CN100404706C - Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant - Google Patents
Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant Download PDFInfo
- Publication number
- CN100404706C CN100404706C CNB2005101372318A CN200510137231A CN100404706C CN 100404706 C CN100404706 C CN 100404706C CN B2005101372318 A CNB2005101372318 A CN B2005101372318A CN 200510137231 A CN200510137231 A CN 200510137231A CN 100404706 C CN100404706 C CN 100404706C
- Authority
- CN
- China
- Prior art keywords
- rare earth
- extraction
- neodymium
- praseodymium
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a technique for extracting and separating rare-earth elements by mixing extraction agents in rare earth sulfate solutions or mixed solutions of rare earth sulfate solutions, rare earth chloride solutions and rare earth nitrate solutions; the mixing extraction agents use rare-earth solutions containing various rare-earth elements as raw materials, and the rare-earth solutions are obtained by processing rare earth ore; the mixing extraction agents are prepared from non-saponifying P204 and one or two of non-soponifying P507, P229, P350, TBP, C272, C301, C302 and HEOPPA. The extraction agents of the technique do not need saponifying, so a large amount of consumption of ammonium base is saved, ammonia-nitrogen wastewater can not be produced, and the problem of pollution caused by the ammonia-nitrogen wastewater is solved. In addition, high-concentration hydrochloric acid or nitric acid, strip liquor of rare earth chloride and strip liquor of rare earth nitrate replace IN sulphuric acid to be used as cleaning solutions; therefore, in the processes of extraction and stripping, the acidity is reduced, and the concentration of rare earth is increased. The technique has the advantages of simple and continuous technical process, and easy control; the consumption rate ammonium bicarbonate of chemical materials is deposited and converted, and the extraction and grouping technology for saponifying P507 is reduced by more than 30%.
Description
Technical field
The present invention relates to a kind of technology of extracting and separating rear earth element.Be raw material specifically to handle the earth solution that contains multiple rare earth element that rare-earth mineral obtains, the technology of the mixed extractant that adopts one or both preparations among non-saponified P204 and non-saponification P507, P229, P350, TBP, C272, C301, C302, HEOPPA extracting and separating rear earth element in the mixing solutions of rare earth sulfate solution or rare earth sulfate solution and re chloride, rare earth nitrate solution.
Background technology
Lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium, 17 elements of scandium are referred to as rare earth element, their character is closely similar, except that the promethium nature did not exist, other element co-existed in the rare-earth mineral, separated relatively difficulty.At present, the rare earth element extraction separating method is a lot, and method commonly used on the general industry has: 1, saponification P507 hydrochloric acid system extracting and separating rear earth element ([1] rare earth chemistry collection of thesis, institute, nineteen eighty-two, Science Press should be changed in Changchun); 2, saponification naphthenate acid system separate the purification yttrium oxide ([2] Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), metallurgical industry press, 2002, P590); 3, TBP nitric acid system extracting and separating rear earth element ([2] Xu Guangxian chief editor, rare earth, the 2nd edition (first volume), metallurgical industry press, 2002, P495); 4, non-saponification P204 extracting and separating rear earth element ([3] Chinese patent CN 86105043) from sulfuric acid system.1st, 2 kinds of method good separating effects are used very extensively, but must adopt ammoniacal liquor or saponification such as sodium hydroxide, bicarbonate of ammonia, produce a large amount of ammonia nitrogen waste waters, and environment is caused bigger pollution.The 3rd kind of method is the technology that French Rhodia, U.S. molybdenum company adopt, and it is to be derived from the rare earth nitrate solution that obtains when handling solitary stone ore to come rare-earth separating, this technology extraction system concentration of nitric acid height, and therefore, the production cost height is in halted state at present substantially.The 4th kind of technology is Beijing Non-Ferrous Metal Research General Academy's invention, extracting and separating rear earth element the rare earth sulfate solution that is applied to when sulfuric acid process is handled the packet header rare-earth mineral, obtain, the non-saponification P204 of this process using extracting and separating, do not produce ammonia nitrogen waste water, alkali consumption is few, but since the sulfuric acid system rare earth concentration low (＜45g/L), equipment extraction agent investment is big; P204 extracting power under acidic conditions is very strong, easily produces emulsification when feed acidity is low, need add a certain amount of acid during extraction, and middle heavy rare earths back extraction is very difficult, strip liquor spent acid height, and acid consumption is big.
Summary of the invention
The present invention is a raw material with the earth solution that contains multiple rare earth element that the processing rare-earth mineral obtains, adopt non-saponified P204 (D2EHPA, two (ethylhexyl dihydrogen phosphates)) with non-saponification P507 (HEH/EHP, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), P229 (two (2-ethylhexyl) phosphonic acids), P350 (methyl-phosphorous acid diformazan heptyl ester), TBP (tributyl phosphate), C272, C301, C302, the mixed extractant (organic phase) of HEOPPA one or both preparations wherein is at rare earth sulfate solution or rare earth sulfate solution and re chloride, extracting and separating rear earth element in the mixing solutions of rare earth nitrate solution (water), or adopt non-saponified P204 at rare earth sulfate solution and re chloride, the technology of extracting and separating rear earth element in the mixing solutions of rare earth nitrate solution.
Purpose of the present invention:
Because sulfuric acid rare earth solubleness is less, the rare earth sulfate solution concentration that obtains when sulfuric acid process is handled rare-earth mineral is the highest can only to reach 50g/L (REO), on the general industry 30-40g/L, in order to improve the leaching yield of rare earth concentration and rare earth and thorium, adopt dilute hydrochloric acid or rare nitric acid to leach the rare earth roasted ore, thereby obtain the sulfuric acid rare earth of high density and the mixed rare earth solution of rare earth chloride or rare earth nitrate, the present invention is a raw material with this solution, adopts extracting rare earth element by non-saponifiable phosphorous mixing extractant.
The present invention replaces H in order to improve the rare earth concentration of organic phase and aqueous phase in the extraction process with high density chlorination rare earth or rare earth nitrate strip liquor
+Concentration is that the sulfuric acid of 1.0mol/L is made washing lotion, makes extraction extracting and separating rear earth element in the mixed system of the sulfuric acid rare earth of high density and rare earth chloride or rare earth nitrate, to reduce sour consumption, improves production capacity, reduces investment.
P204 binding ability with rare earth ion under acidic conditions is very strong, when in rare earth sulfate solution, carrying out Nd-Sm extraction grouping, because extraction quantity, to compare (organic/water, volume ratio) less, must in feed liquid, add sulfuric acid and improve acidity, P204 just can supersaturation emulsification, the present invention adopts one or more the mixed extractant among non-saponified P204 and acid more weak non-saponification P507, P229, P350, TBP, C272, C301, C302, the HEOPPA, emulsification do not occur to realize extraction under the low acidity.
Heavy rare earths P204 back extraction difficulty in containing, strip liquor spent acid height, the acid consumption is big, the present invention adopts one or more the mixed extractant among non-saponified P204 and acid more weak non-saponification P507, P229, P350, TBP, C272, C301, C302, the HEOPPA, to reduce strip liquor spent acid, reduce acid consumption and cost.
