CN115992317A - Method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium - Google Patents
Method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium Download PDFInfo
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- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 152
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 123
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 97
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 52
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- 239000000243 solution Substances 0.000 claims abstract description 132
- 239000012074 organic phase Substances 0.000 claims abstract description 131
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000605 extraction Methods 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 238000005406 washing Methods 0.000 claims abstract description 55
- 238000001556 precipitation Methods 0.000 claims abstract description 46
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
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- 238000002156 mixing Methods 0.000 claims abstract description 13
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- -1 rare earth oxalate Chemical class 0.000 claims description 16
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- 235000011152 sodium sulphate Nutrition 0.000 claims description 16
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- 230000032683 aging Effects 0.000 claims description 11
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
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- 239000000126 substance Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 60
- 229910052742 iron Inorganic materials 0.000 abstract description 31
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 6
- 230000001376 precipitating effect Effects 0.000 abstract description 5
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- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- PZQADQWPBJVVGH-UHFFFAOYSA-N niobium titanium zirconium Chemical compound [Ti].[Zr].[Nb] PZQADQWPBJVVGH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
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- 239000001099 ammonium carbonate Substances 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 description 4
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OYZDSTHSJLIZOU-UHFFFAOYSA-N [Fe].[Nb].[Zr].[Ti] Chemical compound [Fe].[Nb].[Zr].[Ti] OYZDSTHSJLIZOU-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention provides a method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium, and belongs to the technical field of hydrometallurgy. The method adopts a high-temperature high-pressure impurity removal method, generates hydrolysis compounds such as iron vitriol, niobium titanium zirconium and the like through the regulation and control of acidity and oxidizing atmosphere in the solution, the reaction temperature and the like, realizes the efficient removal of impurities under the high acidity condition, simultaneously effectively reduces the sulfate radical concentration in the second filtrate, and creates favorable conditions for the subsequent uranium separation. The invention adopts the method of precipitating rare earth by sulfuric acid double salt and returning beryllium loaded organic phase washing liquid to the precipitation depth to recycle rare earth, and improves the rare earth separation and recycling efficiency by adopting the high-temperature impurity removal method. According to the invention, for the uranium-extracted solution, oxalic acid and alkali solution are used for blending, and the complexation of oxalic acid and residual iron in the solution reduces the competition with beryllium extraction; the pH value of the solution before extraction is adjusted to 1.5-2.5, and the saponification treatment of the beryllium extraction organic phase obviously improves the beryllium extraction separation efficiency.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium.
Background
Rare earth, uranium, beryllium and the like play a key role in new generation information technology, high-end equipment manufacturing, new materials, new energy automobiles, energy conservation, environmental protection and other strategic emerging industries, and are mineral resources essential for national economy development and national defense construction. With the continuous development and production of domestic mineral resources, single mineral resources with large resource quantity and easy exploitation are basically consumed, and multi-metal co-associated minerals become mainstream resources.
Aiming at multi-metal ores containing rare earth uranium beryllium, cheng Quanhui proposes that the beryllium silicon is leached by sulfuric acid, the rare earth is separated by sulfuric acid double salt precipitation, and the rare earth is converted to prepare rare earth hydroxide, and the solution after the rare earth precipitation, the iron removal by neutralization and the rare earth precipitation by oxalic acid are carried out, and the beryllium hydroxide is obtained by neutralization precipitation. The method realizes the separation of beryllium and rare earth to obtain mixed rare earth hydroxide and industrial beryllium oxide, but the neutralization method removes iron, which inevitably has beryllium adsorption and entrainment loss, and the metal recovery rate is not high (Cheng Quanhui. The industrial beryllium oxide and mixed rare earth [ J ]. Rare metals and hard alloy are extracted from the silicon beryllium-aluminum ore, 1999 (4): 5.). Furthermore, this prior art does not relate to the separation of uranium.
