A method of it being enriched with europium from sm-eu-gd chloride solution
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%.