For achieving the above object, the present invention takes following technical scheme:
The earth solution that contains multiple rare earth element that obtains with the processing rare-earth mineral is a raw material, the mixed extractant that adopts one or both preparations among non-saponified P204 and non-saponification P507, P229, P350, TBP, C272, C301, C302, the HEOPPA is at rare earth sulfate solution, or extracting and separating rear earth element in the mixing solutions of rare earth sulfate solution and re chloride or rare earth nitrate solution.
Described earth solution contains multiple rare earth element, be generally sulfuric acid process and handle the rare earth sulfate solution that rare-earth mineral obtains, or the mixed rare earth solution of sulfuric acid rare earth and rare earth chloride or rare earth nitrate, or in rare earth sulfate solution extracting and washing process, add the sulfuric acid rare earth that hydrochloric acid or nitric acid, re chloride, rare earth nitrate solution washing obtain and the mixed rare earth solution of rare earth chloride or rare earth nitrate, its acidity is 0.00001-0.5mol/L, and content of rare earth is 10-300g/L REO; Described extraction agent is diluted to 0.5-1.7mol/L with one or more the organic mixed solvents in kerosene, solvent oil, alkane, the alcohol.
1, described earth solution directly adopts the whole rare earths of the described non-saponification extracting mixed extractant of 0.5-1.7mol/L, and the supported rare earth organic phase adopts 4-7mol/L hydrochloric acid or nitric acid back extraction to produce mixed chlorinated rare earth or mixeding acid rare-earth; Or adopt 4-7mol/L hydrochloric acid or nitric acid washing back extraction (washing acid and back extraction acid integrates), washing section obtains LaCePrNd solution, stripping section obtains the sm-eu-gd enriched substance, two kinds of products all further extracting and separating produce single rare earth compound.
2, described earth solution adopts 0.5-1.7mol/L described non-saponifiable extraction agent carrying out neodymium/samarium fractionation extraction grouping, and washing lotion adopts 4-7mol/L hydrochloric acid or nitric acid or sm-eu-gd rare earth chloride or rare earth nitrate strip liquor (its rare earth concentration is 100-250g/LREO); The supported rare earth organic phase obtains the sm-eu-gd enriched substance with 4-7mol/L hydrochloric acid or nitric acid back extraction; The LaCePrNd raffinate that contains that obtains is neutralized to pH2-5, extracts entirely with the described non-saponifiable extraction agent of 0.5-1.7mol/L again, and 4-7mol/L hydrochloric acid or nitric acid back extraction prepare LaCePrNd rare earth chloride or rare earth nitrate or further extracting and separating single rare earth compound.
After containing the LaCePrNd raffinate and be neutralized to pH2-5 described in (1) 2, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium extracting and separating, washing lotion adopts 4-7mol/L hydrochloric acid or nitric acid or contains the neodymium rare earth chloride or the rare earth nitrate strip liquor, and its rare earth concentration is 100-300g/L REO; The supported rare earth organic phase obtains Neodymium trichloride or neodymium nitrate with 4-7mol/L hydrochloric acid or nitric acid back extraction; Obtain contain the La-Ce-Pr raffinate and be neutralized to PH2-5 again after, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L La-Ce-Pr, 4-7mol/L hydrochloric acid or nitric acid back extraction prepare La-Ce-Pr rare earth chloride or rare earth nitrate.
After containing the LaCePrNd raffinate and be neutralized to pH2-5 described in (2) 2, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium extraction grouping, washing lotion adopts 4-7mol/L hydrochloric acid or nitric acid or contains praseodymium neodymium rare earth chloride or the rare earth nitrate strip liquor, and its rare earth concentration is 100-300g/L REO; The supported rare earth organic phase obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 4-7mol/L hydrochloric acid or nitric acid back extraction; The lanthanum cerium raffinate that contains that obtains is produced the Phosbloc cerium with ammonium bicarbonate precipitation, or after being neutralized to PH2-5, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L lanthanum cerium, 4-7mol/L hydrochloric acid or nitric acid back extraction prepare lanthanum cerium rare earth chloride or rare earth nitrate, and praseodymium neodymium and lanthanum cerium compound be further extracting and separating single rare earth compound all.
The LaCePrNd raffinate that contains described in (3) 2 is neutralized to pH1-5, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet extracting and separating then, adopt 4-7mol/L hydrochloric acid or nitric acid or contain praseodymium neodymium rare earth chloride or the responsible rare earth organic phase of rare earth nitrate strip liquor washing, open a water in extraction section and export out a part of lanthanum cerium solution, its cerium oxide content＞65% is produced rich cerium product through precipitation; Load praseodymium neodymium organic phase obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 4-7mol/L hydrochloric acid or nitric acid back extraction; The lanthanum raffinate that contains that obtains is produced Phosbloc with ammonium bicarbonate precipitation, or after being neutralized to PH2-5, with the non-saponification P204 extraction of 0.5-1.7mol/L, hydrochloric acid or nitric acid back extraction prepare the compound of 99.9-99.99% lanthanum.3, described earth solution is adopted 0.5-1.7mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium fractionation extraction separate, the supported rare earth organic phase is washed (washing acid and back extraction acid integrates) with 4-7mol/L hydrochloric acid or nitric acid back extraction, open a water at washing section and export out praseodymium neodymium muriate or nitrate solution, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The stripping section first step goes out the sm-eu-gd enriched substance; Raffinate is produced the Phosbloc cerium with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L, produces the lanthanum cerium compound through persalt or nitric acid back extraction again.
4, described earth solution is adopted 0.5-1.7mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium fractionation extraction, washing lotion is 4-7mol/L hydrochloric acid or nitric acid, contain praseodymium neodymium sm-eu-gd organic phase and directly enter neodymium/samarium fractionation extraction operation, load organic phases is with containing the washing of sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, use 4-7mol/L hydrochloric acid or nitric acid back extraction then, obtain the sm-eu-gd enriched substance; The raffinate that neodymium/samarium fractionation extraction grouping obtains is praseodymium neodymium muriate or nitrate solution, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The lanthanum cerium raffinate that contains that cerium/praseodymium extraction grouping obtains is produced the Phosbloc cerium with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L, produces the lanthanum cerium compound through persalt or nitric acid back extraction again.
5, described earth solution is adopted 0.5-1.7mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium fractionation extraction grouping, load organic phases is washed (washing acid and back extraction acid integrates) with 4-7mol/L hydrochloric acid or nitric acid back extraction, open a water at washing section and export out Neodymium trichloride or neodymium nitrate solution, can prepare purity and be the compound of about 99.9% neodymium; The stripping section first step goes out the sm-eu-gd enriched substance; After containing the La-Ce-Pr raffinate and being neutralized to pH2-5, extract entirely, produce La-Ce-Pr rare earth chloride or rare earth nitrate with hydrochloric acid or nitric acid back extraction again with the described non-saponifiable extraction agent of 0.5-1.7mol/L.
6, described earth solution is adopted 0.5-1.7mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet fractionation extractions separate, the supported rare earth organic phase is washed (washing acid and back extraction acid integrates) with 4-7mol/L hydrochloric acid or nitric acid back extraction, open a water in extraction section and export out a part of lanthanum cerium solution, its cerium oxide content＞65% is produced rich cerium product through precipitation; Open a water at washing section and export out praseodymium neodymium muriate or nitrate, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The stripping section first step goes out the sm-eu-gd enriched substance; Raffinate is produced Phosbloc with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the non-saponification P204 extraction of 0.5-1.7mol/L, produces the compound of the lanthanum of 99.9-99.99% again through persalt or nitric acid back extraction.
