CN103436719A - Lutetium oxide recovered from cerium-doped lutetium aluminate scintillation crystal waste and recovery method - Google Patents
Lutetium oxide recovered from cerium-doped lutetium aluminate scintillation crystal waste and recovery method Download PDFInfo
- Publication number
- CN103436719A CN103436719A CN2013103840849A CN201310384084A CN103436719A CN 103436719 A CN103436719 A CN 103436719A CN 2013103840849 A CN2013103840849 A CN 2013103840849A CN 201310384084 A CN201310384084 A CN 201310384084A CN 103436719 A CN103436719 A CN 103436719A
- Authority
- CN
- China
- Prior art keywords
- lutetium
- mixed solution
- cerium
- scintillation crystal
- crystal waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a lutetium oxide recovered from cerium-doped lutetium aluminate scintillation crystal waste and a recovery method. The method comprises the following steps of: S1, adding sodium hydroxide and/or potassium hydroxide to the scintillation crystal waste, and roasting the mixture to obtain a roasted material; S2, leaching the roasted material in water and filtering, adding nitric acid and an oxidant to the obtained filter residue, and stirring to obtain a mixed liquor; S3, adding the mixed liquor to an organic extracting agent for extraction to obtain a cerium-containing extract and a lutetium-containing raffinate; S4, adding oxalic acid to the lutetium-containing raffinate, stirring, filtering, and firing the obtained precipitate to obtain lutetium oxide. Due to adoption of the process provided by the invention, the lutetium oxide having the purity reaching up to 99% and a recovery rate reaching up to 99.5% is obtained; the process provided by the invention is short in flow, low in equipment investment, simple and easy to operate; resources are saved and pollution is reduced; therefore, the process has huge practical value; a new way of recovering lutetium from the cerium-doped lutetium aluminate scintillation crystal waste is provided.
Description
Technical field
The present invention relates to rare earth recovery technology field, in particular to a kind of lutecium oxide and recovery method reclaimed from mix Cerium aluminate lutetium scintillation crystal waste material.
Background technology
Lutecium oxide has numerous excellent properties, except the active material of the additive as yttrium iron and yttrium aluminum garnet and energy battery and fluorescent material, can also be used to manufacture specific alloy and scintillation crystal, but the lutetium in lutecium oxide is expensive, the lutecium oxide that how to adopt lower cost to obtain high level is the focus of studying at present always.The method for preparing at present lutecium oxide is mainly through extracting and separating, to obtain from the mixed rare earth solution of sipylite gained, wherein, lutecium oxide shared ratio in mishmetal is less than 1%, and the above-mentioned explained hereafter cycle for preparing lutecium oxide is long, cost is high, is unfavorable for long-term development.Mixing Cerium aluminate lutetium scintillation crystal waste material is to produce in the rejected material of the scintillation crystal for preparing nuclear medicine and nuclear industry field, annual all can produce a large amount of Cerium aluminate lutetium scintillation crystal waste materials of mixing, but for the treatment process of these scintillation crystal waste materials, normally discard or accumulation deposit at present, not only having polluted environment has also wasted and has deposited resource, in view of reasons such as lutetium and aluminium, cerium separation factor more complicated, for how from these scintillation crystal waste materials, lutecium oxide to be recycled, turn waste into wealth, go back at present nobody and carry out any trial.
Summary of the invention
The present invention aims to provide a kind of lutecium oxide and recovery method reclaimed from mix Cerium aluminate lutetium scintillation crystal waste material, adopts the method to obtain the lutecium oxide of high purity and high-recovery.
To achieve these goals, according to an aspect of the present invention, provide a kind of method that reclaims lutecium oxide from the scintillation crystal waste material of mixing the Cerium aluminate lutetium, comprised the following steps: S1, in the scintillation crystal waste material, added sodium hydroxide and/or potassium hydroxide, roasting, obtain calcining matter; S2, calcining matter is carried out to water logging, filter, and add nitric acid and oxygenant in the filter residue obtained, stir, obtain mixed solution; S3, mixed solution is joined in organic extractant, extraction, obtain containing the extract of cerium with containing the raffinate of lutetium; And S4, to containing adding oxalic acid in the raffinate of lutetium, stir, filter, the throw out calcination by obtaining, obtain lutecium oxide.
Further, in sodium hydroxide and/or potassium hydroxide and scintillation crystal waste material, the mol ratio of contained cerium is 6:1～10:1.
Further, the maturing temperature in step S1 is 320 ℃～700 ℃, and roasting time is 0.5～2 hour.
Further, oxygenant is potassium bromate or potassium permanganate; In oxygenant and scintillation crystal waste material, the mol ratio of contained cerium is 5:1～1:1.
Further, mixed solution is carried out also comprising before organic extraction: add concentrated nitric acid in mixed solution, the step that the acidity of adjusting mixed solution is 5～10N.
Further, organic extractant is selected from one or more mixed solutions in the mixed solution of the mixed solution of mixed solution, di (isooctyl) phosphate and kerosene of mixed solution, tbp and kerosene of tbp and whiteruss and isooctyl phosphoric acid di-isooctyl and kerosene.
