flow velocity of the Calcium hydrogen carbonate aqueous solution with 0.56L/min, lanthanum nitrate hexahydrate (0.744mol/L) is with the flow velocity of 1.5L/min, 1.5mol/L extract in P507 organic phase 8 grades of pre-extraction tanks of flow velocity adding with 6L/min, mixing 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 raffinate aqueous pH values is 4.6, REO content 0.0015mol/L.
Load organic phases is directly used in the La/Ce fractionation extraction separates,, obtain 99.99% lanthanum nitrate and 99.9% cerous nitrate through 68 grades of fractionation extractions.Return the preparation that is used for the Calcium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 5
The magnesium oxide water is sized mixing, thin up then, solvent and solute weight ratio is 80: 1, feeds carbon dioxide (concentration is 95%) then, 15 ℃ of reactions 30 minutes down, through clarification filtration, obtains the purified Magnesium hydrogen carbonate aqueous solution (MgO:1.8%).
With the flow velocity of the Magnesium hydrogen carbonate aqueous solution with 2.6L/min, lanthanum-cerium chloride solution (0.928mol/L) is with the flow velocity of 0.8L/min, 1.5mol/L carry out common stream extraction in P507 organic phase 6 grades of pre-extraction tanks of flow velocity adding with 4L/min, mixing 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 raffinate aqueous pH values is 3.0, and REO content is less than 0.001mol/L.
Load organic phases is directly used in the LaCe/Pr fractionation extraction separates,, obtain 99.9% praseodymium chloride and lanthanum-cerium chloride enriched substance through 65 grades of fractionation extractions.Return the preparation that is used for the Magnesium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 6
With the flow velocity of the Calcium hydrogen carbonate aqueous solution (CaO:5%) with 1.4L/min, sulfuric acid LaCePrNd solution (0.25mol/L) is with the flow velocity of 4.46L/min, 1.5mol/L extract in P204 organic phase 6 grades of pre-extraction tanks of flow velocity adding with 6.1L/min, mixing 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 raffinate aqueous pH values 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.
Return the preparation that is used for the Calcium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 7
With the flow velocity of the Magnesium hydrogen carbonate aqueous solution (MgO:1.2%) with 4.6L/min, mix the flow velocity of rare earth sulfate solution (0.25mol/L) with 3.6L/min, 1.5mol/L extract in P507 organic phase 10 grades of pre-extraction tanks of flow velocity adding with 5L/min, through 6 grades of stream, extractions of 4 stage countercurrents altogether, obtain containing the load organic phases of LaCePrNd, its content of rare earth REO is 0.178mol/L, and the raffinate aqueous pH values 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 extracting and separating single rare earth, or process evaporating, concentrating and crystallizing obtains the mixed chlorinated rare earth product.
Return the preparation that is used for the Magnesium hydrogen carbonate aqueous solution behind the carbon dioxide collection with pre-extractive reaction release.
Embodiment 8
With 9M
3Magnesium hydrogen carbonate (MgO:0.5%) and 4M
31.5mol/L the mixed extractant of P507 (80%) and P204 (20%) adds 20M
3Steel basin in mixed 3 minutes, add 1M then
3Praseodymium chloride solution (REO 0.724mol/L) mixed 15 minutes, and 25 ℃ of temperature of reaction 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 raffinate aqueous pH values is 3, REO content 0.0011mol/L.
Load organic phases is directly used in the extracting and separating that contains praseodymium/neodymium mixed chlorinated rare earth solution, through 96 grades of fractionation extraction, obtains 99.9% praseodymium chloride and 99.9% Neodymium trichloride.
Embodiment 9
With 4M
31.5mol/L P507 extraction agent and 0.GM
3Praseodymium chloride solution (REO 1.237mol/L) adds 12M
3Steel basin in mixed 2 minutes, add 3M then
3Magnesium hydrogen carbonate (MgO 1.5%) mixed 30 minutes, and 20 ℃ of temperature of reaction 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 raffinate aqueous pH values is 2.5, REO content 0.0012mol/L.
Load organic phases is directly used in the extracting and separating that contains praseodymium/neodymium mixed chlorinated rare earth solution, through 96 grades of fractionation extraction, obtains 99.9% praseodymium chloride and 99.9% Neodymium trichloride.
Embodiment 10
With 4M
31.5mol/L P507 extraction agent, 0.6M
3Terbium chloride solution (REO 1.237mol/L) and 3M
3Magnesium hydrogen carbonate (MgO 1.5%) adds 12M simultaneously
3Reactive tank in mixed 20 minutes, 35 ℃ of temperature of reaction 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 raffinate aqueous pH values is 4, REO content 0.0005mol/L.
Load organic phases is directly used in the extracting and separating that contains terbium/dysprosium mixed chlorinated rare earth solution, through 96 grades of fractionation extraction, obtains 99.99% terbium chloride and 99.9% Dysprosium trichloride.
Embodiment 11
With 4M
30.7mol/L naphthenic acid and 3M
3Calcium hydrogen carbonate (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 temperature of reaction through clarification in 30 minutes, obtain containing the load organic phases of yttrium, and its concentration is 0.185mol/L, and the raffinate aqueous pH values is 4, REO content 0.0005mol/L.
Load organic phases is directly used in the extracting and separating that contains yttrium mixed chlorinated rare earth solution, through 96 grades of fractionation extractions, obtains Yttrium trichloride and other rareearth enriching material greater than 99.99%.
