CN101319276B - Preextraction method for organic extraction agent, product and uses thereof - Google Patents
Preextraction method for organic extraction agent, product and uses thereof Download PDFInfo
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Abstract
The invention discloses a pre-extraction method for an organic extraction agent, a product and an application thereof in the extraction and separation of rare earths. The pre-extraction method comprises the following steps that: the organic extraction agent is directly mixed with a rare earth solution and alkaline-earth metal compound powder or water slurry containing magnesium and/or calcium for pre-extraction, rare earth metal ions in an aqueous phase are extracted into an organic phase, exchanged nascent hydrogen ions dissolve an alkaline-earth metal compound to maintain the acidity balance of an extraction system so as to produce a loaded organic extraction agent which contains the rare earth metal ions and is used for nonsaponifiable extraction and separation of rare earth elements. In the extraction method, the organic extraction agent does not need liquid ammonia and liquid alkali to saponify, no ammonia nitrogen waste water is produced during the extraction and separation process of the rare earths, the separation cost for the rare earths is greatly reduced, and a large amount of cost for three-waste treatment is saved. The method is suitable for the extraction and separation of the rare earths in all hydrochloric acid systems, sulphuric acid systems and nitric acid systems, has small investment, and takes effect quickly.
Description
Technical field
The present invention relates to a kind of pre-extracting process, product and the application in rare earth extraction separates thereof of organic extractant.Specifically by organic extractant directly with earth solution with contain the alkaline earth metal compound powder of magnesium and/or calcium or water slurry mixes in advance and extracts, rare earth ion in water is extracted into organic phase, the hydrogen in statu nascendi ion exchanged dissolves alkaline earth metal compound, obtains containing the non-saponifiable extraction separation of the load organic extractant of rare earth ion for rare earth element.
Background technology
The separating-purifying of current industrial Rare Earth Elements Determination generally adopts solvent extration, the most frequently used technique has: extraction agent extracting and separating rear earth element ([1] rare earth chemistry collections of thesis in hydrochloric acid system such as saponification P507, P204, C272, institute, nineteen eighty-two, Science Press should be changed in Changchun; [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); Saponification P507 solvent extraction and separation mixed rare earth craft (CN85102210); Organic phase continuous saponification technique (CN95117989.6); Saponification naphthenate acid system separating-purifying yttrium oxide (Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), metallurgical industry press, 2002, P582,590).Above-mentioned extracting and separating extraction agent used all belongs to organic extractant, requirement is extracting and separating under low acidity, its extracting power (partition ratio) is inversely proportional to water balance acidity, a rare earth ion of general extraction will be replaced 3 hydrogen ions and be entered water, therefore must adopt ammoniacal liquor or the mineral alkalis such as sodium hydroxide, bicarbonate of ammonia first to carry out saponification to extraction agent, hydrogen ion is removed to (seeing reaction formula 1), then with rare earth ion, exchange extraction (seeing reaction formula 2).As can be seen here, in extraction process, not only owing to consuming a large amount of ammonia, cause cost to increase, and to produce a large amount of ammonia nitrogen waste waters, water resources is caused to serious pollution, because ammonia nitrogen waste water concentration is lower, recovery difficult is large, 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 current 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.
Summary of the invention
The purpose of this invention is to provide a kind of non-saponifiable extraction that does not produce ammonia nitrogen waste water, the pre-extracting process of organic extractant that production cost is low and be applied to rare earth element separates.
The inventor is according to the characteristic of the acidic extractants such as P507, P204, C272, studied a kind of pre-extracting process of acidic extractant, be about to organic extractant directly with a certain amount of earth solution containing difficult extraction rare earth ion with contain the alkaline earth metal compound powder of magnesium and/or calcium or water slurry mixes in advance and extracts, hydrogen ion exchange (seeing reaction formula 3) in rare earth ion and extraction agent, rare earth ion is extracted in extraction agent, the hydrogen ion that the virning activity exchanged is high dissolves alkaline earth metal compound, generates (seeing reaction formula 4,5) such as water and alkaline-earth metal ions.After pre-extraction containing the extraction agent of difficult extraction rare earth ion when the extracting and separating rear earth element with easy extraction rare earth ion exchanged (seeing reaction formula 6).Through multistage fractionation or counter-current extraction, difficult extraction rare earth ion is separated with easy extraction rare earth ion.