Further, when mixed solution that organic extractant is tbp and whiteruss, per-cent meter by volume, tbp accounts for 10%～60% of described mixed solution, and whiteruss accounts for 40%～90% of described mixed solution.
Further, to also comprising before adding the oxalic acid step in the raffinate of lutetium: will be evaporated containing the raffinate of lutetium, concentrated, and the step of the pH value to 1.5 of the concentrated solution that obtains of adjustment～2.
Further, also comprise the process that the extract containing cerium to obtaining in step S3 is stripped, comprising: add the ascorbic acid solution that mass percent concentration is 0.1～0.5% in extract, stir back extraction 0.5～1 hour; And add the salpeter solution that acidity is 3～8N, agitator treating in the organic extractant after back extraction.
According to a further aspect in the invention, provide a kind of lutecium oxide obtained that reclaims from the scintillation crystal waste material of mixing the Cerium aluminate lutetium, this lutecium oxide adopts above-mentioned any method to reclaim and obtains.
Apply technical scheme of the present invention, by to mixing in Cerium aluminate lutetium scintillation crystal waste material, adding sodium hydroxide and/or potassium hydroxide at high temperature roasting, thereby water extraction, the filtering separation for solid matter that obtain have been removed to impurity aluminum, the cerium of extracting cerium ion remaval doping under acidic conditions after the filter residue dissolving is reoxidized, precipitate rear calcination by what obtain containing the lutetium raffinate, obtained the high-purity mangesium oxide lutetium.Technique provided by the present invention has the advantages such as flow process is short, facility investment is few, simple easy handling, obtained purity up to 99% and the rate of recovery up to 99.5% high-purity mangesium oxide lutetium.Due to the price comparison costliness of Lutetium, the present invention provides a kind of new approach for reclaiming lutetium the scintillation crystal waste material from mixing the Cerium aluminate lutetium, has saved resource, has reduced pollution, has huge practical value.
The accompanying drawing explanation
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention the present invention does not form inappropriate limitation of the present invention for explaining.In the accompanying drawings:
Fig. 1 shows according to the present invention the process flow diagram that reclaims lutecium oxide in exemplary embodiments from mix Cerium aluminate lutetium scintillation crystal waste material.
Embodiment
It should be noted that, in the situation that do not conflict, embodiment and the feature in embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
In the present invention indication to mix Cerium aluminate lutetium scintillation crystal waste material be to obtain the scintillation crystal of using from nuclear medicine, general salic 20～40%, oxidation-containing cerium 0.5～1%, remaining lutecium oxide is 60～80%.
A kind of method that reclaims lutecium oxide from the scintillation crystal waste material of mixing the Cerium aluminate lutetium of a kind of exemplary embodiment according to the present invention as shown in Figure 1, comprises the following steps: S1, in the scintillation crystal waste material, add alkaline matter, roasting, obtain calcining matter; S2, calcining matter is carried out to water logging, filter, and add nitric acid and oxygenant in the filter residue obtained, stir, obtain mixed solution; S3, will in mixed solution, join in organic extractant, extraction, obtain containing the extract of cerium with containing the raffinate of lutetium; S4, to containing adding oxalic acid in the raffinate of lutetium, stir, filter, the throw out calcination by obtaining, obtain lutecium oxide.
By to mixing in Cerium aluminate lutetium scintillation crystal waste material, adding sodium hydroxide and/or potassium hydroxide at high temperature roasting, by the solid matter obtained dissolved, thereby filtering separation removed impurity aluminum, filter residue is dissolved and reoxidizes cerium rear and that the extracting cerium ion remaval adulterates under acidic conditions, by calcination after the precipitation of the raffinate containing lutetium obtained, obtained the high-purity mangesium oxide lutetium.Technique provided by the present invention has the advantages such as flow process is short, facility investment is few, simple easy handling, obtained purity up to 99% and the rate of recovery up to 99.5% high-purity mangesium oxide lutetium.Due to the price comparison costliness of Lutetium, the present invention provides a kind of new approach for reclaiming lutetium the scintillation crystal waste material from mixing the Cerium aluminate lutetium, has saved resource, has reduced pollution, has huge practical value.
For the metallic aluminium by waste material is fully separated from the scintillation crystal waste material of mixing the Cerium aluminate lutetium, the application is chosen in step S1 and adds sodium hydroxide and/or potassium hydroxide, 320 ℃～700 ℃ lower roastings 0.5～2 hour, now sodium hydroxide and/or potassium hydroxide and mix Cerium aluminate lutetium generation chemical reaction, generate sodium aluminate and/or potassium aluminate, cerous hydroxide, hydroxide lutetium, by using the water extraction calcining matter, sodium aluminate and/or potassium aluminate are soluble in water, and cerous hydroxide and hydroxide lutetium are water insoluble, through filtering, just impurity aluminum can be separated.