Disclosure of Invention
The invention aims to provide a method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium, which can improve the separation efficiency of rare earth, uranium and beryllium and realize the efficient separation and recovery of rare earth, uranium and beryllium in a complex system.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium, which comprises the following steps:
mixing sulfuric acid leaching solution containing rare earth uranium beryllium with sodium sulfate, performing precipitation reaction, and performing solid-liquid separation to obtain rare earth sulfuric acid double salt precipitate and first filtrate;
adjusting H in said first filtrate with a calcium-containing substance + The concentration of the mixture is 0.2 to 0.8mol/L, then the temperature is raised to 160 to 210 ℃, and oxygen is introduced to perform high-temperature high-pressure impurity removal reaction to obtain impurity removal slag and second filtrate; the partial pressure of the oxygen is 0.2-1.0 MPa;
carrying out uranium extraction on the second filtrate by utilizing a first organic phase, and separating to obtain a uranium loaded organic phase and a uranium extracted solution; performing back extraction on the uranium loaded organic phase to obtain qualified uranium liquid and a first organic phase;
mixing beryllium loaded organic phase washing liquid with the uranium extracted solution, adding sodium hydroxide or sodium carbonate to adjust the pH value of the obtained mixed solution to be 1.5-2.5, carrying out precipitation and complexation reaction, aging, and carrying out solid-liquid separation to obtain rare earth oxalate precipitation and adjusted solution; the beryllium-loaded organic phase washing liquid is oxalic acid solution and is obtained by washing the beryllium-loaded organic phase of the previous batch;
performing saponification treatment on the second organic phase, and performing beryllium extraction on the adjusted solution by using the saponified second organic phase to obtain a beryllium-loaded organic phase; the second organic phase is P204, TBP and sulfonated kerosene; the volume content of the P204 in the second organic phase is 20-30%, and the volume content of the TBP is 15-30%; the saponification degree of the saponification treatment is 40-65%;
washing the beryllium-loaded organic phase by adopting oxalic acid solution to obtain a beryllium-loaded organic phase washing solution and a washed beryllium-loaded organic phase; back-extracting the washed beryllium loaded organic phase to obtain a second organic phase and beryllium qualified liquid; and returning the beryllium loaded organic phase washing liquid to be mixed with the uranium extraction post-solution of the next batch.
Preferably, after the washing liquid is obtained, the time of the precipitation and the complexation reaction is 30min; the aging time is 2-4 hours.
Preferably, the concentration of rare earth in the sulfuric acid leaching solution containing rare earth uranium beryllium is 8-50 g/L, the concentration of beryllium is 1-5 g/L, the concentration of uranium is 30-1000 mg/L, and H + The concentration is 0.5-1.0 mol/L, and the sulfate radical concentration is 60-130 g/L.
Preferably, the temperature of the precipitation reaction is 90-98 ℃ and the time is 0.5-2 h.
Preferably, the content of rare earth elements in the sulfuric acid leaching solution containing rare earth uranium beryllium is calculated by rare earth oxide, and the mass ratio of the rare earth oxide to sodium sulfate is 1: (2.8-4).
Preferably, the calcium-containing material comprises CaO, ca (OH) or CaCO 3 。
Preferably, the high-temperature high-pressure impurity removal reaction time is 1-4 hours.
Preferably, the first organic phase is kerosene, N235 and TBP; the volume content of N235 in the first organic phase is 1-5%, and the volume content of TBP is 3-10%.
Preferably, the reagent used for carrying out back extraction on the uranium-loaded organic phase is a sodium carbonate solution, and the concentration of the sodium carbonate solution is 80-150 g/L.
Preferably, the first' organic phase is returned to uranium extraction; the second' organic phase is returned to beryllium extraction.
The invention provides a method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium, which comprises the following steps: mixing sulfuric acid leaching solution containing rare earth uranium beryllium with sodium sulfate, performing precipitation reaction, and performing solid-liquid separation to obtain rare earth sulfuric acid double salt precipitate and first filtrate; adjusting H in said first filtrate with a calcium-containing substance + The concentration of the mixture is 0.2 to 0.8mol/L, then the temperature is raised to 160 to 210 ℃, and oxygen is introduced to perform high-temperature high-pressure impurity removal reaction to obtain impurity removal slag and second filtrate; the partial pressure of the oxygen is 0.2-1.0 MPa; carrying out uranium extraction on the second filtrate by utilizing a first organic phase, and separating to obtain a uranium loaded organic phase and a uranium extracted solution; performing back extraction on the uranium loaded organic phase to obtain qualified uranium liquid and a first organic phase; mixing beryllium loaded organic phase washing liquid with the uranium extracted solution, adding sodium hydroxide or sodium carbonate to adjust the pH value of the obtained mixed solution to be 1.5-2.5, carrying out precipitation and complexation reaction, aging, and carrying out solid-liquid separation to obtain rare earth oxalate precipitation and adjusted solution; the beryllium-loaded organic phase washing liquid is oxalic acid solution and is obtained by washing the beryllium-loaded organic phase of the previous batch; performing saponification treatment on the second organic phase, and performing beryllium extraction on the adjusted solution by using the saponified second organic phase to obtain a beryllium-loaded organic phase; the second organic phase is P204, TBP and sulfonated kerosene; the volume content of the P204 in the second organic phase is 20-30%, and the volume content of the TBP is 15-30%; the saponification degree of the saponification treatment is 40-65%; washing the beryllium-loaded organic phase by adopting oxalic acid solution to obtain a beryllium-loaded organic phase washing solution and a washed beryllium-loaded organic phase; back-extracting the washed beryllium loaded organic phase to obtain a second organic phase and beryllium qualified liquid; and returning the beryllium loaded organic phase washing liquid to be mixed with the uranium extraction post-solution of the next batch.
