CN1730680A - Rare-earth element extraction separation process using nonsaponifying organic extractant - Google Patents
Rare-earth element extraction separation process using nonsaponifying organic extractant Download PDFInfo
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Abstract
The invention discloses a process for separating rare-earth elements through extraction by using rare earth solution containing multiple rare-earth elements obtained in the treatment of rare earth ore as raw material, mixing the composite extracting agent prepared from one or two of di(2-ethylhexyl phosphoric acid)} and non-saponified P507 (HEH/EHP), C272, C301, C302, and HEOPPA with the mixed rare-earth solution of one or two from sulphuric acid rare earth solution, hydrochloric acid rare earth solution, and nitric acid rare earth solution. By employing P204 composite extracting agent and substituting 1N of sulphuric acid with high concentration rare earth chloride or nitric rare earth strip liquor as the pickling solution, the acidity in the extraction and back washing procedure can be lowered, and the rare earth concentration can be increased.
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 composite extractant that adopts one or both preparations among non-saponified P204 and non-saponification P507, C272, C301, C302, the HEOPPA rare earth sulfate solution or with the mixed rare earth solution of re chloride, rare earth nitrate solution in the technology of extracting and separating rear earth element.
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 80105043.6) 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 (2-ethylhexyl phosphoric acids)) with non-saponification P507 (HEH/EHP), C272, C301, C302, the composite 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 one or both mixed rare earth solutions in the rare earth nitrate solution, or adopt non-saponified P204 at rare earth sulfate solution and re chloride, the technology of extracting and separating rear earth element in one or both mixed rare earth solutions in the 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 non-saponification acidic phosphorus extractant extracting and separating rear earth element.
The present invention is in order to improve the rare earth concentration of organic phase and aqueous phase in the extraction process, replace the sulfuric acid of 1N 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 system of the sulfuric acid rare earth of high density and rare earth chloride or rare earth nitrate, to reduce sour consumption, improve production capacity, reduce 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 composite extractant among non-saponified P204 and acid more weak non-saponification P507, 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, acid consumption is big, and the present invention adopts one or more the composite extractant among non-saponified P204 and acid more weak non-saponification P507, 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, extracting and separating rear earth element in the composite extractant that adopts one or both preparations among non-saponified P204 and non-saponification P507, C272, C301, C302, the HEOPPA one or both mixed rare earth solutions in rare earth sulfate solution or rare earth sulfate solution and re chloride, rare earth nitrate solution, or adopt extracting and separating rear earth element in non-saponified P204 one or both mixed rare earth solutions in rare earth sulfate solution and re chloride, rare earth nitrate solution.
Earth solution is generally the mixed rare earth solution that sulfuric acid process is handled rare earth sulfate solution that the rare-earth mineral water logging obtains or leached the sulfuric acid rare earth that obtains and rare earth chloride, rare earth nitrate with dilute sulphuric acid or rare nitric acid, or in rare earth sulfate solution extracting and washing process, add hydrochloric acid or nitric acid, re chloride, rare earth nitrate solution as washing lotion, the mixed rare earth solution of sulfuric acid rare earth that obtains and rare earth chloride or rare earth nitrate, its acidity is pH1-5, and content of rare earth is 20-300g/LREO; Described extraction agent is diluted to finite concentration with one or more the organic mixed solvents in kerosene, solvent oil, alkane, the alcohol.
1, rare earth sulfate solution is directly adopted the composite extractant of the non-saponification P204 of 1-1.5mol/L and non-saponification P507 or C272, C302 extract whole rare earths, the supported rare earth extraction agent adopts 5-7N hydrochloric acid or nitric acid back extraction to produce mixed chlorinated rare earth or mixeding acid rare-earth.
2, described earth solution adopts 0.3-1.5mol/L described non-saponifiable extraction agent carrying out neodymium/samarium fractionation extraction grouping, and washing lotion adopts and contains sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, and its rare earth concentration is 100-250g/L REO; The supported rare earth extraction agent obtains the sm-eu-gd enriched substance with 5-7N hydrochloric acid or nitric acid back extraction; The LaCePrNd raffinate that contains that obtains is neutralized to PH2-5, extracts entirely with the non-saponification P204 of 1-1.5mol/L again, and 5-7N hydrochloric acid or nitric acid back extraction prepare LaCePrNd rare earth chloride or rare earth nitrate.