7, described earth solution is adopted 0.5-1.7mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet fractionation extractions separate, open a water in extraction section and export out a part of lanthanum cerium solution, its cerium oxide content＞65% is produced rich cerium product through precipitation; After washing with 4-7mol/L hydrochloric acid or nitric acid back extraction, load organic phases directly enters neodymium/samarium fractionation extraction grouping operation, washing lotion is for containing sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, what obtain contains the sm-eu-gd organic phase through 4-7mol/L hydrochloric acid or nitric acid back extraction, obtains the sm-eu-gd enriched substance; The raffinate that neodymium/samarium extraction grouping obtains is praseodymium neodymium muriate or nitrate, but direct production praseodymium neodymium compound or further extracting and separating prepare Praseodymium trioxide or Neodymium trioxide; The lanthanum raffinate that contains that lanthanum/cerium/praseodymium three outlet extracting and separating obtain is produced Phosbloc with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the non-saponification P204 extraction of 0.5-1.7mol/L, produces the compound of the lanthanum of 99.9-99.99% again through persalt or nitric acid back extraction.
8, a kind of extracting rare earth element by non-saponifiable phosphorous mixing extractant technology, it is characterized in that, handle rare-earth mineral with sulfuric acid process, through water logging, in and the rare earth sulfate solution that obtains of removal of impurities be raw material, adopt the non-saponification P204 of 0.1-1.7mol/L and non-saponification P507 or P229, the mixed extractant of P350 carries out cerium/praseodymium fractionation extraction grouping, be responsible for organic phase and adopt 4-7mol/L hydrochloric acid or nitric acid back extraction washing, washing acid and back extraction acid integrates, open a water at washing section and export out praseodymium neodymium muriate or nitrate, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The stripping section first step goes out the sm-eu-gd enriched substance; The lanthanum cerium raffinate that contains that obtains is produced lanthanum cerium carbonated rare earth with ammonium bicarbonate precipitation, or after being neutralized to pH1-5 with magnesium oxide, adopt the non-saponification P204 of 0.5-1.7mol/L to extract entirely, produce lanthanum cerium chloride or nitrate with hydrochloric acid or nitric acid back extraction again, also further pure lanthanum or the pure cerium compound of extracting and separating production 99.9-99.99%.
Advantage of the present invention:
When 1) non-saponified P204 carries out Nd-Sm extraction grouping in earth solution, because extraction quantity, to compare (organic/water, volume ratio) less, P204 extracting rare-earth in low acidic solution is very capable, must in feed liquid, add sulfuric acid acidity is adjusted to 0.2mol/L from PH4, need add 0.26 ton of vitriol oil by rare earth oxide calculating per ton, P204 just can not produce supersaturation emulsification.The present invention adopts the mixed extractant of one or both preparations among the more weak non-saponification P507 of non-saponified P204 and acidity, P229, P350, TBP, C272, C301, C302, the HEOPPA to carry out extracting and separating in earth solution, the extraction feed liquid need not added acid, and the easy back extraction of the organic extractant of heavy rare earths in the load, strip liquor spent acid is reduced more than 20%, reduce acid consumption about 30%;
2) replace the sulfuric acid of 1mol/L to make washing lotion with high density chlorination rare earth or rare earth nitrate strip liquor, make extraction extracting and separating rear earth element in the mixed rare earth solution of the sulfuric acid rare earth of high density and rare earth chloride or rare earth nitrate, the rare earth concentration of outlet organic phase and washing section aqueous phase improves 3-4 doubly, can improve stripping efficiency, reduce sour consumption 10%, improve throughput, reduce investment more than 10%;
3) used extraction agent does not need saponification, all carries out extracting and separating in acidic medium, and therefore, organic phase and water layering are easy, and system is stable, and the extraction agent loss by solution only is 1/2 of saponification P507, and the value of loss organic phase is less than 1/4 of saponification P507;
4) the technology of the present invention adopts a fractionation extraction can produce pure lanthanum, lanthanum cerium compound, praseodymium neodymium compound and four kinds of market readily marketable products of sm-eu-gd enriched substance, and save the magnesium oxide neutralization, filtered operation, the rare earth yield height, cost is low.
5) adopt the non-saponification organic phase extracting rare-earth separating, extraction process does not produce ammonia nitrogen waste water, and technology is simply continuous, easy to control, and main chemical materials consumption rate ammonium bicarbonate precipitation makes the transition, saponification P507 extraction grouping technology reduces more than 30%, and has saved a large amount of cost for wastewater treatment.
Comparison example 1
1000 gram hamartites and monazite mixed type rare-earth mineral (REO 50%) through sulfuric acid baking, water logging, in and removal of impurities, obtain 11.5 liters of purified rare earth sulfate solutions, its acidity is pH 4, main component is REO 40g/L, Fe＜0.05g/L, P＜0.005g/L, ThO2＜0.001g/L; Add 720 gram ammonium bicarbonate precipitations, washing, filter, obtain carbonated rare earth 945 grams, add concentrated hydrochloric acid 970ml dissolving, add 70 gram bariumchloride sulfate radicals then, obtain containing the re chloride 1703ml of rare earth 260g/l (REO); This solution adopts 1.5mol/l saponification P507 to carry out neodymium/samarium extraction grouping, compare: organic phase/water/washing lotion is 0.79/1/0.073, organic phase saponification deg 50% (consuming liquefied ammonia 72 grams), load organic phases (consumes concentrated hydrochloric acid 52ml with 4mol/L salt acid elution, about 58 grams), through 40 grades of fractionation extractions, the back extraction of 6mol/L hydrochloric acid, the re chloride 40ml that obtains containing sm-eu-gd 245g/L (REO) (consumes concentrated hydrochloric acid 25ml, about 28 grams), can produce sm-eu-gd enriched substance or further extracting and separating; Obtain containing the raffinate 1830ml of LaCePrNd 237g/l, can produce LaCePrNd rare earth chloride product or further extracting and separating.
This technology is raw material production sm-eu-gd enriched substance and LaCePrNd rare earth chloride with the rare earth sulfate solution of handling 1 ton of rare-earth mineral and obtaining, consume 720 kilograms in bicarbonate of ammonia (450 yuan/ton), 70 kilograms of bariumchlorides (2200 yuan/ton), 72 kilograms of ammoniacal liquor (2000 yuan/ton), 1047 liters of concentrated hydrochloric acids (about 1152 kilograms, 560 yuan/ton).Adding up to main chemical materials consuming cost is 324+154+144+645=1267 unit.Rare earth yield is 88.7%.
This technology produces a large amount of ammonia nitrogen waste waters in ammonium bicarbonate precipitation and P507 saponifiable extraction process, and the ammonia nitrogen waste water concentration that the ammonium bicarbonate precipitation process produces is rare, is difficult to reclaim, and chemical materials consumes high.