The method adopts a high-temperature high-pressure impurity removal method, generates hydrolysis compounds such as iron vitriol, niobium titanium zirconium and the like through the regulation and control of acidity and oxidizing atmosphere in the solution, the reaction temperature and the like, realizes the efficient removal of impurities under the high acidity condition, simultaneously effectively reduces the sulfate radical concentration in the second filtrate, and creates favorable conditions for the subsequent uranium separation.
The method adopts sulfuric acid double salt to precipitate rare earth and beryllium loaded organic phase washing liquid to return to the precipitation depth to recover the rare earth, and improves the rare earth separation recovery efficiency by adopting a high-temperature impurity removal method, thereby realizing the efficient separation recovery of the rare earth in a high-acid high-impurity solution system.
According to the invention, for the uranium-extracted solution, oxalic acid and alkali solution are used for blending, and the complexation of oxalic acid and residual iron in the solution reduces the competition with beryllium extraction; the pH value of the solution before extraction is adjusted to 1.5-2.5, and the saponification treatment of the beryllium extraction organic phase obviously improves the beryllium extraction separation efficiency.
The invention returns the loaded organic phase washing liquid to the rare earth precipitation process, thereby further recovering valuable metals in the washing liquid, improving the metal recovery rate and simultaneously avoiding the generation of oxalic acid-containing wastewater.
Drawings
Fig. 1 is a flow chart of the invention for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium.
Detailed Description
The invention provides a method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium, which comprises the following steps:
mixing sulfuric acid leaching solution containing rare earth uranium beryllium with sodium sulfate, performing precipitation reaction, and performing solid-liquid separation to obtain rare earth sulfuric acid double salt precipitate and first filtrate;
adjusting H in said first filtrate with a calcium-containing substance + The concentration of the mixture is 0.2 to 0.8mol/L, then the temperature is raised to 160 to 210 ℃, and oxygen is introduced to perform high-temperature high-pressure impurity removal reaction to obtain impurity removal slag and second filtrate; the partial pressure of the oxygen is 0.2-1.0 MPa;
carrying out uranium extraction on the second filtrate by utilizing a first organic phase, and separating to obtain a uranium loaded organic phase and a uranium extracted solution; performing back extraction on the uranium loaded organic phase to obtain qualified uranium liquid and a first organic phase;
mixing beryllium loaded organic phase washing liquid with the uranium extracted solution, adding sodium hydroxide or sodium carbonate to adjust the pH value of the obtained mixed solution to be 1.5-2.5, carrying out precipitation and complexation reaction, aging, and carrying out solid-liquid separation to obtain rare earth oxalate precipitation and adjusted solution; the beryllium-loaded organic phase washing liquid is oxalic acid solution and is obtained by washing the beryllium-loaded organic phase of the previous batch;
performing saponification treatment on the second organic phase, and performing beryllium extraction on the adjusted solution by using the saponified second organic phase to obtain a beryllium-loaded organic phase; the second organic phase is P204, TBP and sulfonated kerosene; the volume content of the P204 in the second organic phase is 20-30%, and the volume content of the TBP is 15-30%; the saponification degree of the saponification treatment is 40-65%;
washing the beryllium-loaded organic phase by adopting oxalic acid solution to obtain a beryllium-loaded organic phase washing solution and a washed beryllium-loaded organic phase; back-extracting the washed beryllium loaded organic phase to obtain a second organic phase and beryllium qualified liquid; and returning the beryllium loaded organic phase washing liquid to be mixed with the uranium extraction post-solution of the next batch.
The invention mixes sulfuric acid leaching solution containing rare earth uranium beryllium with sodium sulfate, carries out precipitation reaction, and obtains rare earth sulfuric acid double salt precipitation and first filtrate after solid-liquid separation.