In the sodium hydroxide wherein added in step S1 and/or the amount of potassium hydroxide and scintillation crystal waste material, the mol ratio of contained oxide aggregate is 6:1～10:1.If both mol ratios are less than 6:1, can cause the aluminium in the scintillation crystal waste material can not be converted into sodium aluminate and/or potassium aluminate fully, make cerium contained in the scintillation crystal waste material and lutetium can not be converted into cerous hydroxide, hydroxide lutetium fully, so still have some scintillation crystal waste materials and do not react and left behind, make the purity of the lutecium oxide obtained and the rate of recovery decrease; If both mol ratios are greater than 10:1, base excess can cause solution basicity and the viscosity after the calcining matter water logging excessive, affects to filtration fully separating impurity aluminium, thereby affect the purity of lutecium oxide product, in addition, also can increase raw materials cost, also can cause the erosion of equipment simultaneously.
In the water logging process, preferably adopt hot water to carry out water logging.Consider that the fusing point of potassium hydroxide is higher than sodium hydroxide, and the cost ratio sodium hydroxide of potassium hydroxide is high, so preferably adopting low melting point to reach sodium hydroxide cheaply, the present invention carries out roasting with the scintillation crystal waste material of mixing the Cerium aluminate lutetium, make like this separation of impurity aluminum complete, the purity of the final product lutecium oxide obtained and yield is higher and cost is lower.Wherein being chosen in 320 ℃～700 ℃ lower roastings 0.5～2 hour is mainly to consider that the fusing point of sodium hydroxide is 318.4 ℃, if maturing temperature is lower than 320 ℃, can exist sodium hydroxide to melt incomplete problem, thereby cause sodium hydroxide can't fully react with the scintillation crystal waste material, aluminium in the scintillation crystal waste material can not generate sodium aluminate fully, the degree of separating impurity aluminium is thorough not like this, does not reach the purpose of abundant separation; If maturing temperature higher than 700 ℃, can make the sodium aluminate generated resolve into aluminum oxide, thereby also can't reach the purpose of abundant separating impurity aluminium.
Add nitric acid and oxygenant after filtering in the filter cake obtained, a preferred embodiment of the invention, oxygenant is potassium bromate or potassium permanganate.The purpose that adds nitric acid in this step is filter cake to be dissolved as to the solution of nitric acid system, and the purpose that adds oxygenant is for the Ce by contained in filter cake
3+exhaustive oxidation becomes Ce
4+, this is that extraction agent only extracts quadrivalent cerium as the TBP extraction agent, and does not extract the trivalent lutetium because under high acid environment, thereby reaches the purpose that the cerium lutetium separates.In order to guarantee the Ce in filter cake
3+exhaustive oxidation becomes Ce
4+, the oxygenant needs that add are excessive a little, and according to a preferred embodiment of the present invention, oxygenant is potassium bromate or potassium permanganate; Wherein in oxygenant and scintillation crystal waste material, the mol ratio of contained cerium is 5:1～1:1.If in oxygenant and scintillation crystal waste material, the mol ratio of contained cerium is greater than 5:1, make in mixed solution the oxygenant solute concentration increase and occur that viscosity of mixed liquid is excessive, cause phase-splitting bad and affect the degree of cerium impurity separation; Reduce purity and the yield of the lutecium oxide finally obtained; If in oxygenant and scintillation crystal waste material, the mol ratio of contained cerium is less than 1:1, the trivalent cerium in mixed solution can not be oxidized to quadrivalent cerium fully, makes cerium impurity separate not thorough, can reduce equally the purity of product lutecium oxide.
Obtained mixed solution after adding nitric acid and oxygenant, a preferred embodiment of the invention, carrying out also comprising before organic extraction to mixed solution: add concentrated nitric acid in mixed solution, the step that the acidity of adjusting mixed solution is 5～10N.It is to improve the acidity of mixed solution that the acidity of mixed solution is adjusted into to the purpose that 5～10N extracted, and contributes to the extracting and separating of cerium and lutetium; If the acidity of mixed solution lower than 5N, there will be a large amount of lutetiums to be extracted in organic phase, reduce the yield of product lutetium; If the acidity of mixed solution, higher than 10N, there will be the phenomenon that viscosity of mixed liquid is excessive, acid mist is serious, cause phase-splitting bad and affect cerium impurity and separate not exclusively, also can cause work under bad environment and then unhealthful.Therefore the acidity that the present invention preferably carries out before organic extraction adjusting mixed solution to mixed solution is 5～10N, has guaranteed carrying out smoothly of follow-up organic extraction step, can make extraction more fully and completely.
Preferably, organic extractant is selected from one or more mixed solutions in the mixed solution of the mixed solution of mixed solution, di (isooctyl) phosphate and kerosene of mixed solution, tbp and kerosene of tributyl phosphate and whiteruss and isooctyl phosphoric acid di-isooctyl and kerosene.The present invention preferably but be not limited to above-mentioned organic extraction solvent, adopts above-mentioned organic extractant to have that phase-splitting is fast, the easy advantage of back extraction.Wherein adding the oil phase in mixed solution after organic extractant is 5:1～1:1 than O:A.When mixed solution that organic extractant is tbp (TBP) and whiteruss, per-cent meter by volume, TBP accounts for 10%～60% of described mixed solution, and whiteruss accounts for 40%～90% of mixed solution.By mixed solution is carried out to organic extraction, can be so that the Ce in mixed solution
4+enter into organic extractant, lutetium ion is retained in raffinate, so just will mix the cerium adulterated in Cerium aluminate lutetium scintillation crystal waste material and thoroughly remove.