RE
a 3++ 3 (HA)
2==RE
a(HA
2)
3+ 3H
+-----------reaction formula 3
MO+2H+==M
2++ H
2o-----------reaction formula 4
Or M (OH)
2+ 2H
+==M
2++ 2H
2o-----------reaction formula 5
RE
a(HA
2)
3+ RE
b 3+==RE
b(HA
2)
3+ RE
a 3+-----------reaction formula 6
M represents alkaline-earth metal, RE
a 3+represent difficult extraction rare earth ion, RE
b 3+represent the Yi Cui rare earth ion.
Organic extractant is through above-mentioned pre-extraction, and hydrogen ion, alkaline-earth metal ions do not enter extraction separation process basically, makes extraction separation process balance acidity stable, and in rare-earth products, alkaline earth metal content is low.
The concrete technical scheme of the present invention is as follows:
1, the pre-extracting process of this organic extractant comprises the steps:
The blank organic extractant of 0.5-2mol/L, the earth solution containing REO 0.1-1.8mol/L, the alkaline earth metal compound powder that contains magnesium and/or calcium or water slurry are mixed and extract in advance, rare earth ion in water and the exchange of the hydrogen ion in organic phase are extracted into organic phase, the hydrogen ion exchanged dissolves the alkaline earth metal compound containing magnesium and/or calcium, keep pre-extraction system acidity balance, its pH value, between 1.5-5, obtains the load organic extractant containing REO 0.05-0.23mol/L.
Described pre-extraction is to adopt single-stage or the 5-15 level flows altogether and/or reflux type carries out, and the two-phase mixing time is 10-80 minute, and in groove, temperature is controlled at 15-95 ℃.
Described blank organic extractant is the organic extractant after back extraction in extraction separation process, organic extractant for containing in acidic phosphorus extractant, alkyl phosphorus oxide kind of extractants, carboxylic acid extractant-kind or two or more mixed extractants, and to use organic solvent diluting, extractant concentration be 0.5-1.7mol/l.
Described organic extractant is one or more mixed extractants containing in P507, P204, P229, TRPO, C272, C301 and C302, described thinner is one or more the organic solvent in kerosene, solvent oil, alkane, Organic Alcohol, and extractant concentration is 1-1.5mol/l.
The pre-extracting process of described organic extractant, its earth solution is the raffinate of rare earth extraction segregation section containing difficult extraction rare earth component, or with re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixing solutions like the raffinate constituent class, its rare earth concentration REO is 0.1-1mol/L.
The described basic cpd containing magnesium and/or calcium is one or more mixtures in magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium carbonate, calcium hydroxide, medium particle diameter D
50be controlled at 0.1-50 μ m, the content in mixing water is 1-15wt% (pressing magnesium oxide or calcium oxide calculates).Basic cpd containing magnesium and/or calcium is preferably one or more mixtures in magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, and powder is through levigate sieving, medium particle diameter D
50be controlled at 0.5-15 μ m, the content in mixing water is 2-10wt% (pressing magnesium oxide or calcium oxide calculates).
The volume ratio of described organic extractant and water: organic phase/slurries=0.3-10, extracting in advance back loading organic extractant middle-weight rare earths concentration REO is 0.1-0.20mol/L.
After the pre-extraction of described organic extractant, the raffinate aqueous pH values is between 1.5-3, and REO is less than 0.05mol/L.Optimal conditions be the raffinate aqueous pH values between 3-5, REO is less than 0.003mol/L.
Above-mentioned raffinate water can adopt P204 or P507 extraction to reclaim residual rare earth, makes REO in the raffinate water be less than 0.002mol/L.
The load organic extractant that the load that above-mentioned pre-extraction is obtained has a rare earth ion is for the extracting and separating rear earth element: be about to the load organic extractant and carry out rare earth extraction with re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixing solutions and separate; Extracting and separating is to adopt multistage fractionation extraction or counter-current extraction mode to carry out, and in groove, temperature is controlled at 15-90 ℃.
Described rare earth element is at least two kinds in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, yttrium, lutetium, yttrium.
Advantage of the present invention is:
The present invention by organic extractant directly with earth solution with contain the alkaline earth metal compound powder of magnesium and/or calcium or water slurry mixes in advance and extracts, hydrogen ion, alkaline-earth metal ions do not enter extraction separation process, make extraction process balance acidity stable, in rare-earth products, alkaline earth metal content is low, particularly extraction separation process does not need liquefied ammonia or liquid caustic soda to carry out saponification to organic phase, do not produce ammonia nitrogen waste water, can eliminate the pollution of ammonia nitrogen waste water to environment, water consumption and rare-earth products production cost decrease, and save a large amount of three wastes processing costss.The method is applicable to all hydrochloric acid systems, sulfuric acid system and nitric acid system rare earth extraction separates, less investment, instant effect.The Rare Earth Factory that the separating power of take is 3000 tons of ion adsorption type rare earth ores is example, can reduce 2800 tons of liquefied ammonia or 20,000 tons of liquid caustic soda every year, reduces costs ten thousand yuan of 900-1500, reduces 90,000 tons of ammonia nitrogen waste waters, and water consumption reduces 50%.