(1) described contain the LaCePrNd raffinate and be neutralized to pH2-5 after, adopt 0.5-1.5mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium extracting and separating, washing lotion adopts and contains neodymium rare earth chloride or rare earth nitrate strip liquor, its rare earth concentration is 100-300g/LREO; The supported rare earth extraction agent obtains Neodymium trichloride or neodymium nitrate with 5-7N hydrochloric acid or nitric acid back extraction; Obtain contain the La-Ce-Pr raffinate and be neutralized to PH2-5 again after, with the non-saponification P204 extraction of 1-1.5mol/L La-Ce-Pr, 5-7N hydrochloric acid or nitric acid back extraction prepare La-Ce-Pr rare earth chloride or rare earth nitrate.
(2) described contain the LaCePrNd raffinate and be neutralized to pH2-5 after, adopt 1-1.5mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium extraction grouping, washing lotion adopts and contains praseodymium neodymium rare earth chloride or rare earth nitrate strip liquor, its rare earth concentration is 100-300g/LREO; The supported rare earth extraction agent obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 5-7N 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 non-saponification P204 extraction of 1-1.5mol/L lanthanum cerium, 5-7N hydrochloric acid or nitric acid back extraction prepare lanthanum cerium rare earth chloride or rare earth nitrate.
(3) the described LaCePrNd raffinate that contains is neutralized to pH1-5, adopt 1-1.5mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet extracting and separating then, employing contains praseodymium neodymium rare earth chloride or rare earth nitrate strip liquor washing extraction agent, 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; The supported rare earth extraction agent obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 5-7N hydrochloric acid or nitric acid back extraction; The lanthanum raffinate that contains that obtains is produced Phosbloc with ammonium bicarbonate precipitation again, or after being neutralized to PH2-5, with the non-saponification P204 extraction of 1-1.5mol/L, hydrochloric acid or nitric acid back extraction prepare Lanthanum trichloride, lanthanum nitrate or the lanthanum trioxide of 99.9-99.99%.
3, described earth solution is adopted 1-1.5mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium fractionation extraction grouping, washing lotion is for containing neodymium sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, the neodymium extraction agent that contains that obtains directly enters neodymium/samarium extraction grouping operation, the supported rare earth extraction agent is with containing the washing of sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, use 5-7N 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 Neodymium trichloride or neodymium nitrate solution, the Neodymium trioxide of precipitable preparation 99.5-99.9%; Praseodymium/neodymium extraction grouping obtains contain the La-Ce-Pr raffinate and be neutralized to PH2-5 after, extract entirely with the non-saponification P204 of 1-1.5mol/L, again with hydrochloric acid or nitric acid back extraction production La-Ce-Pr rare earth chloride or rare earth nitrate.
4, described earth solution is adopted 1-1.5mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet fractionation extractions separate, the supported rare earth extraction agent is with containing the washing of praseodymium neodymium rare earth chloride or rare earth nitrate solution strip liquor, 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; Neodymium/samarium fractionation extraction grouping is carried out in the direct charging of supported rare earth extraction agent, and washing lotion is for containing sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, and what obtain contains sm-eu-gd through 5-7N 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 of 1-1.5mol/L extraction, produce Lanthanum trichloride, lanthanum nitrate or the lanthanum trioxide of 99.9-99.99% again through persalt or nitric acid back extraction.
5, a kind of technology of non-saponification composite extractant extracting and separating rear earth element, 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 or leach sulfuric acid rare earth and the rare earth chloride that obtains with dilute sulphuric acid or rare nitric acid, the mixed rare earth solution of rare earth nitrate is a raw material, adopt the composite extractant of the non-saponification P204 of 0.5-1.5mol/L and non-saponification P507 or C272 to carry out cerium/praseodymium fractionation extraction grouping, washing lotion adopts rare earth chloride or the rare earth nitrate strip liquor that contains the praseodymium neodymium, 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 1-1.5mol/L to extract entirely, produce lanthanum cerium chloride or nitrate with hydrochloric acid or nitric acid back extraction again, also further lanthanum trioxide or the cerium oxide of extracting and separating production 99.9-99.99%; The praseodymium neodymium sm-eu-gd extraction agent that contains that cerium/praseodymium fractionation extraction grouping obtains directly enters neodymium/samarium fractionation extraction grouping operation as feed liquid, extraction agent still adopts the composite extractant of the non-saponification P204 of 0.5-1.5mol/L and non-saponification P507 or C272, the supported rare earth extraction agent is with containing the washing of sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, use 5-7N 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 chloride neodymium or praseodymium nitrate neodymium solution, but direct production praseodymium chloride neodymium or praseodymium nitrate neodymium product, or further extracting and separating production purity is greater than 99.9% Praseodymium trioxide, Neodymium trioxide.