In order to make the organic extractant can recycle, according to a kind of exemplary embodiment of the present invention, also comprise the process that the extract to obtaining in step S3 is stripped, comprise: add the ascorbic acid solution that mass percent concentration is 0.1～0.5% in extract, stir back extraction 0.5～1 hour; And add the salpeter solution that acidity is 3～8N, agitator treating in the organic extractant after back extraction.The ascorbic acid solution added can be reduced into trivalent cerium by the quadrivalent cerium in extraction agent, thereby plays ceric purpose in the back extraction extraction agent.The xitix that this place adopts is a kind of water-soluble vitamin c, and molecular formula is C
6h
8o
6, due to ascorbic acid solution, easily by light and atmospheric oxidation, need now with the current.Wherein adopting the organic extractant after salpeter solution that acidity is 3～8N washing back extraction is in order to wash away xitix residual in organic extractant, guarantees not affect when organic extractant recycles the percentage extraction of cerium.
In order to obtain highly purified lutecium oxide, need to be to adding in raffinate oxalic acid to make that lutetium element in raffinate is precipitated to get off.The add-on of oxalic acid, also can be excessive according to the lutetium element in raffinate being precipitated as to benchmark fully.A preferred embodiment of the invention also comprised before adding the oxalic acid step in raffinate: by raffinate evaporated, concentrated, and adjust the step of the pH value to 1.5 of the concentrated solution obtained～2.Due to by Ce
3+be oxidized to Ce
4+process in added more concentrated nitric acid, the part concentrated nitric acid remains in raffinate, the stronger acidity that makes raffinate present is unfavorable for lutetium ion precipitation.By adding deionized water to adjust the pH value to 1.5 of concentrated solution～2, by weakening the acidic conditions of raffinate, be conducive to lutetium ion and precipitate, thereby guaranteed purity and the yield of the lutecium oxide product that finally obtains.By the throw out of the oxalic acid lutetium that obtains after filtering through 800 ℃～950 ℃ calcinations after 2～4 hours lutecium oxide.
According to a further aspect in the invention, provide a kind of lutecium oxide obtained that reclaims from the scintillation crystal waste material of mixing the Cerium aluminate lutetium, wherein above-mentioned any method of lutecium oxide employing reclaims and obtains.Adopt the purity of the lutecium oxide product that aforesaid method provided by the present invention prepares to be greater than 99.5%.
Further illustrate beneficial effect of the present invention below in conjunction with specific embodiment:
Embodiment 1
1) take the commercially available scintillation crystal waste material of 50 grams (concrete composition in Table 1) and be placed in corundum crucible, then add sodium hydroxide roasting 2 hours in the retort furnace of 700 ℃, obtain calcining matter; Wherein in sodium hydroxide and scintillation crystal waste material, total mol ratio of institute's oxycompound is 6:1.
2) add hot water leaching 30 minutes in calcining matter, filter, wash 5 times, obtain filter cake.In filter cake, adding appropriate concentrated nitric acid to be heated to 60 ℃ of dissolving filter cakes, until dissolve limpid rear coolingly, is that 5:1(is KBrO by the mol ratio of cerium contained in oxygenant and scintillation crystal waste material
3: CeO
2=5:1) add oxygenant bromic acid potassium, stir 30 minutes, obtain mixed solution.
3) be 10N to the acidity that adds in mixed solution concentrated nitric acid to adjust mixed solution, the mixed solution after acid adjustment is joined in organic extractant and extracted, wherein, comparing O:A is 5:1, and extraction time is 30min.The mixture that organic extractant is TBP and whiteruss (according to the volume percent meter, TBP accounts for 10% of mixture, whiteruss account for mixture 90%).Be extracted thing and raffinate through extraction.
4) by raffinate through 100 ℃ of evaporation concentration 2 hours, then add the pH value to 1.5 that deionized water is regulated concentrated solution.The oxalic acid precipitation lutetium that adds 53 grams in the solution that is 1.5 to the pH value, filter, and obtains oxalic acid lutetium throw out, oxalic acid lutetium throw out obtained to the lutecium oxide product after 2 hours 850 ℃ of calcinations.
Embodiment 2
1) take the 50 commercially available scintillation crystal waste materials of gram (composition is in Table 1) and be placed in corundum crucible, then add sodium hydroxide roasting 0.5 hour in the retort furnace of 320 ℃, obtain calcining matter; Wherein in sodium hydroxide and scintillation crystal waste material, total mol ratio of institute's oxycompound is 10:1.