Claims (16)
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 blank organic extractant and Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution, earth solution simultaneously or substep mix in advance and extract, rare earth ion is extracted in the organic phase, through clarification, obtain load organic phases and raffinate water, load organic phases middle-weight rare earths content REO is 0.05-0.23mol/L, the raffinate aqueous pH values is 1.5-5, the described Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution by magnesium or/and the calcium mineral prepare through roasting-digestion-carbonization method.
(2) load organic phases that will the contain rare earth ion rare earth feed liquid that is used to contain rare earth element more than 2 kinds or 2 kinds carries out extracting and separating, through multi-stage solvent 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 crystal, or further extracting and separating 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 phase/water=0.1-10, the two-phase mixing time is 3-80 minute, 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, it is characterized in that: the extracting and separating of rare earth element described in the step (2) adopts 10-200 level fractionation 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 phase/water=0.1-20, the two-phase mixing time is 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: described rare earth element 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 difficult collection rare earth elements that the described 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 mixing solutions of a kind or several 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 described rare earth feed liquid of step (2) is mixed chloride solution, nitrate solution, sulfate liquor or its mixing solutions 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 described 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 to use organic solvent diluting, extractant concentration be 0.5-1.7mol/l.
8. the technology of a kind of extracting and separating rear earth element according to claim 7, it is characterized in that: described organic extractant is one or more mixed extractants that contain in P507, P204, P229, C272, C301, C302, naphthenic acid 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: magnesium oxide and/or calcium oxide content are 0.1-18wt% in the described Magnesium hydrogen carbonate of step (1) and/or the Calcium hydrogen carbonate aqueous solution.
10. the technology of a kind of extracting and separating rear earth element according to claim 9 is characterized in that: magnesium oxide and/or calcium oxide content are 1-8wt% in the described Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution.
11. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: the described Magnesium hydrogen carbonate of step (1) and/or the Calcium hydrogen carbonate aqueous solution are prepared through roasting-digestion-carbonization method by at least a mineral in magnesite, Wingdale, calcite, rhombspar, marble or the asbestos tailings.
12. the technology of according to claim 11-kind of extracting and separating rear earth element, wherein Magnesium hydrogen carbonate and/or Calcium hydrogen carbonate water solution preparation method are: described mineral were at 700-1000 ℃ of roasting 1-10 hour, size mixing through digestion and water again, solvent and solute weight ratio is 5-1000: 1, feed carbon dioxide then and carry out carbonization, temperature of reaction is controlled at 0-90 ℃, and the reaction times is 0.1-5 hour, after filtration, obtain the purified Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution.
13. the technology of a kind of extracting and separating rear earth element according to claim 1, it is characterized in that: described Magnesium hydrogen carbonate of step (1) and/or Calcium hydrogen carbonate water solution preparation method are as follows: magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide or its mixture water are sized mixing, solvent and solute weight ratio is 5-1000: 1, feed carbon dioxide then and carry out carbonization, temperature of reaction is controlled at 0-90 ℃, reaction times is 0.1-5 hour, after filtration, obtain the purified Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution.
14. technology according to claim 11 or 13 described a kind of extracting and separating rear earth elements, wherein Magnesium hydrogen carbonate and/or Calcium hydrogen carbonate water solution preparation method are: described solvent and solute weight ratio is 10-100: 1, temperature of reaction is controlled at 0-60 ℃, reaction times is 0.5-2 hour, after filtration, obtain the purified Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution.
15. 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-weight rare earths content REO that step (1) obtains is 0.1-0.2mol/L, the raffinate aqueous pH values is between 2-4, and wherein content of rare earth REO is less than 0.002mol/L.
16. the technology of a kind of extracting and separating rear earth element according to claim 1 is characterized in that: the carbon dioxide that step (1) hybrid extraction produces returns the preparation that is used for the Magnesium hydrogen carbonate and/or the Calcium hydrogen carbonate aqueous solution through collecting.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910118985A CN101781706A (en) | 2009-01-15 | 2009-03-11 | Process for separating rare-earth element by extraction |
| CN2010800005518A CN101970700B (en) | 2009-01-15 | 2010-01-14 | Application of aqueous solution of magnesium bicarbonate and/or calcium bicarbonate in the process of extraction separation and purification of metals |
| PCT/CN2010/070182 WO2010081418A1 (en) | 2009-01-15 | 2010-01-14 | Application of aqueous solution of magnesium bicarbonate and/or calcium bicarbonate in the process of extraction separation and purification of metals |
| AU2010205981A AU2010205981B2 (en) | 2009-01-15 | 2010-01-14 | Application of aqueous solution of magnesium bicarbonate and/or calcium bicarbonate in the process of extraction separation and purification of metals |
| MYPI2011003057 MY152064A (en) | 2009-01-15 | 2010-01-14 | Application of aqueous solution of magnesium bicarbonate and/or calcium bicarbonate in the process of extraction separation and purification of metals |
| US13/143,772 US8721998B2 (en) | 2009-01-15 | 2010-01-14 | Use of Mg(HCO3)2 and/or Ca(HCO3)2 aqueous solution in metal extractive separation and purification |
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| CN200910076956.9 | 2009-01-15 | ||
| CN200910118985A CN101781706A (en) | 2009-01-15 | 2009-03-11 | Process for separating rare-earth element by extraction |
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