Embodiment 1
1000 gram hamartites and monazite mixed type rare-earth mineral (REO 50%) through sulfuric acid baking, water logging, in and removal of impurities, obtain 11.5 liters of purified rare earth sulfate solutions, its acidity is pH 4, main component is REO 40g.L, Fe＜0.05g/L, P＜0.005g/L, ThO
2＜0.001g/L, directly the non-saponification P204 (1.0mol/L) of employing 60% carries out Nd/Sm extraction grouping with the mixed extractant of 40% non-saponification P507 (1.0mol/L), adopt 7 grades of extractions, 13 grades of washings, 8 grades of back extractions, compare: organic/feed liquid/washing lotion is 0.25/1/0.015, washing lotion adopts and contains sm-eu-gd 210g/l, the rare earth chloride strip liquor of acidity 1.5mol/L (consumes concentrated hydrochloric acid 110ml, about 121 grams), the washing section rare earth concentration is 245g/l, and the supported rare earth organic phase contains rare earth 18g/l, with the back extraction of 6mol/L hydrochloric acid, obtain containing REO 210g/l, acidity is the sm-eu-gd enriched substance re chloride 47ml (Nd of 1.5mol/L
2O
3/ REO＜0.05%) consume concentrated hydrochloric acid 30ml, about 33 grams), can produce sm-eu-gd enriched substance or further extracting and separating.
The raffinate that obtains (11.7 liters of rare earth sulfate solutions that contain LaCePrNd 38.3g/l, Sm
2O
3/ REO＜0.003%) is neutralized to the PH4 after-filtration with 95 gram magnesium oxide, filtrate adopts 1.5mol/l P204 to extract entirely, the back extraction of 6mol/L hydrochloric acid, obtain containing LaCePrNd 267g/l re chloride 1642ml and (consume concentrated hydrochloric acid 1037ml, about 1141 grams), can produce LaCePrNd rare earth chloride product or further extracting and separating.
This technology is raw material production sm-eu-gd enriched substance and LaCePrNd rare earth chloride with the rare earth sulfate solution of handling 1 ton of rare-earth mineral and obtaining, and total consumption is 1177 liters of concentrated hydrochloric acids (9.5mol/L) (1295 kilograms, 560 yuan/ton), 95 kilograms in magnesium oxide (500 yuan/ton).Adding up to main chemical materials consuming cost is 725+50=775 unit, and rare earth yield is 89.7%.
Compare with comparison example 1, main chemical materials cost reduces by 39%, and the rate of recovery improves 1%, and does not produce ammonia nitrogen waste water in the whole technological process.
Comparison example 2
1000 gram hamartites and monazite mixed type rare-earth mineral (REO 50%) are through sulfuric acid baking, water logging, in and removal of impurities, obtain 12.5 liters of purified rare earth sulfate solutions, its acidity is pH 4, rare earth concentration REO is 36.5g/L, in rare earth sulfate solution, add the 72ml vitriol oil acidity is transferred to 0.2mol/L, adopt the non-saponification P204 of 1.0mol/L to carry out Nd/Sm extraction grouping, adopt 7 grades of extractions, 13 grades of washings, 8 grades of back extractions, compare: organic/feed liquid/washing lotion is 0.2/1/0.06, washing lotion adopts 0.5mol/L H2SO4 (consuming the 22ml vitriol oil), the washing section rare earth concentration is 45g/l, the supported rare earth organic phase contains rare earth 4.2g/l, with the back extraction of 6mol/L hydrochloric acid, obtains containing sm-eu-gd 130g/L (REO), acidity is that the re chloride 74ml of 2.5mol/L (consumes concentrated hydrochloric acid 47ml, about 52 grams), this solution further extracting and separating extracts samarium, europium, gadolinium single rare earth product.
This technological process consumes the vitriol oil (32mol/L) 94ml (173 gram), concentrated hydrochloric acid (9.5mol/L) 47ml (52 gram), and adding up to sour consumption is 225 grams.
Embodiment 2
1000 gram hamartites and monazite mixed type rare-earth mineral (REO 50%) are through sulfuric acid baking, water logging, in and removal of impurities, obtain 12.5 liters of purified rare earth sulfate solutions, its acidity is pH 4, rare earth concentration REO is 36.5g/L, the non-saponification P204 (1.0mol/L) of the direct employing 70% of uncomfortable acidity carries out Nd/Sm extraction grouping with the mixed extractant of 30% non-saponification P507 (1.0mol/L), adopt 7 grades of extractions, 13 grades of washings, 8 grades of back extractions, compare: organic/feed liquid/washing lotion is 0.25/1/0.014, washing lotion adopts and contains sm-eu-gd 215g/l, the re chloride of acidity 1.2mol/L (consumes concentrated hydrochloric acid 111ml, about 122 grams), the washing section rare earth concentration is 255g/l, and the supported rare earth organic phase contains rare earth 18g/l, with the back extraction of 6mol/L hydrochloric acid, obtain containing REO 225g/l, acidity is the sm-eu-gd enriched substance re chloride 43ml (consuming concentrated hydrochloric acid 27ml, about 30 grams) of 1.4mol/L, and this solution further extracting and separating extracts samarium, europium, gadolinium single rare earth product.
The used feed liquid of this technology need not be added sulfuric acid acid adjustment degree, and whole process consumes concentrated hydrochloric acid (9.5mol/L) 137ml (152 gram), does not consume sulfuric acid.Compare with comparison example 2, sour consumption has reduced by 30%.
Comparison example 3
1000 gram hamartites and monazite mixed type rare-earth mineral through sulfuric acid baking, water logging, in and removal of impurities, obtain purified rare earth sulfate solution, its acidity is pH 4, rare earth concentration REO 43g/L, add the vitriol oil solution acidity is transferred to 0.2mol/L, adopt the non-saponification P204 of 1.5mol/L (with No. 200 solvent oil dilutions) to carry out neodymium/samarium fractionation extraction grouping, supported rare earth organic phase 1mol/L H
2SO
4Washing, its content of rare earth is 4g/l, with the back extraction of 6mol/L hydrochloric acid, obtains the sm-eu-gd re chloride of 130g/l, 2.5mol/L, through precipitation preparation sm-eu-gd enriched substance; Contain LaCePrNd raffinate (about 40g/l) and be neutralized to the pH4 after-filtration, carry out cerium/praseodymium fractionation extraction grouping, supported rare earth organic phase 1mol/L H with the non-saponification P204 of 1.5mol/L again with magnesium oxide
2SO
4With the back extraction of 6mol/L hydrochloric acid, obtain the praseodymium neodymium re chloride of 230g/l, 0.8mol/L after the washing, produce praseodymium neodymium oxides or condensing crystal production praseodymium neodymium rare earth chloride (REO＞45%) through precipitation; Contain lanthanum cerium raffinate and be neutralized to the pH4 after-filtration with magnesium oxide, extract entirely with the non-saponification P204 of 1.5mol/L again, the back extraction of 6mol/L hydrochloric acid obtains the lanthanum cerium re chloride of 270g/l, 0.3mol/L, produces lanthanum cerium rare earth chloride (REO＞45%) through condensing crystal.