2) add hot water leaching 30 minutes in calcining matter, filter, wash 4 times, obtain filter cake.In filter cake, adding appropriate concentrated nitric acid to be heated to 60 ℃ of dissolving filter cakes, until dissolve limpid rear coolingly, is that 3:1(is KBrO by the mol ratio of cerium contained in oxygenant and scintillation crystal waste material
3: CeO
2=3:1) add oxygenant bromic acid potassium, stir 30min, obtain mixed solution.
3) be 5N to the acidity that adds in mixed solution concentrated nitric acid to adjust mixed solution, the mixed solution after acid adjustment is joined in organic extractant and extracted, wherein, comparing O:A is 5:1, and extraction time is 30min.The mixture that organic extractant is TBP and whiteruss (according to the volume percent meter, TBP accounts for 60% of mixture, whiteruss account for mixture 40%).Be extracted thing and raffinate through extraction.
4) by raffinate through 120 ℃ of evaporation concentration 1.5 hours, then add the pH value to 2 that deionized water is regulated concentrated solution.The oxalic acid precipitation lutetium that adds 53 grams in the solution that is 2 to the pH value, filter, and obtains oxalic acid lutetium throw out, oxalic acid lutetium throw out obtained to the lutecium oxide product after 2.5 hours 850 ℃ of calcinations.
Embodiment 3
1) take the 50 commercially available scintillation crystal waste materials of gram (composition is in Table 1) and be placed in corundum crucible, then add potassium hydroxide roasting 1.25 hours in the retort furnace of 510 ℃, obtain calcining matter; Wherein in potassium hydroxide and scintillation crystal waste material, the mol ratio of contained oxide aggregate is 8:1.
2) add hot water leaching 30 minutes in calcining matter, filter, wash 4 times, obtain filter cake.In filter cake, adding appropriate concentrated nitric acid to be heated to 60 ℃ of dissolving filter cakes, until dissolve limpid rear coolingly, is that 1:1(is KBrO by the mol ratio of cerium contained in oxygenant and scintillation crystal waste material
3: CeO
2=1:1) add oxygenant bromic acid potassium, stir 30min, obtain mixed solution.
3) be 7.5N to the acidity that adds in mixed solution concentrated nitric acid to adjust mixed solution, the mixed solution after acid adjustment is joined in organic extractant and extracted, wherein, comparing O:A is 5:1, and extraction time is 30min.The mixture that organic extractant is TBP and whiteruss (according to the volume percent meter, TBP accounts for 35% of mixture, whiteruss account for mixture 65%).Be extracted thing and raffinate through extraction.
4) by raffinate through 100 ℃ of evaporation concentration 2.5 hours, then add the pH value to 1.8 that deionized water is regulated concentrated solution.The oxalic acid precipitation lutetium that adds 53 grams in the solution that is 1.8 to the pH value, filter, and obtains oxalic acid lutetium throw out, oxalic acid lutetium throw out obtained to the lutecium oxide product after 2.5 hours 850 ℃ of calcinations.
Embodiment 4
Identical with raw material and the operation steps of embodiment 1, difference is that the mol ratio of contained oxide aggregate in adopted calcination agent sodium hydroxide and scintillation crystal waste material is 5:1.
Embodiment 5
Identical with raw material and the operation steps of embodiment 1, difference is that the mol ratio of contained oxide aggregate in adopted oxygenant sodium hydroxide and scintillation crystal waste material is 11:1.
Embodiment 6
Identical with raw material and the operation steps of embodiment 1, difference is that the mol ratio of cerium contained in added oxygenant bromic acid potassium and scintillation crystal waste material is 7:1.
Embodiment 7
Identical with raw material and the operation steps of embodiment 1, difference is that the mol ratio of cerium contained in added oxygenant bromic acid potassium and scintillation crystal waste material is 1:2.
Embodiment 8
Identical with raw material and the operation steps of embodiment 2, difference is in step 3) that the acidity that adds concentrated nitric acid to adjust mixed solution in mixed solution is 3N.
Embodiment 9
Identical with raw material and the operation steps of embodiment 2, difference is in step 3) that the acidity that adds concentrated nitric acid to adjust mixed solution in mixed solution is 12N.
Comparative Examples 1
Identical with raw material and the operation steps of embodiment 1, difference is that selected calcination agent is not sodium hydroxide or potassium hydroxide, but sodium carbonate.
Adopt plasma emission spectrometer and weighting method to be detected the composition in final product lutecium oxide in embodiment 1～9 and Comparative Examples 1, detected result is specifically in Table 1.
Table 1
Wherein R means the mol ratio of oxide aggregate in calcination agent and scintillation crystal waste material, and N means the mol ratio of cerium contained in oxygenant and scintillation crystal waste material.
Detected result from table 1 is known, and the lutecium oxide product purity that adopts technique of the present invention to prepare is all up to more than 99.5%, and yield surpasses 94%.From the data of embodiment 4 and embodiment 5, can find out, when the mol ratio of the oxide aggregate by the calcination agent that is added sodium hydroxide or potassium hydroxide and scintillation crystal waste material is not within the scope at 6:1～10:1, purity and the rate of recovery of the lutecium oxide product of final preparation can decrease.
