CN107326200A - The method of europium is enriched with a kind of chloride solution from sm-eu-gd - Google Patents
The method of europium is enriched with a kind of chloride solution from sm-eu-gd Download PDFInfo
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- CN107326200A CN107326200A CN201710377261.9A CN201710377261A CN107326200A CN 107326200 A CN107326200 A CN 107326200A CN 201710377261 A CN201710377261 A CN 201710377261A CN 107326200 A CN107326200 A CN 107326200A
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- europium
- chloride solution
- solution
- filter residue
- hydrochloric acid
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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 73
- 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 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 239000012362 glacial acetic acid Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000006166 lysate Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 2
- ONQORTHCHCYWSQ-UHFFFAOYSA-L europium(2+);sulfate Chemical compound [Eu+2].[O-]S([O-])(=O)=O ONQORTHCHCYWSQ-UHFFFAOYSA-L 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 10
- 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
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 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
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000926 separation method Methods 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
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- -1 europium ion Chemical class 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000011701 zinc Substances 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The method of europium is enriched with a kind of chloride solution from sm-eu-gd, is made up of successively following steps：Sm-eu-gd chloride solution is deployed into the solution that REO is 70 ~ 150g/L, glacial acetic acid is added, stirs 10 ~ 30 minutes, regulation pH value is to 1.5 ~ 3 in step 1）Solution in add magnesium sulfate, stir 30 ~ 60 minutes；Then zinc powder is added, is stirred 30 ~ 120 minutes；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium are filtrated to get, uses concentration to wash filter residue containing europium for 0.5 ~ 2mol/L watery hydrochloric acid, washings are used to allocate above-mentioned sm-eu-gd chloride solution；In step 2）Filter residue containing europium in add hydrochloric acid solution, stir 30 ~ 60 minutes；Hydrogen peroxide is added, is stirred 1 ~ 5 hour；By 0.5 ~ 4 times of above-mentioned hydrochloric acid solution addition, it is diluted with water；Stir, be filtrated to get trivalent europium solution, filter residue returns to resolution process again.The method of middle enrichment europium from sm-eu-gd chloride solution of the present invention saves energy consumption, simple to operate, with low cost.
Description
Technical field
The present invention relates to a kind of method that europium is enriched with chloride solution from sm-eu-gd.
Background technology
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 shown
Among display screen, new X-ray medical diagnosis system.Simultaneous oxidation europium applies also for laser, superconductor, magnetic bubble reservoir
Among part, control material, shielding material and the structural material of atomic pile.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 reducing process production high-purity mangesium oxide europium is mainly first reduced trivalent europium ion using zinc powder
Into divalent europium, divalent europium and sulfate radical formation europous sulfate precipitation, with other rare earths separations.Due to using zinc
Powder is reduced, and the part hydrogen ion in solution is reduced into hydrogen precipitation, causes pH value of solution to raise rapidly, some metal ions such as aluminium
Hydroxide Precipitation is formed, the percent reduction of trivalent europium is influenceed, causes europous sulfate to contain aluminum hydroxide precipitation, mistake in precipitating
Filter is difficult, and the europous sulfate purity precipitated is not high, influences later separation；Europous sulfate chemical property is stable, relatively difficult point
Solution, mainly uses following methods at present：1. nitric acid heat is boiled：Oxidation dissolution europous sulfate is boiled using salpeter solution；2. alkali heat is boiled：
Boiled using the mixed liquor or sodium carbonate liquor of sodium carbonate and sodium hydroxide, europous sulfate is converted into the sub- europium of carbonic acid, then will
Carbonic acid Asia europium oxidation dissolution（Xu Guangxian is edited,《Rare earth》, metallurgical industry publishing house, 1995）.Both the above method is required for adding
Heat, consumes substantial amounts of heat energy, and nitric acid and sodium carbonate are expensive, and production cost is higher.
The content of the invention
It is an object of the invention to provide be enriched with europium in a kind of chloride solution simple to operate, with low cost from sm-eu-gd
Method.