The invention has no special requirement on the source of the sulfuric acid leaching solution containing rare earth uranium beryllium, and the sources are well known in the field. In the invention, the sulfuric acid leaching solution containing rare earth uranium beryllium is specifically obtained by mixing concentrated sulfuric acid into polymetallic rough concentrate containing rare earth uranium beryllium for roasting at low temperature, leaching with water, and carrying out solid-liquid separation after leaching is completed. In the invention, the concentration of rare earth in the sulfuric acid leaching solution containing rare earth uranium beryllium is preferably 8-50 g/L, the concentration of beryllium is preferably 1-5 g/L, the concentration of uranium is preferably 30-1000 mg/L, and H + The concentration is preferably 0.5 to 1.0mol/L, and the sulfate radical concentration is preferably 60 to 130g/L. In the invention, the sulfuric acid leaching solution containing rare earth uranium beryllium also contains iron, niobium, titanium and zirconium. In the present invention, the concentrations of iron and titanium are preferably less than 10g/L, and the concentrations of niobium and zirconium are preferably less than 2g/L.
In the invention, the content of rare earth elements in the sulfuric acid leaching solution containing rare earth uranium beryllium is calculated by rare earth oxide, and the mass ratio of the Rare Earth Oxide (REO) to sodium sulfate is preferably 1: (2.8 to 4), more preferably 1: (3-3.5).
In the invention, mixing the sulfuric acid leaching solution containing rare earth uranium beryllium with sodium sulfate preferably comprises: heating sulfuric acid leaching solution containing rare earth uranium beryllium to 80 ℃, adding sodium sulfate while stirring, and then heating to the temperature of precipitation reaction.
In the present invention, the temperature of the precipitation reaction is preferably 90 to 98 ℃, more preferably 92 to 96 ℃; the time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours. In the precipitation reaction process, the light rare earth sulfate can form a double salt which is indissolvable in excessive sodium sulfate or sulfuric acid with sodium sulfate, and the reaction equation is as follows: xRE 2 (SO 4 ) 3 +yNa 2 SO 4 +zH 2 O＝xRE 2 (SO 4 ) 3 ·yNa 2 SO 4 ·zH 2 O。
The invention has the rare earth precipitation rate more than 98% through precipitation reaction.
The method of the invention has no special requirement on the solid-liquid separation mode, and the solid-liquid separation mode well known in the field can be adopted.
After the first filtrate is obtained, the invention adjusts H in the first filtrate by using calcium-containing substances + The concentration of the mixture is 0.2 to 0.8mol/L, then the temperature is raised to 160 to 210 ℃, and oxygen is introduced to perform high-temperature high-pressure impurity removal reaction to obtain impurity removal slag and second filtrate; the partial pressure of the oxygen is 0.2-1.0 MPa.
In the present invention, the calcium-containing substance preferably comprises CaO, ca (OH) or CaCO 3 . The calcium salt can not only regulate the acidity of the first filtrate, but also regulate the sulfate radical concentration (particularly reduce the sulfate radical concentration) of the solution, thereby creating favorable conditions for the subsequent uranium separation.
In the present invention, H in the first filtrate after adjustment + The concentration of (C) is preferably 0.3 to 0.6mol/L, more preferably 0.4 to 0.5mol/L. The invention can improve the precipitation rate of impurity elements such as iron niobium titanium zirconium by adjusting the concentration of hydrogen ions within the range.
In the present invention, the high temperature and high pressure impurity removal reaction is preferably performed in an autoclave. In the present invention, the time for the high temperature and high pressure reaction is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the present invention, the partial pressure of oxygen is preferably 0.3 to 0.9MPa, more preferably 0.4 to 0.8MPa. The invention preferably increases the temperature to 170-200 ℃ to carry out high-temperature high-pressure impurity removal reaction.