When in added oxygenant bromic acid potassium and scintillation crystal waste material, the mol ratio of contained cerium is not within the scope at 5:1～1:1, as more as the oxidant content added in embodiment 6, both mol ratios are 7:1, the amount of the oxygenant added in embodiment 7 is less, both mol ratios are 1:2, and the purity of the lutecium oxide product now obtained and the rate of recovery also can be lower than purity and the rate of recovery of the lutecium oxide in embodiment 1.Concrete analysis, when the add-on of oxygenant is more, in mixed solution, solute concentration increases and just there will be viscosity of mixed liquid excessive, causes phase-splitting bad and affect cerium impurity and separate incomplete; When the add-on of oxygenant is less, trivalent cerium just can not be oxidized to quadrivalent cerium fully, cerium impurity just separates not thorough, the add-on of visible oxygenant is to affect the key factor that cerium separates with lutetium, and selecting suitable oxygenant and addition thereof is the key factor of preparation high purity and high-recovery lutecium oxide product.
Acidity in mixed solution after adding oxygenant is not between 5～10 the time, as the acidity in embodiment 8 is 3N, and the acidity in embodiment 9 is 12 o'clock, the purity of the lutecium oxide product finally obtained and the rate of recovery are all lower than the purity in embodiment 1 and the rate of recovery, concrete analysis, acidity in mixed solution hour, there will be a large amount of lutetiums to be extracted in organic phase, causes the yield of product lutetium seriously on the low side; When if the acidity of mixed solution is larger, there will be that viscosity of mixed liquid is excessive, acid mist is serious, cause phase-splitting bad and affect cerium impurity and separate, visible, the acidity of mixed solution is to affect the key factor that cerium separates with lutetium.In addition, acidity is higher also can affect Working environment, thereby affects HUMAN HEALTH.The advantages such as in addition, recovery process of the present invention has condition easily to be controlled, and product yield is high, and technical process is short, and facility investment is few.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a method that reclaims lutecium oxide from the scintillation crystal waste material of mixing the Cerium aluminate lutetium, is characterized in that, comprises the following steps:
S1, in described scintillation crystal waste material, add sodium hydroxide and/or potassium hydroxide, roasting, obtain calcining matter;
S2, described calcining matter is carried out to water logging, filter, and add nitric acid and oxygenant in the filter residue obtained, stir, obtain mixed solution;
S3, described mixed solution is joined in organic extractant, extraction, obtain containing the extract of cerium with containing the raffinate of lutetium; And
S4, to described, containing adding oxalic acid in the raffinate of lutetium, stir, filter, the throw out calcination by obtaining, obtain described lutecium oxide.
2. method according to claim 1, is characterized in that, in described sodium hydroxide and/or potassium hydroxide and described scintillation crystal waste material, the mol ratio of contained cerium is 6:1～10:1.
3. method according to claim 1, is characterized in that, the maturing temperature in described step S1 is 320 ℃～700 ℃, and roasting time is 0.5～2 hour.
4. method according to claim 1, is characterized in that, described oxygenant is potassium bromate or potassium permanganate; In described oxygenant and described scintillation crystal waste material, the mol ratio of contained cerium is 5:1～1:1.
5. method according to claim 1, is characterized in that, described mixed solution is carried out also comprising before organic extraction:
Add concentrated nitric acid in described mixed solution, the step that the acidity of adjusting described mixed solution is 5～10N.
6. method according to claim 1, it is characterized in that, described organic extractant is selected from one or more mixed solutions in the mixed solution of the mixed solution of mixed solution, di (isooctyl) phosphate and kerosene of mixed solution, tbp and kerosene of tbp and whiteruss and isooctyl phosphoric acid di-isooctyl and kerosene.
7. method according to claim 6, it is characterized in that, when mixed solution that described organic extractant is described tbp and described whiteruss, per-cent meter by volume, described tbp accounts for 10%～60% of described mixed solution, and described whiteruss accounts for 40%～90% of described mixed solution.
8. method according to claim 1, is characterized in that, to described, before adding the oxalic acid step in the raffinate of lutetium, also comprises:
By the described raffinate containing lutetium evaporated, concentrated, and adjust the step of the pH value to 1.5 of the concentrated solution obtained～2.
9. method according to claim 1, is characterized in that, also comprises the described process of being stripped containing the extract of cerium to obtaining in described step S3, comprising:
Add the ascorbic acid solution that mass percent concentration is 0.1～0.5% in described extract, stir back extraction 0.5～1 hour; And
Add the salpeter solution that acidity is 3～8N, agitator treating in the described organic extractant after described back extraction.