Advantage of the present invention:
When 1) non-saponified P204 carries out Nd-Sm extraction grouping in earth solution, because extraction quantity, 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 0.2N 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 non-saponified P204 and acid more weak non-saponification P507, C272, C301, C302, the composite extractant of one or both preparations among the HEOPPA carries 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 1N 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) adopt the non-saponification organic phase extracting rare-earth separating, technology is simply continuous, easy to control, and main chemical materials consumption rate ammonium bicarbonate precipitation makes the transition, and saponification P507 extraction grouping technology reduces about 40%, and extraction process do not produce ammonia nitrogen waste water, can save three wastes processing cost greatly.
Comparison example 1
1000 gram hamartites and monazite mixed type rare-earth mineral (REO50%) through sulfuric acid baking, water logging, in and removal of impurities, obtain 11.5 liters of purified rare earth sulfate solutions, its acidity is pH4, main component is REO40g/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 is with 4N salt acid elution (consuming concentrated hydrochloric acid 52ml, about 58 grams), through 40 grades of fractionation extractions, the back extraction of 6N hydrochloric acid, obtain containing the re chloride 40ml (consuming concentrated hydrochloric acid 25ml, about 28 grams) of sm-eu-gd 245g/L (REO), 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 (REO50%) are through sulfuric acid baking, water logging, in and removal of impurities, obtain 11.5 liters of purified rare earth sulfate solutions, its acidity is pH4, main component is REO40g/L, Fe＜0.05g/L, P＜0.005g/L, ThO2＜0.001g/L, directly the non-saponification P204 (1.0mol/L) of employing 60% carries out Nd/Sm extraction grouping with the composite 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 re chloride of acidity 1.2N (consuming concentrated hydrochloric acid 110ml, about 121 grams), the washing section rare earth concentration is 245g/l, the supported rare earth organic phase contains rare earth 18g/l, with the back extraction of 6N hydrochloric acid, obtain containing REO210g/l, acidity is that the sm-eu-gd enriched substance re chloride 47ml of 1.2N (consumes concentrated hydrochloric acid 30ml, about 33 grams), can produce sm-eu-gd enriched substance or further extracting and separating.
The raffinate that obtains (contain LaCePrNd 38.3g/l rare earth sulfate solution 11.7 liters) 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 6N 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 (9.5N) (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 (REO50%) 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 pH4, rare earth concentration REO is 36.5g/L, in rare earth sulfate solution, add the 72ml vitriol oil acidity is transferred to 0.2N, 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 1NH2SO4 (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 6N hydrochloric acid, obtains containing sm-eu-gd 130g/L (REO), acidity is that the re chloride 74ml of 2.5N (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 (32N) 94ml (173 gram), concentrated hydrochloric acid (9.5N) 47ml (52 gram), and adding up to sour consumption is 225 grams.
Embodiment 2
1000 gram hamartites and monazite mixed type rare-earth mineral (REO50%) 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 pH4, rare earth concentration REO is 36.5g/L, the non-saponification P204 (1.0mol/L) of direct employing 70% carries out Nd/Sm extraction grouping with the composite 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 1.2N (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 6N hydrochloric acid, obtain containing REO215g/l, acidity is the sm-eu-gd enriched substance re chloride 46ml (consuming concentrated hydrochloric acid 29ml, about 32 grams) of 1.2N, and this solution further extracting and separating extracts samarium, europium, gadolinium single rare earth product.
