CN107326200B - A method of it being enriched with europium from sm-eu-gd chloride solution - Google Patents
A method of it being enriched with europium from sm-eu-gd chloride solution Download PDFInfo
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- CN107326200B CN107326200B CN201710377261.9A CN201710377261A CN107326200B CN 107326200 B CN107326200 B CN 107326200B CN 201710377261 A CN201710377261 A CN 201710377261A CN 107326200 B CN107326200 B CN 107326200B
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 75
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 25
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000006166 lysate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 70
- ONQORTHCHCYWSQ-UHFFFAOYSA-L europium(2+);sulfate Chemical compound [Eu+2].[O-]S([O-])(=O)=O ONQORTHCHCYWSQ-UHFFFAOYSA-L 0.000 description 17
- 239000000463 material Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- -1 europium ion Chemical class 0.000 description 3
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
Abstract
A method of it being enriched with europium from sm-eu-gd chloride solution, it is successively made of following steps: sm-eu-gd chloride solution is deployed into the solution that REO is 70 ~ 150g/L, glacial acetic acid is added, stirring 10 ~ 30 minutes, it adjusts pH value and magnesium sulfate is added in the solution of step 1) to 1.5 ~ 3, stir 30 ~ 60 minutes；Then zinc powder is added, stirs 30 ~ 120 minutes；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium is obtained by filtration, uses concentration to wash filter residue containing europium for the dilute hydrochloric acid of 0.5 ~ 2mol/L, washing water is for deploying above-mentioned sm-eu-gd chloride solution；Hydrochloric acid solution is added in the filter residue containing europium of step 2, stirs 30 ~ 60 minutes；Hydrogen peroxide is added, is stirred 1 ~ 5 hour；By 0.5 ~ 4 times of above-mentioned hydrochloric acid solution additional amount, it is diluted with water；It stirs, trivalent europium solution is obtained by filtration, filter residue returns to resolution process again.The method energy saving of middle enrichment europium, easy to operate, low in cost in slave sm-eu-gd chloride solution of the invention.
Description
Technical field
The method that the present invention relates to a kind of to be enriched with europium from sm-eu-gd chloride solution.
Background technique
Europium is good luminescent material activator, such as: Eu3+It is the activator of red illuminating material, Eu2+It is blue-light-emitting
The activator of material.Europium oxide is widely used in LED, trichromatic energy saving lamp, fine definition as luminescent material activator and shows
Among display screen, novel X-ray medical diagnosis system.Simultaneous oxidation europium applies also for laser, superconductor, magnetic bubble reservoir
Among part, the control material of atomic pile, shielding material and structural material.Therefore, europium oxide is new in the photoelectricity quickly grown
Extremely important status and effect are shown in material technology.
The purifying technique of basicity reduction method production high-purity mangesium oxide europium is mainly first restored trivalent europium ion using zinc powder
At divalent europium, divalent europium and sulfate radical form europous sulfate precipitating, with other rare earths separations.Due to using zinc
Powder restores, and the part hydrogen ion in solution is reduced into hydrogen precipitation, causes pH value of solution to increase rapidly, some metal ions such as aluminium
Hydroxide Precipitation is formed, the reduction rate of trivalent europium is influenced, causes to contain aluminum hydroxide precipitation, mistake in europous sulfate precipitating
Filter is difficult, and the europous sulfate purity precipitated is not high, influences later separation；Europous sulfate chemical property is stablized, and more difficult point
Solution, mainly use following methods at present: 1. nitric acid heat are boiled: boiling oxidation dissolution europous sulfate using nitric acid solution；2. alkali heat is boiled:
It is boiled using the mixed liquor or sodium carbonate liquor of sodium carbonate and sodium hydroxide, converts carbonic acid Asia europium for europous sulfate, then will
Carbonic acid Asia europium oxidation dissolution (Xu Guangxian chief editor, " rare earth ", metallurgical industry publishing house, 1995).Both the above method requires to add
Heat consumes a large amount of thermal energy, and nitric acid and sodium carbonate price are more expensive, and production cost is higher.
Summary of the invention
The purpose of the present invention is to provide a kind of easy to operate, low-cost europium is enriched with from sm-eu-gd chloride solution
Method.
Sm-eu-gd chloride solution of the present invention is that the intermediate product that rare earth extraction separates or sm-eu-gd oxide are molten
Product is solved, wherein [Eu3+] concentration be 3 ~ 50g/L, Σ REO be 70 ~ 300g/L, pH be 3 ~ 5, contain a small amount of aluminium ion.