Embodiment
Below with embodiment, method of the present invention and application thereof are described further.
Embodiment 1
Add magnesium oxide (MgO content is 92%) medium particle diameter D in pre-extraction tank
50be 3.5 μ m, the mixed extractant of praseodymium chloride solution (0.35mol/L) and 1.5mol/L P507 (80%) and P204 (20%) extracts in advance; It is 0.80kg/min that magnesium oxide adds speed, and the praseodymium chloride solution flow rate is 38L/min, and the organic phase flow velocity is 67L/min, 20 minutes hybrid extraction time, through 5 grades of stream, 3 stage countercurrent extractions altogether, obtain the load organic phases containing praseodymium, its content of rare earth REO is 0.18mol/L, the raffinate aqueous pH values is 2.0, the raffinate water is directly with the P204 extraction of 1.0mol/L, and organic/water=0.7/1, through 6 grades of extractions, raffinate water Rare-Earth Content REO is 0.0014mol/L, and rare earth yield is 99.8%.The load organic phases obtained is directly used in the Pr/Nd extracting and separating, through 93 grades of fractionation extraction, obtains 99.9% praseodymium chloride and 99.9% Neodymium trichloride.
Embodiment 2
Magnesium oxide powder medium particle diameter D
50be 1.2 μ m, MgO content is 88%, magnesium oxide is with the flow velocity of 0.9kg/min, praseodymium chloride solution (0.85mol/L) is with the flow velocity of 16L/min, 1.5mol/LP507 organic phase adds in pre-extraction tank with the flow velocity of 70L/min, 15 minutes hybrid extraction time, in groove, temperature is 48 ℃, through 4 grades, flow altogether, 3 stage countercurrent extractions, obtain the load organic phases containing praseodymium, its content of rare earth REO is 0.187mol/L, the raffinate aqueous pH values is 2.5, the raffinate water directly extracts with the P204 of 1.0mol/L, organic/water=0.5/1, through 6 grades of extractions, raffinate water content of rare earth REO is 0.002mol/L, rare earth yield is 99.8%.The load organic phases obtained is directly used in the Pr/Nd extracting and separating, through 90 grades of fractionation extraction, obtains 99.5% praseodymium chloride and 99.9% Neodymium trichloride.
Embodiment 3
(MgO content is 88%, medium particle diameter D to add magnesium oxide in pre-extraction tank
50be 1.5 μ m) water slurry (the magnesium oxide solids content is 3wt%), praseodymium chloride solution (1.18mol/L) and 1.5mol/LP507 extract in advance; It is 0.44kg/min that magnesium oxide adds speed, the praseodymium chloride solution flow rate is 5.2L/min, the organic phase flow velocity is 32L/min, 15 minutes hybrid extraction time, through 4 grades of stream extractions altogether, 2 stage countercurrent extractions, 2 grades of clarifications, obtain the load organic phases containing praseodymium, its content of rare earth REO is 0.191mol/L, the raffinate aqueous pH values is 3.0, and raffinate water Rare-Earth Content REO is 0.0026mol/L, and rare earth yield is 99.6%.The load organic phases obtained is directly used in the Pr/Nd extracting and separating, through 86 grades of fractionation extracting and separating, obtains 99.9% praseodymium chloride and 99.5% Neodymium trichloride.
Embodiment 4
In pre-extraction tank, add calcium oxide (CaO content is 91%), lanthanum nitrate hexahydrate (REO 0.526mol/L) and 1.0mol/L P204 to extract in advance; It is 0.45kg/min that calcium oxide adds speed, the lanthanum nitrate hexahydrate flow velocity is 9.2L/min, the organic phase flow velocity is 32L/min, 25 minutes hybrid extraction time, through 7 grades of stream extractions altogether, 3 stage countercurrent extractions, obtain the load organic phases containing lanthanum, its content of rare earth REO is 0.151mol/L, the raffinate aqueous pH values is 4.0, and raffinate water Rare-Earth Content REO is 0.001mol/L, and rare earth yield is 99.8%.The load organic phases obtained is directly used in the La/Ce extracting and separating, through 70 grades of fractionation extracting and separating, obtains 99.99% lanthanum nitrate and 99.9% cerous nitrate.