Embodiment 3
1000 gram hamartites and monazite mixed type rare-earth mineral through sulfuric acid baking, water logging, in and removal of impurities, obtain purified rare earth sulfate solution, its acidity is pH 4.5, rare earth concentration REO is 43g/L, and uncomfortable acidity directly adopts the mixed extractant of the non-saponification P507 of the non-saponification P204 of 70%1.2mol/L and 30%1.2mol/L to carry out cerium/praseodymium fractionation extraction to separate.Last progressive 5.5mol/L hydrochloric acid back extraction supported rare earth organic phase of stripping section, back extraction first step water (strip liquor REO 230g/l, 1.2mol/L, Nd
2O
3/ REO＜0.05%) part enters washing section and does washing lotion, and a part of strip liquor is emitted through precipitation and produced the sm-eu-gd enriched substance; Open a water in the highest one-level of washing section praseodymium neodymium purity and export out praseodymium chloride neodymium solution (235g/l, 0.1mol/L, CeO
2/ REO＜0.01%, Sm
2O
3/ REO＜0.01%), produces praseodymium neodymium rare earth chloride through concentrating; After raffinate is neutralized to pH5 with magnesium oxide, the whole rare earths of extracting mixed extractant of the non-saponification P204 of employing 80%1.5mol/L and the non-saponification P350 of 20%1.5mol/L, load organic phases obtains the lanthanum cerium re chloride of 270g/l, 0.3mol/L with the back extraction of 5.8mol/L hydrochloric acid, produces lanthanum cerium rare earth chloride (REO＞45%) through condensing crystal.
This technology is compared with comparison example 3, and feed liquid need not be added sulfuric acid acid adjustment degree, has also saved one magnesium oxide neutralization, has filtered operation, and a fractionation extraction can be produced three kinds of market readily marketable products, the rare earth yield height, and cost is low.
Embodiment 4
1000 gram hamartites and monazite mixed type rare-earth mineral through sulfuric acid baking, water logging, in and removal of impurities, obtain purified rare earth sulfate solution, its acidity is pH 4, rare earth concentration REO is 43g/L, and uncomfortable acidity directly adopts the non-saponification P204 of 1.5mol/L (with No. 200 solvent oil dilutions) to carry out cerium/praseodymium fractionation extraction grouping.The supported rare earth organic phase is with containing praseodymium neodymium rare earth chloride strip liquor (260g/l REO) washing, load organic phases middle-weight rare earths content is 17g/l, directly enter neodymium/samarium fractionation extraction grouping operation (organic phase charging) as feed liquid, the supported rare earth organic phase that obtains is with containing sm-eu-gd rare earth chloride strip liquor (235g/l REO) washing, use the back extraction of 6mol/L hydrochloric acid then, obtain 235g/l, 1.2mol/L sm-eu-gd re chloride, through precipitation preparation sm-eu-gd enriched substance; Raffinate is 250g/l, 0.2mol/L praseodymium neodymium re chloride, produces praseodymium neodymium oxides or condensing crystal production praseodymium neodymium rare earth chloride (REO＞45%) through precipitation; Contain lanthanum cerium raffinate and be neutralized to the PH4 after-filtration with magnesium oxide, extract entirely with the non-saponification P204 of 1.5mol/L again, the back extraction of 6mol/L hydrochloric acid obtains the lanthanum cerium re chloride of 270g/l, 0.3mol/L, produces lanthanum cerium rare earth chloride (REO＞45%) through condensing crystal.
This technology is compared with comparison example 3, and feed liquid need not be added sulfuric acid acid adjustment degree, has also saved one magnesium oxide neutralization, has filtered operation, and neodymium/samarium extraction packet section rare earth concentration improves more than 4 times, can reduce the investment of extraction tank and organic phase.
Embodiment 5
Feed liquid is the mixed rare earth solution of sulfuric acid rare earth and rare earth chloride, and its acidity is pH 4, and main component is REO 48g/L, Fe＜0.05g/L, P＜0.005g/L, ThO
2＜0.001g/L, the mixed extractant (diluting with kerosene) of the non-saponification P204 of employing 80%1.5mol/L and the non-saponification P229 of 20%1.5mol/L carries out cerium/praseodymium fractionation extraction grouping.The supported rare earth organic phase directly enters neodymium/samarium fractionation extraction grouping operation (organic phase charging) after containing praseodymium neodymium rare earth chloride strip liquor (265g/LREO) washing, the supported rare earth organic phase that obtains is with containing sm-eu-gd rare earth chloride strip liquor (200g/LREO) washing, use the back extraction of 6mol/L hydrochloric acid then, obtain 230g/l, 1.2mol/L sm-eu-gd re chloride, through precipitation preparation sm-eu-gd enriched substance; Raffinate is 265g/l, 0.25mol/L praseodymium neodymium re chloride, produces praseodymium neodymium oxides or condensing crystal production praseodymium neodymium rare earth chloride (REO＞45%) through precipitation; Contain lanthanum cerium raffinate and produce lanthanum cerium carbonate (REO＞45%) with ammonium bicarbonate precipitation.
Embodiment 6
Handle the rare earth sulfate solution that Australian rare-earth mineral obtains: REO 40g/L, pH4, the mixed extractant (diluting with kerosene) of the non-saponification P204 of employing 85%1.3mol/L and the non-saponification C272 of 15%1.3mol/L carries out praseodymium/neodymium fractionation extraction grouping.The supported rare earth organic phase is with after containing the washing of neodymium rare earth chloride strip liquor; Directly enter neodymium/samarium fractionation extraction grouping operation (organic phase charging), the supported rare earth organic phase that obtains is with containing the washing of sm-eu-gd rare earth chloride strip liquor, use the back extraction of 6mol/L hydrochloric acid then, obtain the sm-eu-gd enriched substance, raffinate is a neodymium chloride solution, through precipitation production purity greater than 99.9% Neodymium trioxide; Contain the La-Ce-Pr raffinate and be neutralized to PH4.5 with magnesium oxide, with the non-saponification P204 extraction of 1.5mol/L, the La-Ce-Pr rare earth chloride is produced in the back extraction of 6mol/L nitric acid again.
Embodiment 7
The processing rare earth expands the rare earth sulfate solution that obtains, and (REO 42g/L pH4.5), adopts the mixed extractant that contains non-saponification P204 of 70%1.0mol/L and the non-saponification P507 of 30%1.0mol/L to carry out lanthanum/cerium/praseodymium three outlet fractionation extractions and separates.Last progressive 5.8mol/L hydrochloric acid back extraction supported rare earth organic phase of stripping section, back extraction first step water (strip liquor REO 240g/l, 1.0mol/L, Nd
2O
3/ REO＜0.05%) part enters washing section and does washing lotion, and a part of strip liquor is emitted through precipitation and produced sm-eu-gd enriched substance (Eu
2O
3/ REO＞12%); Open a water in the highest one-level of washing section praseodymium neodymium purity and export out praseodymium chloride neodymium solution (255g/l, 0.1mol/L, CeO
2/ REO＜0.01%, Sm
2O
3/ REO＜0.01%), produces praseodymium neodymium rare earth chloride through concentrating; Open a water in extraction section and export out a part of lanthanum cerium solution, its cerium oxide content＞65% is produced rich cerium carbonate through ammonium bicarbonate precipitation; After containing the lanthanum raffinate and being neutralized to PH 5, with the non-saponification P204 extraction of 1.2mol/L, load organic phases obtains the lanthanum cerium re chloride of 270g/l, 0.1mol/L with the back extraction of 5.5mol/L hydrochloric acid, passes through oxalic acid precipitation, and it is 99.99% lanthanum trioxide that roasting obtains purity.
A fractionation extraction of this technology can be produced pure lanthanum, lanthanum cerium compound, praseodymium neodymium compound and four kinds of market readily marketable products of sm-eu-gd enriched substance, the rare earth yield height, and chemical materials consumption reduces, and product cost is low.