In the high-temperature high-pressure impurity removal reaction process, niobium, titanium, zirconium and the like are subjected to hydrolysis reaction, iron is subjected to iron vitriol generation reaction, iron vitriol is a complex compound containing Na, iron and sulfur, and impurity elements such as iron, niobium, titanium, zirconium and the like are precipitated and separated out. The invention utilizes the characteristics of research objects, namely, high sodium content, high acidity and high sulfate radical concentration, and the sulfate radical concentration in the solution is further reduced while the iron is recovered by finely adjusting the acidity and the sulfate radical concentration (the sulfate radical concentration is adjusted by adding Ca), precipitating iron into the form of iron vitriol by high temperature control and the like, and the method can return the iron to the leaching process. In addition, the iron vitriol generated at 160-210 ℃ in the invention has the advantage of lower water content, and can reduce the consumption of washing, drying and calcining the subsequent precipitation slag. Through high-temperature high-pressure impurity removal, the concentration of iron, niobium, titanium and zirconium in the second filtrate can be respectively reduced to below 180mg/L, below 2mg/L, below 4mg/L and below 2mg/L.
After obtaining the second filtrate, the invention utilizes the first organic phase to carry out uranium extraction relative to the second filtrate, and uranium loaded organic phase and uranium extracted solution are obtained after separation.
In the present invention, the first organic phase is preferably kerosene, N235 and TBP; the volume content of N235 in the first organic phase is preferably 1-5%, and the volume content of TBP is preferably 3-10%. In the present invention, the uranium extraction is preferably countercurrent extraction, more preferably 3 to 5 stages countercurrent extraction. In the invention, after uranium extraction, the concentration of uranium in the obtained uranium extracted solution can be reduced to below 0.9mg/L, and the uranium extraction rate reaches above 98.6%.
After obtaining the uranium loaded organic phase, the invention carries out back extraction on the uranium loaded organic phase to obtain uranium qualified liquid and a first organic phase.
In the present invention, the reagent used for the back extraction of the uranium-bearing organic phase is preferably a sodium carbonate solution, and the concentration of the sodium carbonate solution is preferably 80 to 150g/L, more preferably 100 to 120g/L. The present invention has no special requirements for the stripping process, and stripping processes well known in the art can be used.
After obtaining the uranium qualified liquid and the first' organic phase, the invention preferably precipitates the uranium qualified liquid to obtain a uranium product; the first' organic phase is preferably returned to uranium extraction.
Mixing beryllium loaded organic phase washing liquid with the uranium extracted solution, adding sodium hydroxide or sodium carbonate to adjust the pH value of the obtained mixed solution to be 1.5-2.5, carrying out precipitation and complexation reaction, aging, and carrying out solid-liquid separation to obtain rare earth oxalate precipitation and adjusted solution; the beryllium-loaded organic phase washing liquid is obtained by washing the beryllium-loaded organic phase of the previous batch by oxalic acid solution.
In the invention, the beryllium loaded organic phase washing liquid is obtained by performing beryllium extraction on the uranium extracted solution through a saponified second organic phase, thus obtaining a beryllium loaded organic phase, and then washing the obtained beryllium loaded organic phase by using oxalic acid solution.
In the present invention, the time of the precipitation and complexation reaction is preferably 30min; the aging time is preferably 2 to 4 hours. In the precipitation and complexation reaction process, oxalic acid and rare earth generate oxalic acid rare earth; oxalic acid is complexed with iron, aluminum, etc., to produce a complex anion. The invention promotes the growth of the generated rare earth oxalate micro-particles by aging. In the prior art, after the beryllium loaded organic phase is washed by oxalic acid, the washing liquid is directly treated as wastewater, and as the washing liquid also contains low-content beryllium, valuable metal is lost, and the water treatment cost is increased. The method can be used for deeply precipitating and separating rare earth (improving the recovery rate of rare earth), complexing impurity ions (reducing the extraction of impurities such as iron and aluminum in the beryllium extraction process) and improving the recovery rate of beryllium (washing liquid enters an extraction system again and beryllium in the washing liquid can be further recovered) after the washing liquid is returned to be prepared.
After the adjusted solution is obtained, the second organic phase is subjected to saponification treatment, and the adjusted solution is subjected to beryllium extraction by utilizing the saponified second organic phase to obtain a beryllium-loaded organic phase.
In the present invention, the second organic phase is P204, TBP and sulfonated kerosene; the volume content of the P204 in the second organic phase is 20-30%, and the volume content of the TBP is 15-30%; the saponification degree of the saponification treatment is 40-65%. In the present invention, the saponification degree refers to the ratio of neutralizing hydrogen in the second organic phase with an alkali solution. In the present invention, the reagent used for the saponification treatment is preferably a NaOH solution. The saponification treatment process is not particularly limited, and saponification treatment processes well known in the art can be adopted. The P204 extractant is an acidic extractant, and the extraction process is an exchange process of hydrogen ions and metal ions in the solution, but the hydrogen ions enter the solution to increase the acidity of the solution and influence the extraction rate of the metal, and the method comprises the steps of treating the solution with alkali before extraction to ensure that Na and H are mixed + Exchange with OH at the same time - Neutralization, the purpose of avoiding the increase of acidity of the solution is achieved.