Embodiment 5
In pre-extraction tank, add magnesium hydroxide slurries (MgO content is 35%) water slurry, terbium chloride solution (0.837mol/L) and 1.5mol/L P507 to extract in advance; It is 0.71kg/min that magnesium hydroxide slurries adds speed, the terbium chloride solution flow rate is 4.8L/min, the organic phase flow velocity is 22L/min, 25 minutes hybrid extraction time, through 3 grades of stream extractions altogether, 3 stage countercurrent extractions, obtain the load organic phases containing terbium, its content of rare earth REO is 0.182mol/L, the raffinate aqueous pH values is 3.5, and raffinate water Rare-Earth Content REO is 0.002mol/L, and rare earth yield is 99.6%.The load organic phases obtained is directly used in the Tb/Dy fractionation extraction separates, and through 72 grades of fractionation extractions, obtains 99.9% Dysprosium trichloride and 99.99% terbium chloride.
Embodiment 6
(MgO content is 47%, medium particle diameter D to add magnesiumcarbonate in pre-extraction tank
50be 1.1 μ m), lanthanum-cerium chloride solution (0.837mol/L) and 1.5mol/L P507 extract in advance; It is 0.47kg/min that magnesiumcarbonate adds speed, the lanthanum-cerium chloride solution flow rate is 4.8L/min, the organic phase flow velocity is 22L/min, 30 minutes hybrid extraction time, through 4 grades of stream extractions altogether, 3 stage countercurrent extractions, obtain the load organic phases containing the lanthanum cerium, its content of rare earth REO is 0.182mol/L, the raffinate aqueous pH values is that 3.0, REO is 0.0029mol/L, and rare earth yield is 99.7%.The load organic phases obtained is directly used in the Ce/Pr fractionation extraction separates, and through 75 grades of fractionation extractions, obtains lanthanum-cerium chloride and praseodymium chloride neodymium.
Embodiment 7
In pre-extraction tank, add magnesium oxide water slurry (the magnesium oxide solids content is 7.5wt%), lanthanum sulfat solution and 1.3mol/L P204 to extract in advance, it is 0.30kg/min that magnesium oxide adds speed, lanthanum sulfat solution (0.29mol/L) flow velocity is 16L/min, the organic phase flow velocity is 32L/min, 15 minutes hybrid extraction time, through 3 grades of stream extractions altogether, 3 stage countercurrent extractions, obtain the load organic phases containing lanthanum, its content of rare earth REO is 0.143mol/L, the raffinate aqueous pH values is 3.0, raffinate water Rare-Earth Content REO is 0.0027mol/L, and rare earth yield is 99.1%.The load organic phases obtained is directly used in the La/Ce extracting and separating, through 70 grades of fractionation extracting and separating, obtains 99.99% Lanthanum trichloride and 99.9% Cerium II Chloride.
Claims (13)
1. the pre-extracting process of an organic extractant is characterized in that:
The blank organic extractant of 0.5-2mol/L, the earth solution containing REO 0.1-1.8mol/L, the alkaline earth metal compound powder that contains magnesium and/or calcium or water slurry are mixed and extract in advance, rare earth ion in water and the exchange of the hydrogen ion in organic phase are extracted in organic phase, the hydrogen ion exchanged dissolves the alkaline earth metal compound containing magnesium and/or calcium, water balance pH value is 1.5-5, obtains load organic extractant and raffinate water containing REO 0.05-0.23mol/L.
2. the pre-extracting process of organic extractant according to claim 1 is characterized in that: described pre-extraction is to adopt single-stage or the 5-15 level flows altogether and/or reflux type carries out, and the two-phase mixing time is 10-80 minute, and in groove, temperature is controlled at 15-95 ℃.
3. the pre-extracting process of organic extractant according to claim 1, it is characterized in that: described blank organic extractant is the organic extractant after back extraction in extraction separation process, organic extractant is one or more the mixed extractant containing in acidic phosphorus extractant, alkyl phosphorus oxide kind of extractants, carboxylic acid extractant, and to use organic solvent diluting, extractant concentration be 0.5-1.7mol/l.
4. the pre-extracting process of organic extractant according to claim 3, it is characterized in that: described organic extractant is one or more mixed extractants containing in P507, P204, P229, TRPO, C272, C301 and C302, described organic solvent is one or more organic solvents in kerosene, solvent oil, alkane, Organic Alcohol, and extractant concentration is 1-1.5mol/l.
5. the pre-extracting process of organic extractant according to claim 1, it is characterized in that: described earth solution is the raffinate of rare earth extraction segregation section containing difficult extraction rare earth component, or with re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixing solutions like the raffinate constituent class, its rare earth concentration REO is 0.1-1mol/L.