Embodiment 8
Sulfuric acid rare earth and rare earth chloride mixing solutions: REO 48g/L, pH4 adopts non-saponification P204 of 90%1.3mol/L and the non-saponification P507 of 10%1.3mol/L (diluting with kerosene) mixed extractant to carry out lanthanum/cerium/praseodymium three outlet fractionation extractions and separates.The supported rare earth organic phase is opened a water outlet (the 3rd outlet) in extraction section and is gone out a part of lanthanum cerium solution (cerium＞65%) with containing praseodymium neodymium rare earth chloride (260g/L) washing, produces rich cerium product through precipitation; Contain the direct charging of praseodymium neodymium sm-eu-gd organic phase and carry out neodymium/samarium fractionation extraction grouping, the supported rare earth organic phase is used the back extraction of 6mol/L hydrochloric acid then with containing the washing of sm-eu-gd rare earth chloride strip liquor, obtains the sm-eu-gd enriched substance, raffinate is a praseodymium neodymium muriate, produces the praseodymium neodymium oxides through precipitation; The raffinate that lanthanum/cerium/praseodymium three outlets obtain is neutralized to pH4 with magnesium oxide, and with the non-saponification P204 extraction of 1.3mol/L, Lanthanum trichloride or the lanthanum trioxide of 99.9-99.99% produced in the back extraction of 6mol/L hydrochloric acid again
Embodiment 9
1000 gram Baotou rare earth ore concentrates obtain purified rare earth sulfate solution through sulfuric acid baking, water logging, removal of impurities, and its acidity is pH 4.5, and main component is REO 32g/L, Fe＜0.05g/L, P＜0.005g/L, ThO
2＜0.001g/L, directly the mixed extractant (diluting with kerosene) of the non-saponification P507 of the non-saponification P204 of employing 85%1.5mol/L and 15%1.5mol/L extracts whole rare earths, the 6mol/L hydrochloric acid back extraction of supported rare earth organic phase, through 6 grades of extractions, wash sulfate radical, calcium, magnesium for 3 grades, 10 grades of back extractions, obtaining concentration is the mixed chlorinated rare earth solution of 260g/l REO, this solution obtains mixed chlorinated rare earth product (REO 〉=45%), REO＜0.15g/l in the raffinate through condensing crystal.
Embodiment 10
1000 gram Baotou rare earth ore concentrates obtain purified rare earth sulfate solution through sulfuric acid baking, water logging, removal of impurities, and its acidity is pH 4.5, and main component is REO 32g/L, Fe＜0.05g/L, P＜0.005g/L, ThO
2＜0.001g/L, directly the mixed extractant (diluting with kerosene) of the non-saponification P507 of the non-saponification P204 of employing 80%1.5mol/L and 20%1.5mol/L extracts whole rare earths, adopt 7 grades of extractions, 15 grades of washings, 8 grades of back extractions. stripping section advances 5.5mol/L hydrochloric acid back extraction supported rare earth organic phase, a back extraction first step water part directly enters washing section as washing lotion, and a part is emitted and produced the sm-eu-gd enriched substance; Washing section is opened a water and is exported out LaCePrNd re chloride (about REO 240g/l), and this solution obtains LaCePrNd rare earth chloride product (REO 〉=45%) through condensing crystal; REO＜0.2g/l in the raffinate.
Embodiment 11
1000 gram hamartites and monazite mixed type rare-earth mineral (REO 50%) are through sulfuric acid baking, water logging, in and removal of impurities, obtain purified rare earth sulfate solution, its acidity is pH 4, rare earth concentration is REO 40g/L, the non-saponification P204 (1.0mol/L) of direct employing 50% carries out Nd/Sm extraction grouping with the mixed extractant of 50% non-saponification P507 (1.0mol/L), adopt 8 grades of extractions, 15 grades of washings, 8 grades of back extractions, washing lotion adopts and contains sm-eu-gd 210g/l, the re chloride of acidity 1.4mol/L, the supported rare earth organic phase contains rare earth 17g/l, with the back extraction of 5.7mol/L hydrochloric acid, obtain containing REO 210g/l, acidity is the sm-eu-gd re chloride of 1.4mol/L, produces sm-eu-gd enriched substance or further extracting and separating extraction samarium through precipitation, europium, gadolinium single rare earth product.
The LaCePrNd raffinate that contains that obtains is neutralized to pH4 with magnesium oxide, adopt the non-saponification P204 of 80%1.3mol/L to carry out praseodymium/neodymium fractionation extraction with the mixed extractant (diluting with kerosene) of the non-saponification P350 of 20%1.3mol/L then and separate, washing lotion adopts and contains neodymium rare earth nitrate strip liquor (REO 250g/L); The 6mol/L nitric acid back extraction of supported rare earth organic phase, through 30 grades of extractions, 38 grades of washings, 6 grades of back extractions obtain neodymium nitrate; Raffinate is neutralized to PH4.5 with magnesium oxide, and with the non-saponification P204 extraction of 1.5mol/L La-Ce-Pr, the back extraction of 6mol/L hydrochloric acid prepares the La-Ce-Pr rare earth chloride.
Embodiment 12
The fore portion operation is with embodiment 2.
The LaCePrNd raffinate that contains that obtains is neutralized to pH4 with magnesium oxide, adopts the mixed extractant (with No. 200 solvent oils dilutions) of the non-saponification C302 of the non-saponification P204 of 90%1.5mol/L and 10%1.5mol/L to carry out cerium/praseodymium fractionation extraction grouping then.Washing lotion adopts and contains praseodymium neodymium rare earth chloride strip liquor (REO 268g/L); The 6.3mol/L hydrochloric acid back extraction of supported rare earth organic phase, through 23 grades of extractions, 32 grades of washings, 6 grades of back extractions obtain the praseodymium chloride neodymium; Raffinate is neutralized to PH4.5 with magnesium oxide, and with the non-saponification P204 extraction of 1.5mol/L lanthanum cerium, the back extraction of 6mol/L hydrochloric acid prepares lanthanum cerium rare earth chloride;
Embodiment 13
The fore portion operation is with embodiment 2.
The LaCePrNd raffinate that contains that obtains is neutralized to pH4 with magnesium oxide, adopts the non-saponification P204 of 1.2mol/L (with No. 200 sulfonated kerosene dilutions) organic phase to carry out lanthanum/cerium/praseodymium three outlet extracting and separating then.Employing contains praseodymium neodymium rare earth chloride strip liquor (REO240g/L) washing organic phase, opens a water outlet (the 3rd outlet) 22 grades of extraction sections and goes out a part of lanthanum cerium solution (cerium＞65%), produces rich cerium product through precipitation; The supported rare earth organic phase obtains the praseodymium chloride neodymium with the back extraction of 6.2mol/L hydrochloric acid; It is 99.9% Phosbloc that raffinate obtains purity with ammonium bicarbonate precipitation, and calcination obtains lanthanum trioxide.
Claims (11)
1. the technology of an extracting rare earth element by non-saponifiable phosphorous mixing extractant, it is characterized in that: the earth solution that contains multiple rare earth element that obtains with the processing rare-earth mineral is a raw material, the mixed extractant that adopts one or both preparations among non-saponified P204 and non-saponification P507, P229, P350, TBP, C272, C301, C302, the HEOPPA is at rare earth sulfate solution, or extracting and separating rear earth element in the mixing solutions of rare earth sulfate solution and re chloride or rare earth nitrate solution.