In the present invention, the beryllium extraction is preferably countercurrent extraction, more preferably 4 to 10 stages countercurrent extraction. In the invention, the beryllium extraction rate is more than or equal to 99.90%, the iron extraction rate is less than 30%, and the beryllium-iron separation coefficient is 2350.
After the beryllium loaded organic phase is obtained, the invention adopts oxalic acid solution to wash the beryllium loaded organic phase to obtain washing liquid and washed beryllium loaded organic phase.
In the present invention, the mass concentration of the oxalic acid solution is preferably 4 to 10%, more preferably 6 to 8%. In the present invention, the volume ratio of the beryllium-loaded organic phase to the oxalic acid solution (i.e., O/A as compared with washing) is preferably (5 to 10): 1, more preferably (6 to 9): 1. the complexing ability of oxalic acid and iron is strong, and the invention washes out the iron ions in the beryllium loaded organic phase by washing, thereby realizing the efficient separation and recovery of beryllium. After the washing, the removal rate of iron can reach 96% at maximum.
After the washed beryllium loaded organic phase is obtained, the method carries out back extraction on the washed beryllium loaded organic phase to obtain a second organic phase and beryllium qualified liquid.
In the present invention, the reagent used for the back extraction is preferably an ammonium carbonate solution, and the concentration of the ammonium carbonate solution is preferably 200 to 300g/L. In the present invention, the volume ratio of the beryllium loaded organic phase to the ammonium carbonate solution after washing (i.e., the back extraction ratio O/A) is preferably (2 to 4): 1. In the invention, the back extraction rate of beryllium reaches more than 97 percent. The invention preferably prepares the beryllium oxide product from the qualified beryllium solution, and the second organic phase returns to beryllium extraction for recycling.
After the washing liquid is obtained, the washing liquid is returned to be mixed with the uranium extracted solution of the next batch, sodium hydroxide or sodium carbonate is added to adjust the pH value of the obtained mixed solution to be 1.5-2.5, precipitation and complexation reaction are carried out, aging is carried out, and rare earth oxalate precipitation and adjusted solution are obtained through solid-liquid separation; and carrying out beryllium extraction on the adjusted solution.
The method for separating rare earth uranium beryllium from sulfuric acid leaching solution containing rare earth uranium beryllium provided by the present invention is described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Some sulfuric acid leaching solution containing rare earth uranium beryllium, wherein C (REO) = 37.63g/L, C (U) =36 mg/L, C (BeO) =4.6 g/L, C (Fe) =9.2 g/L, C (Nb) =0.66 g/L, C (Ti) =2.43 g/L, C (Zr) =0.28 g/L, C (SO) 4 2- )＝125g/L，C(H + ) =1.2 mol/L. The following steps are performed according to the flow shown in fig. 1:
(1) Heating sulfuric acid leaching solution containing rare earth uranium beryllium to 80 ℃, adding sodium sulfate while stirring, wherein the sodium sulfate is added according to w (REO) w (Na 2 SO 4 ) =1:3.2 addition; and after the sodium sulfate is added, heating the solution to 95 ℃, carrying out precipitation reaction for 2 hours, and carrying out solid-liquid separation after the reaction is finished to obtain rare earth sulfuric acid double salt precipitate and a first filtrate.
(2) The first filtrate was adjusted with CaO in solution C (H + ) =0.5 mol/L, which was then poured into an autoclave; heating the solution to 180 ℃ in a reaction kettle, introducing oxygen after reaching the reaction temperature, keeping the oxygen partial pressure of 0.6MPa, reacting for 2 hours, and carrying out solid-liquid separation after the reaction is completed to obtain impurity-removing slag and a first stepAnd (2) filtering the second filtrate. In the impurity removing process, the impurity elements of iron, niobium, titanium and zirconium are precipitated, and the concentration of the iron, niobium, titanium and zirconium in the solution is respectively reduced to 180mg/L, 2mg/L, 4mg/L and 2mg/L.
(3) Carrying out uranium extraction on the second filtrate by adopting 3% N235+5% TBP+92% kerosene, and reducing the uranium concentration in the solution to 0.9mg/L through 3-stage countercurrent extraction to obtain a uranium-extracted solution and a uranium-loaded organic phase; the uranium-loaded organic phase adopts 100g/LNa 2 CO 3 Performing back extraction to obtain qualified uranium liquid; the organic phase after back extraction returns to uranium extraction for recycling.