Sm-eu-gd chloride solution of the present invention is that intermediate product or sm-eu-gd oxide that rare earth extraction is separated 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 that europium is enriched with the chloride solution of the present invention from sm-eu-gd is comprised the steps of successively：
1）Dispensing: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, regulation pH value to 1.5 ~ 3；
2）Reduction:At room temperature, in step 1）Solution in add magnesium sulfate, stir 30 ~ 60 minutes；Then zinc powder is added, is stirred
Mix 30 ~ 120 minutes；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium are filtrated to get, concentration is used for 0.5 ~ 2mol/L watery hydrochloric acid
Filter residue containing europium is washed, washings are used to allocate above-mentioned sm-eu-gd chloride solution；
3）Decompose:At room temperature, in step 2）Filter residue containing europium in add hydrochloric acid solution, stir 30 ~ 60 minutes；Add dioxygen
Water, is stirred 1 ~ 5 hour；By 0.5 ~ 4 times of above-mentioned hydrochloric acid solution addition, it is diluted with water；Stir, to be filtrated to get trivalent europium molten
Liquid, filter residue returns to resolution process again.
The present invention presses glacial acetic acid:Sm-eu-gd chloride solution volume ratio 5 ~ 15:1000, glacial acetic acid is added to sm-eu-gd chlorine
Soda acid cushioning liquid is formed in compound solution, in zinc powder reduction trivalent europium, the pH of solution stablizes relatively, it is ensured that trivalent europium
Percent reduction, enters in precipitation slag, reduction effect is good while avoiding other metal ion formation hydroxide precipitations.
In the solution for adding glacial acetic acid, by magnesium sulfate:Sm-eu-gd chloride solution mass ratio 5 ~ 15:100 add sulfuric acid
Magnesium, introduces sulfate radical so that trivalent europium, which is reduced into after divalent europium, generates europous sulfate precipitation.
By zinc powder:The mass ratio 0.5 ~ 2 of europium in sm-eu-gd chloride solution:1 adds zinc powder, and trivalent europium is reduced into divalence
Europium, divalent europium and sulfate radical formation is precipitated, and other trivalent rare earths do not form precipitation, and divalent europium and other trivalent rare earths have been carried out point
From；Filter residue after reduction filtering is europous sulfate precipitation and the unreacted zinc powder in part.Europous sulfate chemical property is stable, insoluble
In soda acid, it is difficult to react with other materials.Because filter residue containing europium is the unreacted zinc powder of europous sulfate and part, zinc powder tool
There is reproducibility, the present invention is first dissolved the zinc powder in filter residue containing europium using hydrochloric acid, to reduce follow-up europous sulfate oxidation Decomposition
When consume oxidant, chemical equation is as follows：2HCl + Zn →ZnCl2 + H2。
Press hydrochloric acid solution mass ratio 1 respectively in filter residue containing europium:2 ~ 6 and hydrogen peroxide mass ratio 1:0.1 ~ 0.5 add 4 ~
10mol/L hydrochloric acid solution and concentration is 20 ~ 50%wt hydrogen peroxide.Hydrogen peroxide oxidation is added in the hydrochloric acid solution of filter residue containing europium
Europous sulfate is decomposed, chlorine and heat is produced, the heat energy released using reaction and the strong oxidizing property of chlorine are by the two of europous sulfate
Valency europium is oxidized to trivalent europium, and europous sulfate is decomposed, and generates water-soluble europium sulfate and Europium chloride.Due to europium sulfate solubility not
It is enough big, only 40g/L or so, in order to prevent that trivalent europium, with europium sulfate Precipitation, is diluted with water after decomposition after solution from cooling down, and is changed
Learn reaction equation as follows：
2HCl + H2O2 →Cl2 + 2H2O；
3Cl2 + 6EuSO4 →2Eu2(SO4)3 + 2EuCl3。
The method that the present invention is enriched with europium from sm-eu-gd chloride solution saves energy consumption, simple to operate, with low cost.