This technological process consumes concentrated hydrochloric acid (9.5N) 140ml (154 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 pH4, rare earth concentration REO43g/L, add the vitriol oil solution acidity is transferred to 0.2N, 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 1NH
2SO
4Washing, its content of rare earth is 4g/l, with the back extraction of 6N hydrochloric acid, obtains the sm-eu-gd re chloride of 130g/l, 2.5N, 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 1NH with the non-saponification P204 of 1.5mol/L again with magnesium oxide
2SO
4With the back extraction of 6N hydrochloric acid, obtain the praseodymium neodymium re chloride of 230g/l, 0.8N 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, the back extraction of 6N hydrochloric acid obtains the lanthanum cerium re chloride of 270g/l, 0.3N, 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 pH4, 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/lREO) 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 (180g/lREO) washing, use the back extraction of 6N hydrochloric acid then, obtain 180g/l, 1.5N sm-eu-gd re chloride, through precipitation preparation sm-eu-gd enriched substance; Raffinate is 260g/l, 0.3N 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, the back extraction of 6N hydrochloric acid obtains the lanthanum cerium re chloride of 270g/l, 0.3N, 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 4
1000 gram hamartites and monazite mixed type rare-earth mineral through sulfuric acid baking, the rare HCl solution of 0.1mol/L leach, in and removal of impurities, obtain the mixed rare earth solution of purified sulfuric acid rare earth and rare earth chloride, its acidity is pH4, main component is REO48g/L, Fe＜0.05g/L, P＜0.005g/L, ThO2＜0.001g/L, the composite extractant (diluting with kerosene) of the non-saponification P204 of employing 80%1.5mol/L and the non-saponification P507 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 6N hydrochloric acid then, obtain 200g/l, 1.2N sm-eu-gd re chloride, through precipitation preparation sm-eu-gd enriched substance; Raffinate is 265g/l, 0.25N 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, the back extraction of 6N hydrochloric acid obtains the lanthanum cerium re chloride of 270g/l, 0.3N, produces lanthanum cerium rare earth chloride (REO＞45%) through condensing crystal.
Embodiment 5
Handle the rare earth sulfate solution that Australian rare-earth mineral obtains: REO40g/L, pH4, the composite extractant (diluting with kerosene) of the non-saponification P204 of employing 80%1.3mol/L and the non-saponification C272 of 20%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 6N 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 6N hydrochloric acid again.
Embodiment 6
Sulfuric acid rare earth and rare earth chloride mixing solutions: REO48g/L, pH4 adopts non-saponification P204 of 90%1.3mol/L and the non-saponification P507 of 10%1.3mol/L (diluting with kerosene) composite 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; Neodymium/samarium fractionation extraction grouping is carried out in the direct charging of supported rare earth organic phase, the supported rare earth organic phase with the back extraction of 6N hydrochloric acid, obtains the sm-eu-gd enriched substance with containing the washing of sm-eu-gd rare earth chloride strip liquor, 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 6N hydrochloric acid again
Embodiment 7
1000 gram Baotou rare earth ore concentrates are through sulfuric acid baking, water logging, removal of impurities, obtain purified rare earth sulfate solution, its acidity is pH4, main component is REO32g/L, Fe＜0.05g/L, P＜0.005g/L, ThO2＜0.001g/L, directly the composite 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, and the supported rare earth organic phase is with the back extraction of 6N hydrochloric acid, through 6 grades of extractions, wash sulfate radical for 3 grades, calcium, magnesium, 10 grades of back extractions, obtaining concentration is the mixed chlorinated rare earth solution of 260g/lREO, this solution obtains mixed chlorinated rare earth product (REO 〉=45%) through condensing crystal.
Embodiment 8
1000 gram hamartites and monazite mixed type rare-earth mineral (REO50%) are through sulfuric acid baking, water logging, in and removal of impurities, obtain purified rare earth sulfate solution, its acidity is pH4, rare earth concentration is REO40g/L, the non-saponification P204 (1.0mol/L) of direct employing 50% carries out Nd/Sm extraction grouping with the composite 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 1.0N, the supported rare earth organic phase contains rare earth 17g/l, with the back extraction of 6N hydrochloric acid, obtain containing REO210g/l, acidity is the sm-eu-gd re chloride of 1.0N, 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 composite extractant (diluting with kerosene) of the non-saponification P507 of 20%1.3mol/L then and separate, washing lotion adopts and contains neodymium rare earth nitrate strip liquor (REO250g/L); The 6N 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 6N hydrochloric acid prepares the La-Ce-Pr rare earth chloride.
Embodiment 9
The fore portion operation is with embodiment 2.