(4) Adding the beryllium loaded organic phase washing liquid into the uranium extraction post-solution, and stirring for 10min; and adding sodium carbonate to adjust the pH value of the solution to 1.5-2.5, carrying out precipitation and complexation reaction for 30min, aging for 2h after the reaction is finished, and filtering to obtain rare earth oxalate and an adjusted filtrate. The concentration of rare earth in the solution is reduced to 30mg/L.
(5) The composition of the beryllium extraction organic phase is 30% of P204+20% of TBP+50% of sulfonated kerosene, and the organic phase is firstly saponified by 400g/LNaOH solution, and the saponification degree is controlled to be 40%. The beryllium extraction adopts four-stage countercurrent extraction, the beryllium extraction rate in the solution is more than or equal to 99.90 percent, the iron extraction rate is less than 30 percent, and the beryllium-iron separation coefficient is 2350. The beryllium-loaded organic phase washing detergent is 5% oxalic acid solution, the washing ratio (O/A) is 5:1, the iron washing removal rate of the loaded organic phase after washing can reach 96%, and the washing liquid returns to the solution step (4). The organic phase is loaded after washing, 260g/L ammonium carbonate solution is adopted to strip beryllium, and the stripping ratio is 97% compared with (O/A) 3:1. And preparing a beryllium oxide product by the beryllium back-extraction liquid, and returning the organic phase to the beryllium extraction for recycling.
The total recovery rate of rare earth is 99.92%, the total recovery rate of uranium is 90.5%, and the total recovery rate of beryllium is 91.2%.
Comparative example 1
The difference with the embodiment 1 is that the prior art is adopted, the sulfuric acid leaching solution containing rare earth uranium beryllium is heated to 90 ℃, sodium sulfate is added according to 1.5 times of the theoretical addition amount, and the mixture is stirred for 2 hours; and (3) carrying out solid-liquid separation after the reaction is completed to obtain rare earth sulfuric acid double salt precipitation and rare earth precipitation solution. Then adjusting the solution after precipitating the rare earth by using NaOH solution, adding hydrogen peroxide at the same time, and reacting for 2 hours at 95 ℃; and filtering and separating after the reaction is finished to obtain precipitation slag and solution after iron removal. The solution after iron removal adopts 201 x 7 anion exchange adsorption to separate uranium, and the volume ratio of resin to solution is 1:50, the contact time is 4h; and (5) separating after the adsorption is completed to obtain uranium adsorption resin and uranium separated solution. Heating the uranium separated solution to 90 ℃, adjusting the pH to 7-8 by ammonia water, and stirring for reacting for 4 hours; filtering and separating after the reaction is completed to obtain beryllium hydroxide precipitate and beryllium precipitating solution. Because the content of impurity elements in the leaching solution is high, valuable elements such as beryllium, rare earth, uranium and the like are adsorbed in the iron precipitation process, and the loss is large; because the sulfate radical concentration in the solution is higher, the uranium recovery rate in the ion exchange adsorption process only reaches 40%; because neutralization precipitation is not thorough in impurity removal, the content of uranium, iron, titanium and sulfate radical in the beryllium hydroxide precipitation is higher, and the quality of the beryllium hydroxide product is reduced. According to the treatment method, the rare earth recovery rate is 94.8%, and the beryllium recovery rate is 85%.
From the above examples and comparative examples, the present invention has the following advantages:
(1) Compared with the prior art, the method has the advantages that the rare earth recovery rate is improved by 5%, the beryllium recovery rate is improved by 6%, and the comprehensive recovery of uranium is realized by adopting the measures of high-temperature high-pressure impurity removal method, rare earth uranium beryllium separation process regulation and control, process solution return and the like.
(2) The cost of the reagent is low. In order to reduce the slag generation amount and valuable metal loss in the iron removal process in the prior art, ammonia water is adopted as a neutralizer, sodium chlorate is adopted as an oxidant to remove iron and aluminum, so that the reagent cost is high; meanwhile, the solution acidity is larger, the volume of the adjusted solution is obviously increased, and the subsequent ammonia-containing wastewater treatment cost is increased. The invention changes CaO, ca (OH) 2 Or CaCO (CaCO) 3 The solution is pre-adjusted, and the acidity and sulfate radical concentration of the solution are regulated and controlled, so that the reagent cost is obviously reduced.