10. one kind is reclaimed the lutecium oxide obtained from the scintillation crystal waste material of mixing the Cerium aluminate lutetium, it is characterized in that, described lutecium oxide adopts any one method recovery in claim 1 to 9 to obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310384084.9A CN103436719B (en) | 2013-08-29 | 2013-08-29 | From mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310384084.9A CN103436719B (en) | 2013-08-29 | 2013-08-29 | From mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103436719A true CN103436719A (en) | 2013-12-11 |
| CN103436719B CN103436719B (en) | 2015-07-29 |
Family
ID=49690432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310384084.9A Active CN103436719B (en) | 2013-08-29 | 2013-08-29 | From mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103436719B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274362A (en) * | 2015-11-05 | 2016-01-27 | 江西理工大学 | Method for reinforcement-reduction leaching of rare earth in ion absorption type rare earth mine |
| CN106191478A (en) * | 2016-08-31 | 2016-12-07 | 虔东稀土集团股份有限公司 | A kind of recovery method of lutecium element |
| CN109055783A (en) * | 2018-08-15 | 2018-12-21 | 湖南稀土金属材料研究院 | The recovery method of the middle rare earth of waste material containing rare earth oxide |
| CN110042245A (en) * | 2019-03-29 | 2019-07-23 | 甘肃稀土新材料股份有限公司 | A method of the recycling purification lutetium from silicic acid lutetium yttrium scintillation crystal waste |
| CN110306059A (en) * | 2019-07-30 | 2019-10-08 | 江西省科学院应用化学研究所 | A method of rare earth in recycling cerium dopping yttrium luetcium silicate waste material |
| CN113735156A (en) * | 2021-08-12 | 2021-12-03 | 湖南稀土金属材料研究院有限责任公司 | Preparation method of ultrapure cerium dioxide |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041183A (en) * | 1988-09-16 | 1990-04-11 | 日本重化学工业株式会社 | The separation method of rare earth element |
| CN1410564A (en) * | 2001-09-21 | 2003-04-16 | 内蒙古包钢稀土高科技股份有限公司 | Method for extracting cerium from cerium-containing rare earth sulfuric acid solution by oxidation |
| CN1675131A (en) * | 2002-06-07 | 2005-09-28 | 昭和电工株式会社 | Process for recovering rare earth oxide from waste liquid containing rare earth element, and process for producing rare earth oxide using same |
| CN101012501A (en) * | 2007-02-05 | 2007-08-08 | 金坛市西南化工研究所 | Method for fully separating high-purity rare earth oxide from yttrium-rich rare earth ore |
| CN101307391A (en) * | 2008-07-11 | 2008-11-19 | 广州有色金属研究院 | Process for recovering rare earth element in waste florescent lamps |
| CN101705380A (en) * | 2009-11-30 | 2010-05-12 | 北京有色金属研究总院 | Method for recovering rare earth from rare earth-containing aluminum-silicon materials |
| CN101748275A (en) * | 2009-12-22 | 2010-06-23 | 江阴加华新材料资源有限公司 | Preparation method of low-thorium lutetium oxide |
| CN101985694A (en) * | 2010-10-26 | 2011-03-16 | 赣县金鹰稀土实业有限公司 | Preparation method for recovering high-purity yttrium europium from fluorescent powder scrap |
| CN102115822A (en) * | 2010-11-18 | 2011-07-06 | 吴泉锦 | Method for recovering rare earth oxide from fluorescent powder and polishing powder waste |
| CN102634667A (en) * | 2012-04-26 | 2012-08-15 | 中国科学院城市环境研究所 | Method for recycling rear-earth elements form abandoned fluorescent lamps |
| CN103131874A (en) * | 2011-12-02 | 2013-06-05 | 荆门市格林美新材料有限公司 | Method recovering rare earth from precise instrument waste glass materials |
-
2013
- 2013-08-29 CN CN201310384084.9A patent/CN103436719B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041183A (en) * | 1988-09-16 | 1990-04-11 | 日本重化学工业株式会社 | The separation method of rare earth element |
| CN1410564A (en) * | 2001-09-21 | 2003-04-16 | 内蒙古包钢稀土高科技股份有限公司 | Method for extracting cerium from cerium-containing rare earth sulfuric acid solution by oxidation |
| CN1675131A (en) * | 2002-06-07 | 2005-09-28 | 昭和电工株式会社 | Process for recovering rare earth oxide from waste liquid containing rare earth element, and process for producing rare earth oxide using same |
| CN101012501A (en) * | 2007-02-05 | 2007-08-08 | 金坛市西南化工研究所 | Method for fully separating high-purity rare earth oxide from yttrium-rich rare earth ore |
| CN101307391A (en) * | 2008-07-11 | 2008-11-19 | 广州有色金属研究院 | Process for recovering rare earth element in waste florescent lamps |
| CN101705380A (en) * | 2009-11-30 | 2010-05-12 | 北京有色金属研究总院 | Method for recovering rare earth from rare earth-containing aluminum-silicon materials |
| CN101748275A (en) * | 2009-12-22 | 2010-06-23 | 江阴加华新材料资源有限公司 | Preparation method of low-thorium lutetium oxide |
| CN101985694A (en) * | 2010-10-26 | 2011-03-16 | 赣县金鹰稀土实业有限公司 | Preparation method for recovering high-purity yttrium europium from fluorescent powder scrap |
| CN102115822A (en) * | 2010-11-18 | 2011-07-06 | 吴泉锦 | Method for recovering rare earth oxide from fluorescent powder and polishing powder waste |