The method of the present invention that europium is enriched with from sm-eu-gd chloride solution successively comprises the steps of:
1) ingredient: sm-eu-gd chloride solution is deployed into the solution that REO is 70 ~ 150g/L, glacial acetic acid, stirring 10 is added
~ 30 minutes, pH value was adjusted to 1.5 ~ 3；
2) it restores: at room temperature, magnesium sulfate being added in the solution of step 1), stir 30 ~ 60 minutes；Then zinc is added
Powder stirs 30 ~ 120 minutes；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium is obtained by filtration, uses concentration for the dilute of 0.5 ~ 2mol/L
Salt acid elution filter residue containing europium, washing water is for deploying above-mentioned sm-eu-gd chloride solution；
3) it decomposes: at room temperature, hydrochloric acid solution being added in the filter residue containing europium of step 2, stir 30 ~ 60 minutes；It adds
Hydrogen peroxide stirs 1 ~ 5 hour；By 0.5 ~ 4 times of above-mentioned hydrochloric acid solution additional amount, it is diluted with water；It stirs, trivalent europium is obtained by filtration
Solution, filter residue return to resolution process again.
The present invention presses glacial acetic acid: glacial acetic acid is added to sm-eu-gd chlorine by sm-eu-gd chloride solution 5 ~ 15:1000 of volume ratio
Soda acid buffer solution is formed in compound solution, in zinc powder reduction trivalent europium, the pH of solution is relatively stable, ensure that trivalent europium
Reduction rate, while avoiding other metal ions and forming hydroxide and precipitate and entering in precipitation slag, reduction effect is good.
In the solution that glacial acetic acid is added, by magnesium sulfate: sulfuric acid is added in sm-eu-gd 5 ~ 15:100 of chloride solution mass ratio
Magnesium introduces sulfate radical so that trivalent europium generates europous sulfate precipitating after being reduced into divalent europium.
By zinc powder: zinc powder is added in 0.5 ~ 2:1 of mass ratio of europium in sm-eu-gd chloride solution, and trivalent europium is reduced into divalent
Europium, divalent europium and sulfate radical, which are formed, to be precipitated, and other trivalent rare earths do not form precipitating, and divalent europium and other trivalent rare earths have carried out point
From；Restoring filtered filter residue is europous sulfate precipitating and the unreacted zinc powder in part.Europous sulfate chemical property is stablized, insoluble
In soda acid, it is not easy to react with other materials.Since filter residue containing europium is the unreacted zinc powder of europous sulfate and part, zinc powder tool
There is reproducibility, the present invention first uses hydrochloric acid to dissolve the zinc powder in filter residue containing europium, to reduce subsequent europous sulfate oxygenolysis
When consume oxidant, chemical equation is as follows: 2HCl+Zn → ZnCl2 + H2。
4 are added by hydrochloric acid solution mass ratio 1:2 ~ 6 and hydrogen peroxide mass ratio 1:0.1 ~ 0.5 respectively in filter residue containing europium ~
The hydrochloric acid solution and concentration of 10mol/L is the hydrogen peroxide of 20 ~ 50%wt.Hydrogen peroxide oxidation is added in the hydrochloric acid solution of filter residue containing europium
Europous sulfate is decomposed, chlorine and heat are generated, the strong oxidizing property of the thermal energy and chlorine released using reaction is by the two of europous sulfate
Valence europium is oxidized to trivalent europium, and europous sulfate decomposes, and generates water-soluble europium sulfate and Europium chloride.Not due to europium sulfate solubility
Enough big, only 40g/L or so, trivalent europium is diluted with water after decomposition after solution is cooling in order to prevent with europium sulfate Precipitation, is changed
It is as follows to learn reaction equation:
2HCl + H2O2 →Cl2 + 2H2O；
3Cl2 + 6EuSO4 →2Eu2(SO4)3 + 2EuCl3。
The present invention is enriched with the method energy saving of europium from sm-eu-gd chloride solution, easy to operate, low in cost.