2. technology as claimed in claim 1, it is characterized in that, described earth solution is that sulfuric acid process is handled the rare earth sulfate solution that rare-earth mineral obtains, or the mixed rare earth solution of sulfuric acid rare earth and rare earth chloride or rare earth nitrate, or in rare earth sulfate solution extracting and washing process, add the sulfuric acid rare earth that hydrochloric acid or nitric acid, re chloride, rare earth nitrate solution washing obtain and the mixed rare earth solution of rare earth chloride or rare earth nitrate, its acidity is 0.00001-0.5mol/L, and content of rare earth is 10-300g/L REO; Described extraction agent is diluted to 0.5-1.7mol/L with one or more the organic mixed solvents in kerosene, solvent oil, alkane, the alcohol.
3. technology as claimed in claim 1, it is characterized in that, described earth solution directly adopts the whole rare earths of the described non-saponification extracting mixed extractant of 0.5-1.7mol/L, and the supported rare earth organic phase adopts 4-7mol/L hydrochloric acid or nitric acid back extraction to produce mixed chlorinated rare earth or mixeding acid rare-earth; Or adopt 4-7mol/L hydrochloric acid or nitric acid washing back extraction, wash acid and back extraction acid and integrate, washing section obtains LaCePrNd solution, stripping section obtains the sm-eu-gd enriched substance, two kinds of products all further extracting and separating produce single rare earth compound.
4. technology as claimed in claim 1, it is characterized in that, described earth solution adopts 0.1-1.7mol/L described non-saponifiable extraction agent carrying out neodymium/samarium fractionation extraction grouping, washing lotion adopts 4-7mol/L hydrochloric acid or nitric acid or contains the sm-eu-gd rare earth chloride or the rare earth nitrate strip liquor, and its rare earth concentration is 100-250g/L REO; The supported rare earth organic phase obtains the sm-eu-gd enriched substance with 4-7mol/L hydrochloric acid or nitric acid back extraction; The LaCePrNd raffinate that contains that obtains is neutralized to pH2-5, extracts entirely with the described non-saponifiable extraction agent of 0.5-1.7mol/L again, and 4-7mol/L hydrochloric acid or nitric acid back extraction prepare LaCePrNd rare earth chloride or rare earth nitrate or further extracting and separating single rare earth compound.
5. technology as claimed in claim 4, it is characterized in that, described contain the LaCePrNd raffinate and be neutralized to pH2-5 after, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium extracting and separating, washing lotion adopts 4-7mol/L hydrochloric acid or nitric acid or contains the neodymium rare earth chloride or the rare earth nitrate strip liquor, and its rare earth concentration is 100-300g/L REO; The supported rare earth organic phase obtains Neodymium trichloride or neodymium nitrate with 4-7mol/L hydrochloric acid or nitric acid back extraction; Obtain contain the La-Ce-Pr raffinate and be neutralized to pH2-5 again after, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L La-Ce-Pr, 4-7mol/L hydrochloric acid or nitric acid back extraction prepare La-Ce-Pr rare earth chloride or rare earth nitrate.
6. technology as claimed in claim 4, it is characterized in that, described contain the LaCePrNd raffinate and be neutralized to pH2-5 after, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium extraction grouping, washing lotion adopts 4-7mol/L hydrochloric acid or nitric acid or contains praseodymium neodymium rare earth chloride or the rare earth nitrate strip liquor, and its rare earth concentration is 100-300g/L REO; The supported rare earth organic phase obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 4-7mol/L hydrochloric acid or nitric acid back extraction; The lanthanum cerium raffinate that contains that obtains is produced the Phosbloc cerium with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L lanthanum cerium, 4-7mol/L hydrochloric acid or nitric acid back extraction prepare lanthanum cerium rare earth chloride or rare earth nitrate, and praseodymium neodymium and lanthanum cerium compound be further extracting and separating single rare earth compound all.
7. technology as claimed in claim 4, it is characterized in that, the described LaCePrNd raffinate that contains is neutralized to pH2-5, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet extracting and separating then, employing contains 4-7mol/L hydrochloric acid or nitric acid or praseodymium neodymium rare earth chloride or the responsible rare earth organic phase of rare earth nitrate strip liquor washing, open a water in extraction section and export out a part of lanthanum cerium solution, its cerium oxide content＞65% is produced rich cerium product through precipitation; Load praseodymium neodymium organic phase obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 4-7mol/L hydrochloric acid or nitric acid back extraction; The lanthanum raffinate that contains that obtains is produced Phosbloc or lanthanum trioxide with ammonium bicarbonate precipitation again, or after being neutralized to pH2-5, with the non-saponification P204 extraction of 0.5-1.7mol/L, hydrochloric acid or nitric acid back extraction prepare the compound of the lanthanum of 99.9-99.99%.
8. technology as claimed in claim 1, it is characterized in that, described earth solution adopts 0.5-1.7mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium fractionation extraction grouping, load organic phases is washed with 4-7mol/L hydrochloric acid or nitric acid back extraction, washing acid and back extraction acid integrates, open a water at washing section and export out Neodymium trichloride or neodymium nitrate solution, can prepare purity and be the compound of about 99.9% neodymium; The stripping section first step goes out the sm-eu-gd enriched substance; After containing the La-Ce-Pr raffinate and being neutralized to pH2-5, extract entirely, produce La-Ce-Pr rare earth chloride or rare earth nitrate with hydrochloric acid or nitric acid back extraction again with the described non-saponifiable extraction agent of 0.5-1.7mol/L.
9. technology as claimed in claim 1, it is characterized in that, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium fractionation extraction to separate described earth solution, the supported rare earth organic phase is washed with 4-7mol/L hydrochloric acid or nitric acid back extraction, washing acid and back extraction acid integrates, open a water at washing section and export out praseodymium neodymium muriate or nitrate, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The stripping section first step goes out the sm-eu-gd enriched substance; Raffinate is produced the Phosbloc cerium with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the described non-saponifiable extraction agent extraction of 0.5-1.7mol/L, produces the lanthanum cerium compound through persalt or nitric acid back extraction again.
10. technology as claimed in claim 1, it is characterized in that, adopt 0.5-1.7mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet fractionation extractions to separate described earth solution, the supported rare earth organic phase is washed with 4-7mol/L hydrochloric acid or nitric acid back extraction, washing acid and back extraction acid integrates, open a water in extraction section and export out a part of lanthanum cerium solution, its cerium oxide content＞65% is produced rich cerium product through precipitation; Open a water at washing section and export out praseodymium neodymium muriate or nitrate, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The stripping section first step goes out the sm-eu-gd enriched substance; Raffinate is produced Phosbloc with ammonium bicarbonate precipitation, or after being neutralized to pH2-5, with the non-saponification P204 extraction of 0.5-1.7mol/L, produces the compound of the lanthanum of 99.9-99.99% again through persalt or nitric acid back extraction.