The LaCePrNd raffinate that contains that obtains is neutralized to pH4 with magnesium oxide, adopts the composite 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 (REO268g/L); The 6.3N 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 6N hydrochloric acid prepares lanthanum cerium rare earth chloride;
Embodiment 10
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 solvent oil 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 6.2N hydrochloric acid; It is 99.9% Phosbloc that raffinate obtains purity with ammonium bicarbonate precipitation, and calcination obtains lanthanum trioxide.
Claims (11)
1, a kind of technology of non-saponification organic extractant extracting and separating rear earth element, it is characterized in that: to handle the earth solution that contains multiple rare earth element that rare-earth mineral obtains is raw material, extracting and separating rear earth element in the composite extractant that adopts one or both preparations among non-saponified P204 and non-saponification P507, C272, C301, C302, the HEOPPA one or both mixed rare earth solutions in rare earth sulfate solution or rare earth sulfate solution and re chloride, rare earth nitrate solution.
2, a kind of technology of non-saponification organic extractant extracting and separating rear earth element, it is characterized in that: to handle the earth solution that contains multiple rare earth element that rare-earth mineral obtains is raw material, adopts extracting and separating rear earth element in non-saponified P204 one or both mixed rare earth solutions in rare earth sulfate solution and re chloride, rare earth nitrate solution.
3, technology as claimed in claim 1 or 2, it is characterized in that, described earth solution is that sulfuric acid process is handled rare earth sulfate solution that the rare-earth mineral water logging obtains or leached the mixed rare earth solution of the sulfuric acid rare earth that obtains and rare earth chloride, rare earth nitrate with dilute sulphuric acid or rare nitric acid, or in rare earth sulfate solution extracting and washing process, add hydrochloric acid or nitric acid, re chloride, rare earth nitrate solution as washing lotion, the mixed rare earth solution of sulfuric acid rare earth that obtains and rare earth chloride or rare earth nitrate, its acidity is pH1-5, and content of rare earth is 20-300g/L REO; Described extraction agent is diluted to finite concentration with one or more the organic mixed solvents in kerosene, solvent oil, alkane, the alcohol.
4, technology as claimed in claim 1, it is characterized in that, rare earth sulfate solution directly adopts the composite extractant of the non-saponification P204 of 1-1.5mol/L and non-saponification P507 or C272, C302 to extract whole rare earths, and the supported rare earth extraction agent adopts 5-7N hydrochloric acid or nitric acid back extraction to produce mixed chlorinated rare earth or mixeding acid rare-earth.
5, technology as claimed in claim 1 or 2, it is characterized in that, described earth solution adopts 0.3-1.5mol/L described non-saponifiable extraction agent carrying out neodymium/samarium fractionation extraction grouping, and washing lotion adopts and contains sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, and its rare earth concentration is 100-250g/L REO; The supported rare earth extraction agent obtains the sm-eu-gd enriched substance with 5-7N hydrochloric acid or nitric acid back extraction; The LaCePrNd raffinate that contains that obtains is neutralized to PH2-5, extracts entirely with the non-saponification P204 of 1-1.5mol/L again, and 5-7N hydrochloric acid or nitric acid back extraction prepare LaCePrNd rare earth chloride or rare earth nitrate.
6, technology as claimed in claim 5, it is characterized in that, described contain the LaCePrNd raffinate and be neutralized to pH2-5 after, adopt 0.5-1.5mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium extracting and separating, washing lotion adopts and contains neodymium rare earth chloride or rare earth nitrate strip liquor, and its rare earth concentration is 100-300g/L REO; The supported rare earth extraction agent obtains Neodymium trichloride or neodymium nitrate with 5-7N hydrochloric acid or nitric acid back extraction; Obtain contain the La-Ce-Pr raffinate and be neutralized to PH2-5 again after, with the non-saponification P204 extraction of 1-1.5mol/L La-Ce-Pr, 5-7N hydrochloric acid or nitric acid back extraction prepare La-Ce-Pr rare earth chloride or rare earth nitrate.
7, technology as claimed in claim 5, it is characterized in that, described contain the LaCePrNd raffinate and be neutralized to pH2-5 after, adopt 1-1.5mol/L described non-saponifiable extraction agent carrying out cerium/praseodymium extraction grouping, washing lotion adopts and contains praseodymium neodymium rare earth chloride or rare earth nitrate strip liquor, and its rare earth concentration is 100-300g/L REO; The supported rare earth extraction agent obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 5-7N 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 non-saponification P204 extraction of 1-1.5mol/L lanthanum cerium, 5-7N hydrochloric acid or nitric acid back extraction prepare lanthanum cerium rare earth chloride or rare earth nitrate.