6. the pre-extracting process of organic extractant according to claim 1, it is characterized in that: the described basic cpd containing magnesium and/or calcium is one or more mixtures in magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium carbonate, calcium hydroxide, medium particle diameter D
50be controlled at 0.1-50 μ m, magnesium, calcium total content in mixing water are calculated as 1-15wt% by magnesium oxide and/or calcium oxide.
7. the pre-extracting process of organic extractant according to claim 6, it is characterized in that: the described basic cpd containing magnesium and/or calcium is one or more mixtures in magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, powder is through levigate sieving, medium particle diameter D
50be controlled at 0.5-15 μ m, magnesium, calcium total content in mixing water are calculated as 2-10wt% by magnesium oxide and/or calcium oxide.
8. the pre-extracting process of organic extractant according to claim 1, it is characterized in that: the volume ratio of described organic extractant and water: organic phase/slurries=0.3-10, extracting in advance back loading organic extractant middle-weight rare earths concentration REO is 0.1-0.20mol/L.
9. the pre-extracting process of organic extractant according to claim 1, it is characterized in that: described raffinate aqueous pH values is between 1.5-3, and REO is less than 0.05mol/L.
10. the pre-extracting process of organic extractant according to claim 1, it is characterized in that: described raffinate aqueous pH values is between 3-5, and REO is less than 0.003mol/L.
11. the pre-extracting process according to claim 1,9 described organic extractants is characterized in that: described raffinate water adopts P204 or P507 extraction to reclaim residual rare earth, makes REO in the raffinate water be less than 0.002mol/L.
12. the method for the direct extracting and separating rear earth element of load organic extractant obtained according to claim 1, it is characterized in that: described load organic extractant middle-weight rare earths concentration REO is 0.05-0.23mol/L, and the non-saponifiable extraction that is directly used in re chloride, rare earth nitrate solution, rare earth sulfate solution or its mixing solutions middle-weight rare earths containing two or more rare earth element separates; Described extracting and separating is to adopt multistage fractionation extraction or counter-current extraction mode to carry out, and in groove, temperature is controlled at 15-90 ℃.
13. the method for organic extractant extracting and separating rear earth element according to claim 12 is characterized in that: described rare earth element is at least two kinds in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium.
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| AU2010205981B2 (en) * | 2009-01-15 | 2013-09-26 | Grirem Advanced Materials Co., Ltd | Application of aqueous solution of magnesium bicarbonate and/or calcium bicarbonate in the process of extraction separation and purification of metals |
| CN101994004B (en) * | 2009-08-11 | 2012-07-11 | 北京有色金属研究总院 | Process for extracting and separating rare-earth elements |
| CN102071314B (en) * | 2011-01-31 | 2012-02-15 | 赣州力赛科新技术有限公司 | Alkaline earth metal saponification and extraction method of acidic extractant |
| BR112017001370B1 (en) * | 2014-12-31 | 2021-03-16 | Grirem Advanced Materials Co., Ltd. | method for recovery of rare earths by fractional extraction |
| CN108950252B (en) * | 2018-08-12 | 2020-07-28 | 南昌航空大学 | Separation method for co-production of pure samarium and pure terbium by fractional extraction |
| CN109097606B (en) * | 2018-08-16 | 2020-07-28 | 南昌航空大学 | Separation process for co-producing pure dysprosium and pure thulium by fractional extraction |
| CN109097571B (en) * | 2018-10-16 | 2019-11-29 | 南昌航空大学 | A kind of process of co-producing high-purity lanthanum and high-purity yttrium |
| CN110129562A (en) * | 2019-07-03 | 2019-08-16 | 德庆兴邦稀土新材料有限公司 | A kind of method for saponification of rare earth organic extractant |
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| CN86105043A (en) * | 1986-08-23 | 1988-03-09 | 北京有色金属研究总院 | Extracting and separating rear earth element from sulfuric acid system |
| CN1730681A (en) * | 2004-08-04 | 2006-02-08 | 胡建康 | Production method of acid extractant saponifying organic phase used in rare earth extraction separation |
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| CN100513600C (en) * | 2006-04-07 | 2009-07-15 | 北京有色金属研究总院 | Technique for extracting and separating rare earth elements from non-saponification system |
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| CN86105043A (en) * | 1986-08-23 | 1988-03-09 | 北京有色金属研究总院 | Extracting and separating rear earth element from sulfuric acid system |
| CN1730681A (en) * | 2004-08-04 | 2006-02-08 | 胡建康 | Production method of acid extractant saponifying organic phase used in rare earth extraction separation |
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