Specific embodiment
Embodiment 1
Certain sm-eu-gd chloride solution 100L, wherein [Eu3+] concentration be 50g/L, Σ REO be 300g/L, pH 4.5,
[Al3+] concentration be 1.2g/L.The solution is diluted to the solution that REO is 150g/L, by glacial acetic acid: sm-eu-gd chloride solution body
Glacial acetic acid is added in sm-eu-gd chloride solution by product than 15:1000, is stirred 30 minutes, adjusts pH value to 2 or so；In room
Under temperature, by magnesium sulfate: magnesium sulfate is added in sm-eu-gd chloride solution by sm-eu-gd chloride solution mass ratio 15:100,
Stirring 60 minutes；Then zinc powder: the mass ratio 2:1 of europium in sm-eu-gd chloride solution is pressed, zinc powder reduction is added, stirs 120 points
Clock；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium is finally obtained by filtration；Using concentration is the washing of the hydrochloric acid solution of 2mol/L containing europium
Filter residue, washing water are returned for deploying above-mentioned sm-eu-gd chloride solution；By filter residue containing europium: hydrochloric acid solution mass ratio is 1:6, will
Filter residue containing europium is added in the hydrochloric acid solution that concentration is 10mol/L, is stirred 60 minutes；Then by filter residue: hydrogen peroxide mass ratio is
The hydrogen peroxide that concentration is 50%wt is added in 1:0.5, stirs 5 hours；It is finally diluted by the water of 4 times of above-mentioned hydrochloric acid solution additional amount, mistake
Filter obtains trivalent europium solution 80L, and filter residue is undecomposed europous sulfate, and weight 0.3Kg, filter residue returns to resolution process again.Through analyzing,
Wherein [Eu3+] concentration be 60g/L, [Sm3++Gd3+] it is 10g/L, europium direct yield is 96%.
Embodiment 2
Certain sm-eu-gd chloride solution 100L, wherein [Eu3+] concentration be 4g/L, Σ REO be 75g/L, pH 3.0, [Al3 +] concentration be 0.5g/L.The solution is diluted to the solution that REO is 70g/L, by glacial acetic acid: sm-eu-gd chloride solution volume ratio
Glacial acetic acid is added in sm-eu-gd chloride solution by 5:1000, is stirred 10 minutes, adjusts pH value to 2 or so；At room temperature,
By magnesium sulfate: magnesium sulfate is added in sm-eu-gd chloride solution by sm-eu-gd chloride solution mass ratio 5:100, stirring 30
Minute；Then zinc powder: the mass ratio 0.5:1 of europium in sm-eu-gd chloride solution is pressed, zinc powder reduction is added, is stirred 40 minutes；Most
After filter residue containing europium and the chloride filtrate of gadolinium containing samarium is obtained by filtration；Concentration is used to filter for the washing of the hydrochloric acid solution of 0.5mol/L containing europium
Slag, washing water are returned for deploying above-mentioned sm-eu-gd chloride solution；By filter residue containing europium: hydrochloric acid solution mass ratio is 1:3, will be contained
Europium filter residue is added in the hydrochloric acid solution that concentration is 4mol/L, is stirred 30 minutes；Then press filter residue: hydrogen peroxide mass ratio is 1:
0.1 is added the hydrogen peroxide that concentration is 20%wt, stirs 1 hour；It is finally diluted by the water of 0.5 times of above-mentioned hydrochloric acid solution additional amount, mistake
Filter obtains trivalent europium solution 10L, and filter residue is undecomposed europous sulfate, and weight 0.1Kg, filter residue returns to resolution process again.Through analyzing,
Wherein [Eu3+] concentration be 36g/L, [Sm3++Gd3+] it is 7g/L, europium direct yield is 90%.
Embodiment 3
Certain sm-eu-gd chloride solution 100L, wherein [Eu3+] concentration be 20g/L, Σ REO be 150g/L, pH 4.0,
[Al3+] concentration be 1.5g/L.The solution is diluted to the solution that REO is 100g/L, by glacial acetic acid: sm-eu-gd chloride solution body
Glacial acetic acid is added in sm-eu-gd chloride solution by product than 10:1000, is stirred 20 minutes, adjusts pH value to 2.5 or so；?
At room temperature, by magnesium sulfate: magnesium sulfate is added to sm-eu-gd chloride solution by sm-eu-gd chloride solution mass ratio 10:100
In, it stirs 40 minutes；Then zinc powder: the mass ratio 1:1 of europium in sm-eu-gd chloride solution is pressed, zinc powder reduction, stirring 80 is added
Minute；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium is finally obtained by filtration；Concentration is used to wash for the hydrochloric acid solution of 1.0mol/L
Filter residue containing europium, washing water are returned for deploying above-mentioned sm-eu-gd chloride solution；By filter residue containing europium: hydrochloric acid solution mass ratio is 1:
4, filter residue containing europium is added in the hydrochloric acid solution that concentration is 6mol/L, is stirred 30 minutes；Then filter residue: hydrogen peroxide mass ratio is pressed
The hydrogen peroxide that concentration is 40%wt is added for 1:0.3, stirs 3 hours；Finally diluted by the water of 2 times of above-mentioned hydrochloric acid solution additional amount,
Trivalent europium solution 26L is obtained by filtration, filter residue is undecomposed europous sulfate, and weight 0.3Kg, filter residue returns to resolution process again.Through dividing
Analysis, wherein [Eu3+] concentration be 72g/L, [Sm3++Gd3+] it is 9g/L, europium direct yield is 94%.