| CN103131874A (en) * | 2011-12-02 | 2013-06-05 | 荆门市格林美新材料有限公司 | Method recovering rare earth from precise instrument waste glass materials |
| CN102634667A (en) * | 2012-04-26 | 2012-08-15 | 中国科学院城市环境研究所 | Method for recycling rear-earth elements form abandoned fluorescent lamps |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274362A (en) * | 2015-11-05 | 2016-01-27 | 江西理工大学 | Method for reinforcement-reduction leaching of rare earth in ion absorption type rare earth mine |
| CN105274362B (en) * | 2015-11-05 | 2017-05-03 | 江西理工大学 | Method for reinforcement-reduction leaching of rare earth in ion absorption type rare earth mine |
| CN106191478A (en) * | 2016-08-31 | 2016-12-07 | 虔东稀土集团股份有限公司 | A kind of recovery method of lutecium element |
| CN106191478B (en) * | 2016-08-31 | 2018-12-18 | 虔东稀土集团股份有限公司 | A kind of recovery method of lutetium element |
| CN109055783A (en) * | 2018-08-15 | 2018-12-21 | 湖南稀土金属材料研究院 | The recovery method of the middle rare earth of waste material containing rare earth oxide |
| CN109055783B (en) * | 2018-08-15 | 2021-06-04 | 湖南稀土金属材料研究院 | Method for recovering rare earth oxide from waste containing rare earth oxide |
| CN110042245A (en) * | 2019-03-29 | 2019-07-23 | 甘肃稀土新材料股份有限公司 | A method of the recycling purification lutetium from silicic acid lutetium yttrium scintillation crystal waste |
| CN110306059A (en) * | 2019-07-30 | 2019-10-08 | 江西省科学院应用化学研究所 | A method of rare earth in recycling cerium dopping yttrium luetcium silicate waste material |
| CN110306059B (en) * | 2019-07-30 | 2020-12-25 | 江西省科学院应用化学研究所 | Method for recycling rare earth in cerium-doped lutetium yttrium silicate waste |
| CN113735156A (en) * | 2021-08-12 | 2021-12-03 | 湖南稀土金属材料研究院有限责任公司 | Preparation method of ultrapure cerium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103436719B (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103361486B (en) | Method for extracting high purity scandium oxide and titanium from waste acid solution containing scandium and titanium | |
| CN103436719A (en) | Lutetium oxide recovered from cerium-doped lutetium aluminate scintillation crystal waste and recovery method | |
| CN102312098B (en) | Method for separation and purification of fluorescent grade yttrium oxide and europium oxide from waste phosphor powder | |
| CN102660688B (en) | Method for recovering rare earth from waste rare earth luminescent material | |
| CN103194609B (en) | Method for preparing scandium oxide by using rough scandium extracted from waste acid water of titanium dioxide as raw material | |
| CN102796876B (en) | Method for extracting scandium oxide from titanium slag chloride waste | |
| CN102994781B (en) | Method for separation and purification of thorium | |
| CN103773966B (en) | The extraction and application method of neodymium iron boron waste material | |
| CN102745735B (en) | A kind of method reclaiming discarded red fluorescence powder rare earth elements | |
| US20230265541A1 (en) | method for recovering rare-earth in cerium-based rare-earth polishing powder waste by two-step acid leaching gradient separation | |
| CN104928475B (en) | A kind of recovery method of the aluminium scrap silicon containing rare earth | |
| CN104928504B (en) | A kind of recovery method of aluminium scrap silicon middle rare earth | |
| CN102690962A (en) | Method for recovering scandium in waste acidic water from titanium dioxide production | |
| CN103695671A (en) | Method for recycling and purifying scandium oxide powder from waste acid in zirconium salt production | |
| CN106636689A (en) | Method for extracting rare earth from precipitation sludge of rare earth wastewater pool | |
| CN102424420A (en) | Method for preparing niobium pentoxide by using ferrocolumbium as raw material | |
| CN103243220A (en) | Treatment method of fused salt chlorination slag | |
| CN105039698A (en) | Method of high-effectively recycling rare earth from waste CRT fluorescent powder | |
| CN106756023A (en) | The method that depth separates calcium and magnesium impurity in manganese sulfate | |
| CN108220631A (en) | A kind of method using aluminum-extracted pulverized fuel ash process condensing crystallizing mother liquor scandium | |
| CN103540746B (en) | Method of separating lanthanum from rare earth nitrate slurry as well as rare earth ore concentrate separation method | |
| CN108950251A (en) | The recovery method of rare earth element | |
| CN102465203B (en) | Method for directly preparing cerium fluoride by extraction and separation | |
| CN102701262B (en) | Method for recovering scandium from titanium dioxide wastewater on large scale | |
| CN103922383A (en) | Extraction separation method for rare earth and zinc in reverse extraction raffinate obtained in reduction extraction separation of europium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |