CN103436719B - From mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste - Google Patents
From mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste Download PDFInfo
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- CN103436719B CN103436719B CN201310384084.9A CN201310384084A CN103436719B CN 103436719 B CN103436719 B CN 103436719B CN 201310384084 A CN201310384084 A CN 201310384084A CN 103436719 B CN103436719 B CN 103436719B
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Abstract
The invention discloses a kind of from mixing the lutecium oxide and recovery method that reclaim the scintillation crystal waste of Cerium aluminate lutetium.The method comprises the following steps: S1, in scintillation crystal waste, add sodium hydroxide and/or potassium hydroxide, roasting, obtains calcining matter; S2, calcining matter is carried out 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 the extract containing cerium and the raffinate containing lutetium; And S4, to containing lutetium raffinate in add oxalic acid, stir, filter, by the throw out calcination obtained, obtain lutecium oxide.Adopt technique of the present invention to obtain high purity 99% and the rate of recovery up to 99.5% lutecium oxide, present invention process flow process is short, facility investment is few, simple easy handling, save resource, decrease pollution, there is huge practical value, provide and a kind ofly from the scintillation crystal waste of mixing Cerium aluminate lutetium, reclaim the new approach of lutetium.
Description
Technical field
The present invention relates to rare earth recovery technology field, in particular to a kind of from mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste.
Background technology
Lutecium oxide has numerous excellent properties, except being used as yttrium iron and the additive of yttrium aluminum garnet and the active material of 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 how adopting lower cost to obtain high level is the focus of research at present always.The method preparing lutecium oxide at present mainly obtains through extracting and separating from the mixed rare earth solution of sipylite gained, wherein, the ratio shared in mishmetal of lutecium oxide is less than 1%, and the above-mentioned explained hereafter cycle of preparing lutecium oxide is long, cost is high, is unfavorable for long-term development.Mixing Cerium aluminate lutetium scintillation crystal waste is produce in the rejected material of the scintillation crystal preparing nuclear medicine and nuclear industry field, annual all can generation a large amount of mixes Cerium aluminate lutetium scintillation crystal waste, but the treatment process at present for these scintillation crystal waste is normally discarded or accumulation deposit, not only pollute environment to waste and deposit resource, in view of lutetium and the reason such as aluminium, cerium separation factor more complicated, for how to recycle lutecium oxide from these scintillation crystal waste, turn waste into wealth, go back nobody at present and carry out any trial.
Summary of the invention
The present invention aims to provide a kind of from mixing the lutecium oxide and recovery method that reclaim Cerium aluminate lutetium scintillation crystal waste, 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 reclaiming lutecium oxide from the scintillation crystal waste of mixing Cerium aluminate lutetium, comprise the following steps: S1, in scintillation crystal waste, add sodium hydroxide and/or potassium hydroxide, roasting, obtains calcining matter; S2, calcining matter is carried out 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 the extract containing cerium and the raffinate containing lutetium; And S4, to containing lutetium raffinate in add oxalic acid, stir, filter, by the throw out calcination obtained, obtain lutecium oxide.
Further, in sodium hydroxide and/or potassium hydroxide and scintillation crystal waste, the mol ratio of contained cerium is 6:1 ~ 10:1.
Further, the maturing temperature in step S1 is 320 DEG C ~ 700 DEG C, and roasting time is 0.5 ~ 2 hour.
Further, oxygenant is potassium bromate or potassium permanganate; The mol ratio of cerium contained in oxygenant and scintillation crystal waste is 5:1 ~ 1:1.
Further, also comprise: in mixed solution, add concentrated nitric acid to mixed solution before carrying out organic extraction, the acidity of adjustment mixed solution is the step of 5 ~ 10N.
Further, organic extractant is selected from one or more mixed solutions in the mixed solution of the mixed solution of tbp and whiteruss, tbp and kerosene, di (isooctyl) phosphate and the mixed solution of kerosene and the mixed solution of isooctyl phosphoric acid di-isooctyl and kerosene.
Further, when organic extractant is the mixed solution of tbp and whiteruss, by volume percentages, tbp accounts for 10% ~ 60% of described mixed solution, and whiteruss accounts for 40% ~ 90% of described mixed solution.
Further, also comprise to before adding oxalic acid step in the raffinate of lutetium: the raffinate containing lutetium is carried out evaporate, concentrate, and adjust the step of pH value to 1.5 ~ 2 of the concentrated solution obtained.
Further, also comprising the process of stripping containing the extract of cerium to obtaining in step S3, comprising: in extract, add the ascorbic acid solution that mass percent concentration is 0.1 ~ 0.5%, stir back extraction 0.5 ~ 1 hour; And in the organic extractant after back extraction, add the salpeter solution that acidity is 3 ~ 8N, agitator treating.
According to a further aspect in the invention, provide and a kind ofly from the scintillation crystal waste of mixing Cerium aluminate lutetium, reclaim the lutecium oxide obtained, this lutecium oxide adopts any one method above-mentioned to reclaim and obtains.
Apply technical scheme of the present invention, by adding sodium hydroxide and/or potassium hydroxide also at high temperature roasting to mixing in Cerium aluminate lutetium scintillation crystal waste, by the solid matter water extraction obtained, filtering separation thus eliminate impurity aluminum, filter residue is dissolved the cerium of extracting cerium ion remaval doping in acid condition after reoxidizing, precipitate rear calcination by what obtain containing lutetium raffinate, obtain 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, obtain high purity 99% and the rate of recovery up to 99.5% high-purity mangesium oxide lutetium.Because the price comparison of Lutetium is expensive, the present invention reclaims lutetium to provide a kind of new approach from the scintillation crystal waste of mixing Cerium aluminate lutetium, has saved resource, has decreased pollution, had huge practical value.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 show according in exemplary embodiments of the present invention from mixing the process flow diagram reclaiming lutecium oxide Cerium aluminate lutetium scintillation crystal waste.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
In the present invention, the Cerium aluminate lutetium scintillation crystal waste of mixing of indication obtains from the scintillation crystal of nuclear medicine, generally salic 20 ~ 40%, and oxidation-containing cerium 0.5 ~ 1%, remaining lutecium oxide is 60 ~ 80%.
A kind of method reclaiming lutecium oxide from the scintillation crystal waste of mixing 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 scintillation crystal waste, add alkaline matter, roasting, obtains calcining matter; S2, calcining matter is carried out water logging, filter, and add nitric acid and oxygenant in the filter residue obtained, stir, obtain mixed solution; S3, will join in organic extractant in mixed solution, extraction, obtain the extract containing cerium and the raffinate containing lutetium; S4, to containing lutetium raffinate in add oxalic acid, stir, filter, by the throw out calcination obtained, obtain lutecium oxide.
By adding sodium hydroxide and/or potassium hydroxide also at high temperature roasting to mixing in Cerium aluminate lutetium scintillation crystal waste, the solid matter obtained is carried out dissolve, filtering separation thus eliminate impurity aluminum, filter residue to be dissolved after reoxidizing and the cerium that adulterates of extracting cerium ion remaval in acid condition, by the rear calcination of the precipitation of the raffinate containing lutetium obtained, obtain 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, obtain high purity 99% and the rate of recovery up to 99.5% high-purity mangesium oxide lutetium.Because the price comparison of Lutetium is expensive, the present invention reclaims lutetium to provide a kind of new approach from the scintillation crystal waste of mixing Cerium aluminate lutetium, has saved resource, has decreased pollution, had huge practical value.
In order to the metallic aluminium in waste material is fully separated from the scintillation crystal waste of mixing Cerium aluminate lutetium, the application selects to add sodium hydroxide and/or potassium hydroxide in step sl, roasting 0.5 ~ 2 hour at 320 DEG C ~ 700 DEG C, 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 water extraction calcining matter, sodium aluminate and/or potassium aluminate soluble in water, and cerous hydroxide and hydroxide lutetium water insoluble, through filtration 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, the mol ratio of contained oxide aggregate is 6:1 ~ 10:1.If both mol ratios are less than 6:1, the aluminium in scintillation crystal waste can be caused can not to be converted into sodium aluminate and/or potassium aluminate completely, make cerium contained in scintillation crystal waste and lutetium can not be converted into cerous hydroxide, hydroxide lutetium completely, so still have some scintillation crystal waste do not react and left behind, the purity of the lutecium oxide obtained and the rate of recovery are decreased; If both mol ratios are greater than 10:1, base excess can cause the solution basicity after calcining matter water logging and viscosity excessive, give completely filter and separating impurity aluminium affect, thus affect the purity of lutecium oxide product, in addition, also can increase raw materials cost, also can cause the erosion of equipment simultaneously.
In 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 the present invention preferably adopts the sodium hydroxide of low melting point and low cost to carry out roasting with the scintillation crystal waste of mixing Cerium aluminate lutetium, make the separation of impurity aluminum complete like this, the purity of the final product lutecium oxide obtained and yield is higher and cost is lower.Roasting at 320 DEG C ~ 700 DEG C is wherein selected within 0.5 ~ 2 hour, mainly to consider that the fusing point of sodium hydroxide is 318.4 DEG C, if maturing temperature is lower than 320 DEG C, then can there is sodium hydroxide and melt incomplete problem, thus cause sodium hydroxide and scintillation crystal waste fully to react, aluminium in scintillation crystal waste can not generate sodium aluminate completely, the degree of such separating impurity aluminium is thorough not, does not reach the object be fully separated; If maturing temperature is higher than 700 DEG C, then the sodium aluminate of generation can be made to resolve into aluminum oxide, thus also cannot reach the object of abundant separating impurity aluminium.
In the filter cake obtained, add nitric acid and oxygenant, a preferred embodiment of the invention after filtering, oxygenant is potassium bromate or potassium permanganate.The object adding nitric acid in this step is solution filter cake being dissolved as nitric acid system, and the object adding oxygenant is in order to by Ce contained in filter cake
3+exhaustive oxidation becomes Ce
4+, this is because under high acid environment, extraction agent such as TBP extraction agent only extracts quadrivalent cerium, and does not extract trivalent lutetium, thus reaches the object of cerium lutetium separation.In order to ensure the Ce in filter cake
3+exhaustive oxidation becomes Ce
4+, the oxygenant needs added are excessive a little, and according to a preferred embodiment of the present invention, oxygenant is potassium bromate or potassium permanganate; The mol ratio of wherein contained in oxygenant and scintillation crystal waste cerium is 5:1 ~ 1:1.If the mol ratio of cerium contained in oxygenant and scintillation crystal waste is greater than 5:1, then makes oxygenant solute concentration in mixed solution increase and occur that viscosity of mixed liquid is excessive, cause phase-splitting bad and affect the degree that cerium impurity is separated; Reduce purity and the yield of the lutecium oxide finally obtained; If the mol ratio of contained cerium is less than 1:1 in oxygenant and scintillation crystal waste, then the trivalent cerium in mixed solution can not be oxidized to quadrivalent cerium completely, cerium impurity is separated thorough, can reduces the purity of product lutecium oxide equally.
Obtain mixed solution after adding nitric acid and oxygenant, a preferred embodiment of the invention, also comprise before carrying out organic extraction to mixed solution: in mixed solution, add concentrated nitric acid, the acidity of adjustment mixed solution is the step of 5 ~ 10N.The acidity of mixed solution being adjusted to the object that 5 ~ 10N carries out extracting is improve the acidity of mixed solution, contributes to the extracting and separating of cerium and lutetium; If the acidity of mixed solution is lower than 5N, then there will be a large amount of lutetiums and be extracted in organic phase, reduce the yield of product lutetium; If the acidity of mixed solution is higher than 10N, then 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 be separated not exclusively, also can cause work under bad environment and then unhealthful.Therefore the present invention adjusts the acidity of mixed solution before preferably carrying out organic extraction to mixed solution is 5 ~ 10N, ensure that carrying out smoothly of follow-up organic extractions, 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 tributyl phosphate and whiteruss, tbp and kerosene, di (isooctyl) phosphate and the mixed solution of kerosene and the mixed solution of isooctyl phosphoric acid di-isooctyl and kerosene.Preferably but be not limited to above-mentioned organic extraction solvent, phase-splitting is fast, the advantage of easily back extraction to adopt above-mentioned organic extractant to have in the present invention.Oil phase after wherein adding organic extractant in mixed solution is 5:1 ~ 1:1 than O:A.When organic extractant is the mixed solution of tbp (TBP) and whiteruss, by volume percentages, TBP accounts for 10% ~ 60% of described mixed solution, and whiteruss accounts for 40% ~ 90% of mixed solution.By carrying out organic extraction to mixed solution, the Ce in mixed solution can be made
4+enter into organic extractant, lutetium ion is retained in raffinate, so just thoroughly removes mixing the cerium adulterated in Cerium aluminate lutetium scintillation crystal waste.
In order to make organic extractant can recycle, according to a kind of exemplary embodiment of the present invention, also comprise the process that the extract obtained in step S3 is stripped, comprise: in extract, add the ascorbic acid solution that mass percent concentration is 0.1 ~ 0.5%, stir back extraction 0.5 ~ 1 hour; And in the organic extractant after back extraction, add the salpeter solution that acidity is 3 ~ 8N, agitator treating.Quadrivalent cerium in extraction agent can be reduced into trivalent cerium by the ascorbic acid solution added, thus plays ceric object in 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, because ascorbic acid solution is easily by light and atmospheric oxidation, need now with the current.Wherein employing acidity is the organic extractant after the salpeter solution washing back extraction of 3 ~ 8N is to wash away xitix residual in organic extractant, not affecting the percentage extraction of cerium when ensureing that organic extractant recycles.
In order to obtain highly purified lutecium oxide, needing to add oxalic acid in raffinate and making that the 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 benchmark completely.A preferred embodiment of the invention, also comprises before adding oxalic acid step in raffinate: carried out by raffinate evaporating, concentrating, and adjust the step of pH value to 1.5 ~ 2 of the concentrated solution obtained.Due to by Ce
3+be oxidized to Ce
4+process in add more concentrated nitric acid, part concentrated nitric acid remains in raffinate, and the stronger acidity that raffinate is presented, is unfavorable for that lutetium ion precipitates.By adding pH value to 1.5 ~ 2 of deionized water adjustment concentrated solution, by weakening the acidic conditions of raffinate, being conducive to lutetium ion precipitation, thus ensure that purity and the yield of the lutecium oxide product finally obtained.The throw out of the oxalic acid lutetium obtained after filtration is obtained lutecium oxide through 800 DEG C ~ 950 DEG C calcinations after 2 ~ 4 hours.
According to a further aspect in the invention, provide and a kind ofly from the scintillation crystal waste of mixing Cerium aluminate lutetium, reclaim the lutecium oxide obtained, wherein lutecium oxide adopts any one method above-mentioned to carry out recovery to obtain.The purity of the lutecium oxide product adopting aforesaid method provided by the present invention to prepare is greater than 99.5%.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
1) take 50 grams of commercially available scintillation crystal waste (concrete composition is in table 1) and be placed in corundum crucible, then add sodium hydroxide roasting 2 hours in the retort furnace of 700 DEG C, obtain calcining matter; Wherein in sodium hydroxide and scintillation crystal waste, oxidiferous total mol ratio is 6:1.
2) in calcining matter, add hot water and leach 30 minutes, filter, wash 5 times, obtain filter cake.In filter cake, adding appropriate concentrated nitric acid be heated to 60 DEG C of dissolving filter cakes, until dissolve limpid rear cooling, is 5:1(and KBrO by the mol ratio of cerium contained in oxygenant and scintillation crystal waste
3: CeO
2=5:1) add oxygenant potassium bromate, stir 30 minutes, obtain mixed solution.
3) acidity adding concentrated nitric acid adjustment mixed solution in mixed solution is 10N, and joined in organic extractant by the mixed solution after acid adjustment and extract, wherein, comparing O:A is 5:1, and extraction time is 30min.Organic extractant is the mixture (according to volume percentage, TBP accounts for 10% of mixture, and whiteruss accounts for 90% of mixture) of TBP and whiteruss.Thing and raffinate is extracted through extraction.
4) by raffinate through 100 DEG C of evaporation concentration 2 hours, then add the pH value to 1.5 that deionized water regulates concentrated solution.Be in the solution of 1.5, add the oxalic acid precipitation lutetium of 53 grams to pH value, filter, obtain oxalic acid lutetium throw out, by oxalic acid lutetium throw out 850 DEG C of calcinations after 2 hours lutecium oxide product.
Embodiment 2
1) take 50 grams of commercially available scintillation crystal waste (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 DEG C, obtain calcining matter; Wherein in sodium hydroxide and scintillation crystal waste, oxidiferous total mol ratio is 10:1.
2) in calcining matter, add hot water and leach 30 minutes, filter, wash 4 times, obtain filter cake.In filter cake, adding appropriate concentrated nitric acid be heated to 60 DEG C of dissolving filter cakes, until dissolve limpid rear cooling, is 3:1(and KBrO by the mol ratio of cerium contained in oxygenant and scintillation crystal waste
3: CeO
2=3:1) add oxygenant potassium bromate, stir 30min, obtain mixed solution.
3) acidity adding concentrated nitric acid adjustment mixed solution in mixed solution is 5N, and joined in organic extractant by the mixed solution after acid adjustment and extract, wherein, comparing O:A is 5:1, and extraction time is 30min.Organic extractant is the mixture (according to volume percentage, TBP accounts for 60% of mixture, and whiteruss accounts for 40% of mixture) of TBP and whiteruss.Thing and raffinate is extracted through extraction.
4) by raffinate through 120 DEG C of evaporation concentration 1.5 hours, then add the pH value to 2 that deionized water regulates concentrated solution.Be in the solution of 2, add the oxalic acid precipitation lutetium of 53 grams to pH value, filter, obtain oxalic acid lutetium throw out, by oxalic acid lutetium throw out 850 DEG C of calcinations after 2.5 hours lutecium oxide product.
Embodiment 3
1) take 50 grams of commercially available scintillation crystal waste (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 DEG C, obtain calcining matter; Wherein in potassium hydroxide and scintillation crystal waste, the mol ratio of contained oxide aggregate is 8:1.
2) in calcining matter, add hot water and leach 30 minutes, filter, wash 4 times, obtain filter cake.In filter cake, adding appropriate concentrated nitric acid be heated to 60 DEG C of dissolving filter cakes, until dissolve limpid rear cooling, is 1:1(and KBrO by the mol ratio of cerium contained in oxygenant and scintillation crystal waste
3: CeO
2=1:1) add oxygenant potassium bromate, stir 30min, obtain mixed solution.
3) acidity adding concentrated nitric acid adjustment mixed solution in mixed solution is 7.5N, and joined in organic extractant by the mixed solution after acid adjustment and extract, wherein, comparing O:A is 5:1, and extraction time is 30min.Organic extractant is the mixture (according to volume percentage, TBP accounts for 35% of mixture, and whiteruss accounts for 65% of mixture) of TBP and whiteruss.Thing and raffinate is extracted through extraction.
4) by raffinate through 100 DEG C of evaporation concentration 2.5 hours, then add the pH value to 1.8 that deionized water regulates concentrated solution.Be in the solution of 1.8, add the oxalic acid precipitation lutetium of 53 grams to pH value, filter, obtain oxalic acid lutetium throw out, by oxalic acid lutetium throw out 850 DEG C of calcinations after 2.5 hours lutecium oxide product.
Embodiment 4
Identical with operation steps with the raw material of embodiment 1, difference is that the mol ratio of contained oxide aggregate in adopted calcination agent sodium hydroxide and scintillation crystal waste is 5:1.
Embodiment 5
Identical with operation steps with the raw material of embodiment 1, difference is that the mol ratio of contained oxide aggregate in adopted oxygenant sodium hydroxide and scintillation crystal waste is 11:1.
Embodiment 6
Identical with operation steps with the raw material of embodiment 1, difference is that the mol ratio of cerium contained in added oxygenant potassium bromate and scintillation crystal waste is 7:1.
Embodiment 7
Identical with operation steps with the raw material of embodiment 1, difference is that the mol ratio of cerium contained in added oxygenant potassium bromate and scintillation crystal waste is 1:2.
Embodiment 8
Identical with operation steps with the raw material of embodiment 2, difference is that the acidity adding concentrated nitric acid adjustment mixed solution in step 3) in mixed solution is 3N.
Embodiment 9
Identical with operation steps with the raw material of embodiment 2, difference is that the acidity adding concentrated nitric acid adjustment mixed solution in step 3) in mixed solution is 12N.
Comparative example 1
Identical with operation steps with the raw material 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 detect the composition in final product lutecium oxide in embodiment 1 ~ 9 and comparative example 1, detected result is specifically in table 1.
Table 1
Wherein R represents the mol ratio of oxide aggregate in calcination agent and scintillation crystal waste, and N represents the mol ratio of cerium contained in oxygenant and scintillation crystal waste.
Detected result from table 1 is known, and the lutecium oxide product purity adopting technique of the present invention to prepare is all up to more than 99.5%, and yield is more than 94%.As can be seen from the data of embodiment 4 and embodiment 5, when by the mol ratio of the oxide aggregate in the calcination agent being added sodium hydroxide or potassium hydroxide and scintillation crystal waste not within the scope of 6:1 ~ 10:1 time, purity and the rate of recovery of the lutecium oxide product of final preparation can decrease.
When the mol ratio of cerium contained in added oxygenant potassium bromate and scintillation crystal waste is not within the scope of 5:1 ~ 1:1, oxidant content as added in embodiment 6 is more, 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 lower than the purity of the lutecium oxide in embodiment 1 and the rate of recovery.Concrete analysis, when the add-on of oxygenant is more, in mixed solution, solute concentration increases that just to there will be viscosity of mixed liquid excessive, causes phase-splitting bad and affects cerium impurity and be separated not exclusively; When the add-on of oxygenant is less, trivalent cerium just can not be oxidized to quadrivalent cerium completely, cerium impurity is just separated not thorough, the add-on of visible oxygenant affects the key factor that cerium is separated with lutetium, selects suitable oxygenant and addition thereof to be the key factors of preparation high purity and high-recovery lutecium oxide product.
When add the acidity in the mixed solution after oxygenant not between 5 ~ 10 time, if the acidity in embodiment 8 is 3N, and the acidity in embodiment 9 is when being 12, 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, when the acidity in mixed solution is less, then there will be a large amount of lutetiums and be extracted in organic phase, cause the yield of product lutetium seriously on the low side; If when the acidity of mixed solution is larger, then there will be that viscosity of mixed liquid is excessive, acid mist is serious, cause phase-splitting bad and affect cerium impurity and be separated, visible, the acidity of mixed solution affects the key factor that cerium is separated with lutetium.In addition, acidity is higher also can affect Working environment, thus affects HUMAN HEALTH.The advantages such as in addition, recovery process of the present invention has condition and easily controls, 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 amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. from the scintillation crystal waste of mixing Cerium aluminate lutetium, reclaim a method for lutecium oxide, it is characterized in that, comprise the following steps:
S1, in described scintillation crystal waste, add sodium hydroxide and/or potassium hydroxide, roasting, obtain calcining matter;
S2, described calcining matter is carried out water logging, filter, and in the filter residue obtained, add nitric acid and make Ce in described filter residue
3+be oxidized to Ce
4+oxygenant, stir, obtain mixed solution, in described mixed solution, add concentrated nitric acid, the acidity adjusting described mixed solution is 5 ~ 10N;
S3, described mixed solution is joined in organic extractant, extraction, obtain the extract containing cerium and the raffinate containing lutetium; And
S4, in the described raffinate containing lutetium, add oxalic acid, stir, filter, by the throw out calcination obtained, 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, 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 DEG C ~ 700 DEG C, 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; The mol ratio of cerium contained in described oxygenant and described scintillation crystal waste is 5:1 ~ 1:1.
5. 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 tbp and whiteruss, tbp and kerosene, di (isooctyl) phosphate and the mixed solution of kerosene and the mixed solution of isooctyl phosphoric acid di-isooctyl and kerosene.
6. method according to claim 5, it is characterized in that, when described organic extractant is the mixed solution of described tbp and described whiteruss, by volume percentages, described tbp accounts for 10% ~ 60% of described mixed solution, and described whiteruss accounts for 40% ~ 90% of described mixed solution.
7. method according to claim 1, is characterized in that, also comprises before adding oxalic acid step in the raffinate of lutetium to described:
The described raffinate containing lutetium is carried out evaporating, concentrating, and adjusts the step of pH value to 1.5 ~ 2 of the concentrated solution obtained.
8. method according to claim 1, is characterized in that, also comprises the process of stripping to the extract containing cerium described in obtaining in described step S3, comprising:
In described extract, add the ascorbic acid solution that mass percent concentration is 0.1 ~ 0.5%, stir back extraction 0.5 ~ 1 hour; And
The salpeter solution that acidity is 3 ~ 8N is added, agitator treating in the described organic extractant after described back extraction.
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| 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 |
| 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 |
| 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 |
| CN110042245B (en) * | 2019-03-29 | 2020-12-01 | 甘肃稀土新材料股份有限公司 | Method for recovering and purifying lutetium from lutetium yttrium silicate scintillation crystal waste |
| 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 |
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| 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 |
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| 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 |
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