8, technology as claimed in claim 5, it is characterized in that, the described LaCePrNd raffinate that contains is neutralized to pH1-5, adopt 1-1.5mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet extracting and separating then, employing contains praseodymium neodymium rare earth chloride or rare earth nitrate strip liquor washing extraction agent, 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; The supported rare earth extraction agent obtains praseodymium chloride neodymium or praseodymium nitrate neodymium with 5-7N 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 1-1.5mol/L, hydrochloric acid or nitric acid back extraction prepare Lanthanum trichloride, lanthanum nitrate or the lanthanum trioxide of 99.9-99.99%.
9, technology as claimed in claim 1 or 2, it is characterized in that, described earth solution adopts 1-1.5mol/L described non-saponifiable extraction agent carrying out praseodymium/neodymium fractionation extraction grouping, washing lotion is for containing neodymium rare earth chloride or rare earth nitrate strip liquor, the neodymium sm-eu-gd extraction agent that contains that obtains directly enters neodymium/samarium extraction grouping operation, the supported rare earth extraction agent is used 5-7N hydrochloric acid or nitric acid back extraction then with containing the washing of sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, obtains the sm-eu-gd enriched substance; The raffinate that neodymium/samarium fractionation extraction grouping obtains is Neodymium trichloride or neodymium nitrate solution, the Neodymium trioxide of precipitable preparation 99.5-99.9%; Praseodymium/neodymium extraction grouping obtains contain the La-Ce-Pr raffinate and be neutralized to PH2-5 after, extract entirely with the non-saponification P204 of 1-1.5mol/L, again with hydrochloric acid or nitric acid back extraction production La-Ce-Pr rare earth chloride or rare earth nitrate.
10, technology as claimed in claim 1 or 2, it is characterized in that, described earth solution adopts 1-1.5mol/L described non-saponifiable extraction agent carrying out lanthanum/cerium/praseodymium three outlet fractionation extractions to separate, the supported rare earth extraction agent is with containing the washing of praseodymium neodymium rare earth chloride or rare earth nitrate solution strip liquor, 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; Neodymium/samarium fractionation extraction grouping is carried out in the direct charging of supported rare earth extraction agent, and washing lotion is for containing sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, and what obtain contains sm-eu-gd through 5-7N 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 or lanthanum trioxide with ammonium bicarbonate precipitation, or after being neutralized to PH2-5, with the non-saponification P204 of 1-1.5mol/L extraction, produce Lanthanum trichloride, lanthanum nitrate or the lanthanum trioxide of 99.9-99.99% again through persalt or nitric acid back extraction.
11, a kind of technology of non-saponification composite extractant extracting and separating rear earth element, 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 or leach sulfuric acid rare earth and the rare earth chloride that obtains with dilute sulphuric acid or rare nitric acid, the mixed rare earth solution of rare earth nitrate is a raw material, adopt the composite extractant of the non-saponification P204 of 0.5-1.5mol/L and non-saponification P507 or C272 to carry out cerium/praseodymium fractionation extraction grouping, washing lotion adopts rare earth chloride or the rare earth nitrate strip liquor that contains praseodymium neodymium sm-eu-gd, 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 1-1.5mol/L to extract entirely, produce lanthanum cerium chloride or nitrate with hydrochloric acid or nitric acid back extraction again, also further lanthanum trioxide or the cerium oxide of extracting and separating production 99.9-99.99%; The praseodymium neodymium sm-eu-gd extraction agent that contains that cerium/praseodymium fractionation extraction grouping obtains directly enters neodymium/samarium fractionation extraction grouping operation as feed liquid, extraction agent still adopts the composite extractant of the non-saponification P204 of 0.5-1.5mol/L and non-saponification P507 or C272, the supported rare earth extraction agent is with containing the washing of sm-eu-gd rare earth chloride or rare earth nitrate strip liquor, use 5-7N 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 chloride neodymium or praseodymium nitrate neodymium solution, but direct production praseodymium chloride neodymium or praseodymium nitrate neodymium product, or further extracting and separating production purity is greater than 99.9% Praseodymium trioxide, Neodymium trioxide.
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