Claims (6)
1. a kind of method for being enriched with europium from sm-eu-gd chloride solution, the sm-eu-gd chloride solution is rare earth extraction separation
Intermediate product or sm-eu-gd oxide lysate, wherein [Eu3+] concentration is 3 ~ 50g/L, Σ REO is 70 ~ 300g/L, and pH is
3 ~ 5, containing a small amount of aluminium ion, it is characterized in that successively comprising the steps of:
1) ingredient: sm-eu-gd chloride solution is deployed into the solution that REO is 70 ~ 150g/L, glacial acetic acid, stirring 10 ~ 30 is added
Minute, pH value is adjusted to 1.5 ~ 3；
2) it restores: at room temperature, magnesium sulfate being added in the solution of step 1), stir 30 ~ 60 minutes；Then zinc powder is added, stirs
It mixes 30 ~ 120 minutes；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium is obtained by filtration, uses concentration for the dilute hydrochloric acid of 0.5 ~ 2mol/L
Filter residue containing europium is washed, washing water is for deploying above-mentioned sm-eu-gd chloride solution；
3) it decomposes: at room temperature, hydrochloric acid solution being added in the filter residue containing europium of step 2, stir 30 ~ 60 minutes；Add dioxygen
Water stirs 1 ~ 5 hour；By 0.5 ~ 4 times of above-mentioned hydrochloric acid solution additional amount, it is diluted with water；It stirs, that trivalent europium is obtained by filtration is molten
Liquid, filter residue return to resolution process again.
2. the method according to claim 1 for being enriched with europium from sm-eu-gd chloride solution, it is characterized in that the glacial acetic acid
Additional amount be glacial acetic acid: 5 ~ 15:1000 of sm-eu-gd chloride solution volume ratio.
3. the method according to claim 1 for being enriched with europium from sm-eu-gd chloride solution, it is characterized in that the magnesium sulfate
Additional amount be magnesium sulfate: 5 ~ 15:100 of sm-eu-gd chloride solution mass ratio.
4. the method according to claim 1 that europium is enriched with from sm-eu-gd chloride solution, it is characterized in that the zinc powder
Additional amount is zinc powder: 0.5 ~ 2:1 of mass ratio of europium in sm-eu-gd chloride solution.
5. the method according to claim 1 for being enriched with europium from sm-eu-gd chloride solution, it is characterized in that the hydrochloric acid is molten
The additional amount of liquid is filter residue containing europium: hydrochloric acid solution mass ratio 1:2 ~ 6, and concentration of hydrochloric acid solution is 4 ~ 10mol/L.
6. the method according to claim 1 for being enriched with europium from sm-eu-gd chloride solution, it is characterized in that the hydrogen peroxide
Additional amount be filter residue containing europium: hydrogen peroxide mass ratio 1:0.1 ~ 0.5, the concentration of hydrogen peroxide is 20 ~ 50%wt.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706973A (en) * | 2004-06-12 | 2005-12-14 | 包头市京瑞新材料有限公司 | Zinc powder reduction process of preparing europium-enriched solution |
| CN101012509A (en) * | 2007-02-05 | 2007-08-08 | 常州华南化工有限公司 | Method for preparing ultra-thin highly-pure europium oxide by europium-rich sulfuric acid rare earth |
| 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 |
| CN102337405A (en) * | 2011-10-28 | 2012-02-01 | 包头市京瑞新材料有限公司 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
| AU2013255066A1 (en) * | 2012-05-04 | 2014-11-27 | Vale S.A. | System and method for rare earths extraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1706973A (en) * | 2004-06-12 | 2005-12-14 | 包头市京瑞新材料有限公司 | Zinc powder reduction process of preparing europium-enriched solution |
| CN101012509A (en) * | 2007-02-05 | 2007-08-08 | 常州华南化工有限公司 | Method for preparing ultra-thin highly-pure europium oxide by europium-rich sulfuric acid rare earth |
| 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 |
| CN102337405A (en) * | 2011-10-28 | 2012-02-01 | 包头市京瑞新材料有限公司 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
| AU2013255066A1 (en) * | 2012-05-04 | 2014-11-27 | Vale S.A. | System and method for rare earths extraction |
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