11. extracting rare earth element by non-saponifiable phosphorous mixing extractant technology, it is characterized in that, handle rare-earth mineral with sulfuric acid process, through water logging, in and the rare earth sulfate solution that obtains of removal of impurities be raw material, adopt the non-saponification P204 of 0.1-1.7mol/L and non-saponification P507 or P229, the mixed extractant of P350 carries out cerium/praseodymium fractionation extraction grouping, be responsible for organic phase and adopt 4-7mol/L hydrochloric acid or nitric acid back extraction washing, washing acid and back extraction acid integrates, open a water at washing section and export out praseodymium neodymium muriate or nitrate, but direct production praseodymium neodymium compound or further extracting and separating prepare pure praseodymium and pure neodymium compound; The stripping section first step goes out the sm-eu-gd enriched substance; The lanthanum cerium raffinate that contains that obtains is produced lanthanum cerium carbonated rare earth with ammonium bicarbonate precipitation, or after being neutralized to pH1-5 with magnesium oxide, adopt the non-saponification P204 of 0.5-1.7mol/L to extract entirely, produce lanthanum cerium chloride or nitrate with hydrochloric acid or nitric acid back extraction again, also further pure lanthanum or the pure cerium compound of extracting and separating production 99.9-99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101372318A CN100404706C (en) | 2005-09-05 | 2005-12-31 | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510098261.2 | 2005-09-05 | ||
| CNA2005100982612A CN1730680A (en) | 2005-09-05 | 2005-09-05 | Rare-earth element extraction separation process using nonsaponifying organic extractant |
| CNB2005101372318A CN100404706C (en) | 2005-09-05 | 2005-12-31 | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1804063A CN1804063A (en) | 2006-07-19 |
| CN100404706C true CN100404706C (en) | 2008-07-23 |
Family
ID=36866208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101372318A Active CN100404706C (en) | 2005-09-05 | 2005-12-31 | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100404706C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101363079A (en) * | 2007-08-10 | 2009-02-11 | 有研稀土新材料股份有限公司 | Smelting method of iron rich mengite rare-earth mine |
| WO2009021389A1 (en) * | 2007-08-10 | 2009-02-19 | Grirem Advanced Materials Co., Ltd. | A PROCESS OF SMELTING MONAZITE RARE EARTH ORE RICH IN Fe |
| IN2014DN10242A (en) * | 2012-05-04 | 2015-08-07 | Vale Sa | |
| CN103468981B (en) * | 2013-09-06 | 2014-09-24 | 中铝稀土（常熟）有限公司 | Rare earth liquid metering and conveying device for rare earth extraction tank |
| US10597754B2 (en) * | 2014-05-15 | 2020-03-24 | Vale S.A. | System and process for selective rare earth extraction with sulphur recovery |
| CN104195335B (en) * | 2014-09-19 | 2017-02-15 | 厦门稀土材料研究所 | Extraction separation method for heavy rare earth elements |
| CN107557576A (en) * | 2017-08-15 | 2018-01-09 | 广东省稀有金属研究所 | A kind of method of the Extraction of rare earth from halmeic deposit |
| CN108893625B (en) * | 2018-07-05 | 2020-08-18 | 南昌航空大学 | Process for preparing high-purity lanthanum by extraction method |
| CN108570567A (en) * | 2018-08-01 | 2018-09-25 | 赣州有色冶金研究所 | A kind of method and apparatus of rare earth extraction separation |
| CN110964930B (en) * | 2018-09-30 | 2021-07-27 | 深圳市金航深海矿产开发集团有限公司 | Method for preparing yttrium-doped ternary positive electrode material and precursor thereof by using seabed polymetallic nodule |
| CN112126802B (en) * | 2020-08-14 | 2022-06-14 | 南昌大学 | Rare earth alkaline precipitation, transformation, decomposition and separation method |
| CN113462910B (en) * | 2021-06-30 | 2023-06-20 | 福建省长汀金龙稀土有限公司 | Enrichment method of rare earth ions |
| CN115786744B (en) * | 2022-12-29 | 2024-06-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting scandium by combining titanium white waste acid and fused salt chlorination dust collection slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708958A (en) * | 1995-09-12 | 1998-01-13 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Method of separating trivalent actinides and rare earth elements |
| CN1455009A (en) * | 2003-05-17 | 2003-11-12 | 包头稀土研究院 | Preparation of rare earth chloride from long-chain fatty acid extracting transformation and back-extraction process thereof |
-
2005
- 2005-12-31 CN CNB2005101372318A patent/CN100404706C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708958A (en) * | 1995-09-12 | 1998-01-13 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Method of separating trivalent actinides and rare earth elements |
| CN1455009A (en) * | 2003-05-17 | 2003-11-12 | 包头稀土研究院 | Preparation of rare earth chloride from long-chain fatty acid extracting transformation and back-extraction process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1804063A (en) | 2006-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100404706C (en) | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant | |
| CN100513600C (en) | Technique for extracting and separating rare earth elements from non-saponification system | |
| CN1730680A (en) | Rare-earth element extraction separation process using nonsaponifying organic extractant | |
| CN101294244B (en) | Technique for extraction separation of quadravalence cerium, thorium, fluorine and cerium less tervalence rare earth from sulphuric acid rare earth solution | |
| CN104294063B (en) | The method of low concentration of rare earth solution extraction and recovery rare earth | |
| CN106367622B (en) | It is a kind of using aluminum sulfate as the ion adsorption type re efficient green extracting method of leaching agent | |
| CN100584967C (en) | Method for separating highly-pure rare-earth oxide from rare earth mine for reinforced baking by sulfuric acid | |
| CN102146512B (en) | Hamartite smelting separation process | |
| US9752213B2 (en) | Method for comprehensively recovering rare earth elements and fluorine element in a bastnaesite treatment process | |
| CN102453801B (en) | Method for separating zirconium and hafnium | |
| CN100584970C (en) | A kind of hybrid extraction method of extracting and separating rear earth element and extraction agent | |
| CN101787451B (en) | Method for improving efficiency of acidic organophosphorus extractant for extraction separation of rare-earth elements | |
| CN101319275A (en) | Process for solvent extraction separation purification of rare earth element | |
| CN100584969C (en) | Technique for extraction separation of quadravalence cerium, thorium and cerium less tervalence rare earth from sulphuric acid rare earth solution | |
| CN102041384A (en) | Synergistic extraction separation method of rare-earth elements | |
| CN107226484A (en) | A kind of method that compound extracting prepares vanadic anhydride | |
| CN101319276B (en) | Preextraction method for organic extraction agent, product and uses thereof | |
| CN108950249A (en) | A kind of vanadium aluminum separation method of vanadium-containing shale pickle liquor | |
| EP0541002B1 (en) | Process for recovering sulfuric acid from metal sulfate-containing waste sulfuric acid | |
| CN106399685B (en) | A kind of uranium, iron, thorium, rare-earth extraction separating process | |
| CN103540746B (en) | Method of separating lanthanum from rare earth nitrate slurry as well as rare earth ore concentrate separation method | |
| CN102139907A (en) | Method for separating and recycling cerium-containing compound from cerium-containing solution | |
| CN101164890A (en) | Method for separating cerium, reclaiming fluorin and preparing cerous fluoride ultra-micro powder for mixed extraction system | |
| CN111254295B (en) | Method for extracting and separating gallium from sulfuric acid leaching solution of zinc replacement slag and application thereof | |
| CN104651613B (en) | Method for separating and recovering rare earth from waste rare earth type Y molecular sieve catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Beijing Tai dry law firm Zhu Bin Document name: Review of business letter |