(3) The waste residue is less in production amount and contains less harmful elements. The invention adopts a high-temperature high-pressure impurity removal method, thereby realizing the efficient removal of impurity elements under the condition of higher acidity. Compared with the prior art, the uranium loss rate in the impurity removal process is reduced by 83%, the beryllium loss rate is reduced by 50%, and the yield of the generated impurity removal slag is reduced by 65%; the content of residual uranium and beryllium in the slag can be reduced below the limit value of dangerous waste, so that the influence on the environment is greatly reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The method for separating the rare earth uranium beryllium from the sulfuric acid leaching solution containing the rare earth uranium beryllium is characterized by comprising the following steps of:
mixing sulfuric acid leaching solution containing rare earth uranium beryllium with sodium sulfate, performing precipitation reaction, and performing solid-liquid separation to obtain rare earth sulfuric acid double salt precipitate and first filtrate;
adjusting H in said first filtrate with a calcium-containing substance + The concentration of the mixture is 0.2 to 0.8mol/L, then the temperature is raised to 160 to 210 ℃, and oxygen is introduced to perform high-temperature high-pressure impurity removal reaction to obtain impurity removal slag and second filtrate; the partial pressure of the oxygen is 0.2-1.0 MPa;
carrying out uranium extraction on the second filtrate by utilizing a first organic phase, and separating to obtain a uranium loaded organic phase and a uranium extracted solution; performing back extraction on the uranium loaded organic phase to obtain qualified uranium liquid and a first organic phase;
mixing beryllium loaded organic phase washing liquid with the uranium extracted solution, adding sodium hydroxide or sodium carbonate to adjust the pH value of the obtained mixed solution to be 1.5-2.5, carrying out precipitation and complexation reaction, aging, and carrying out solid-liquid separation to obtain rare earth oxalate precipitation and adjusted solution; the beryllium-loaded organic phase washing liquid is oxalic acid solution and is obtained by washing the beryllium-loaded organic phase of the previous batch;
performing saponification treatment on the second organic phase, and performing beryllium extraction on the adjusted solution by using the saponified second organic phase to obtain a beryllium-loaded organic phase; the second organic phase is P204, TBP and sulfonated kerosene; the volume content of the P204 in the second organic phase is 20-30%, and the volume content of the TBP is 15-30%; the saponification degree of the saponification treatment is 40-65%;
washing the beryllium-loaded organic phase by adopting oxalic acid solution to obtain a beryllium-loaded organic phase washing solution and a washed beryllium-loaded organic phase; back-extracting the washed beryllium loaded organic phase to obtain a second organic phase and beryllium qualified liquid; and returning the beryllium loaded organic phase washing liquid to be mixed with the uranium extraction post-solution of the next batch.
2. The method according to claim 1, wherein the time for the precipitation and complexation reaction after the washing liquid is obtained is 30min; the aging time is 2-4 hours.
3. The method according to claim 1, wherein the concentration of rare earth in the sulfuric acid leaching solution containing rare earth uranium and beryllium is 8-50 g/L, the concentration of beryllium is 1-5 g/L, the concentration of uranium is 30-1000 mg/L, and H + The concentration is 0.5-1.0 mol/L, and the sulfate radical concentration is 60-130 g/L.
4. The method according to claim 1, wherein the precipitation reaction is carried out at a temperature of 90 to 98 ℃ for a time of 0.5 to 2 hours.
5. The method according to claim 1, wherein the content of rare earth elements in the sulfuric acid leaching solution containing rare earth uranium beryllium is calculated as rare earth oxide, and the mass ratio of the rare earth oxide to sodium sulfate is 1: (2.8-4).
6. The method according to claim 1, wherein the calcium-containing substance comprises CaO, ca (OH) or CaCO 3 。
7. The method according to claim 1, wherein the high temperature and high pressure impurity removal reaction time is 1 to 4 hours.
8. The method of claim 1, wherein the first organic phase is kerosene, N235, and TBP; the volume content of N235 in the first organic phase is 1-5%, and the volume content of TBP is 3-10%.
9. The method according to claim 1, characterized in that the reagent used for the back-extraction of the uranium loaded organic phase is a sodium carbonate solution having a concentration of 80-150 g/L.
10. The method of claim 1, wherein the first' organic phase is returned to uranium extraction; the second' organic phase is returned to beryllium extraction.
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