Embodiment
Embodiment 1
Certain sm-eu-gd chloride solution 100L, wherein [Eu3+] concentration be 50g/L, Σ REO be 300g/L, pH is 4.5, [Al3+]
Concentration is 1.2g/L.The solution is diluted to the solution that REO is 150g/L, by glacial acetic acid:Sm-eu-gd chloride solution volume ratio
15:1000, glacial acetic acid is added in sm-eu-gd chloride solution, stirred 30 minutes, regulation pH value to 2 or so；At room temperature,
By magnesium sulfate:Sm-eu-gd chloride solution mass ratio 15:100, magnesium sulfate is added in sm-eu-gd chloride solution, stirring 60
Minute；Then zinc powder is pressed:The mass ratio 2 of europium in sm-eu-gd chloride solution:1, zinc powder reduction is added, is stirred 120 minutes；Finally
It is filtrated to get filter residue containing europium and the chloride filtrate of gadolinium containing samarium；Use concentration to wash filter residue containing europium for 2mol/L hydrochloric acid solution, wash
Water is washed to return for allocating above-mentioned sm-eu-gd chloride solution；By filter residue containing europium:Hydrochloric acid solution mass ratio is 1:6, europium filter will be contained
Slag is added in the hydrochloric acid solution that concentration is 10mol/L, is stirred 60 minutes；Then filter residue is pressed:Hydrogen peroxide mass ratio is 1:0.5 adds
Enter the hydrogen peroxide that concentration is 50%wt, stir 5 hours；Finally dilute, be filtrated to get by the water of above-mentioned 4 times of hydrochloric acid solution addition
Trivalent europium solution 80L, filter residue is undecomposed europous sulfate, and weight 0.3Kg, filter residue returns to resolution process again.Through analysis, 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 is 3.0, [Al3+] dense
Spend for 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 5:
1000, glacial acetic acid is added in sm-eu-gd chloride solution, stirred 10 minutes, regulation pH value to 2 or so；At room temperature, press
Magnesium sulfate:Sm-eu-gd chloride solution mass ratio 5:100, magnesium sulfate is added in sm-eu-gd chloride solution, 30 points are stirred
Clock；Then zinc powder is pressed:The mass ratio 0.5 of europium in sm-eu-gd chloride solution:1, zinc powder reduction is added, is stirred 40 minutes；Finally
It is filtrated to get filter residue containing europium and the chloride filtrate of gadolinium containing samarium；Concentration is used to wash filter residue containing europium for 0.5mol/L hydrochloric acid solution,
Washings are returned for allocating above-mentioned sm-eu-gd chloride solution；By filter residue containing europium:Hydrochloric acid solution mass ratio is 1:3, europium will be contained
Filter residue is added in the hydrochloric acid solution that concentration is 4mol/L, is stirred 30 minutes；Then filter residue is pressed:Hydrogen peroxide mass ratio is 1:0.1
The hydrogen peroxide that concentration is 20%wt is added, is stirred 1 hour；Finally diluted by the water of above-mentioned 0.5 times of hydrochloric acid solution addition, filtering
Trivalent europium solution 10L is obtained, filter residue is undecomposed europous sulfate, weight 0.1Kg, filter residue returns to resolution process again.Through analyzing, its
In [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 is 4.0, [Al3+]
Concentration is 1.5g/L.The solution is diluted to the solution that REO is 100g/L, by glacial acetic acid:Sm-eu-gd chloride solution volume ratio
10:1000, glacial acetic acid is added in sm-eu-gd chloride solution, stirred 20 minutes, regulation pH value to 2.5 or so；In room temperature
Under, by magnesium sulfate:Sm-eu-gd chloride solution mass ratio 10:100, magnesium sulfate is added in sm-eu-gd chloride solution, stirred
Mix 40 minutes；Then zinc powder is pressed:The mass ratio 1 of europium in sm-eu-gd chloride solution:1, zinc powder reduction is added, is stirred 80 minutes；
Finally it is filtrated to get filter residue containing europium and the chloride filtrate of gadolinium containing samarium；The hydrochloric acid solution washing that concentration is 1.0mol/L is used to be filtered containing europium
Slag, washings are returned for allocating above-mentioned sm-eu-gd chloride solution；By filter residue containing europium:Hydrochloric acid solution mass ratio is 1:4, it will contain
Europium filter residue is added in the hydrochloric acid solution that concentration is 6mol/L, is stirred 30 minutes；Then filter residue is pressed:Hydrogen peroxide mass ratio is 1:
0.3 adds the hydrogen peroxide that concentration is 40%wt, stirs 3 hours；Finally diluted by the water of above-mentioned 2 times of hydrochloric acid solution addition, filtering
Trivalent europium solution 26L is obtained, filter residue is undecomposed europous sulfate, weight 0.3Kg, filter residue returns to resolution process again.Through analyzing, its
In [Eu3+] concentration be 72g/L, [Sm3++Gd3+] it is 9g/L, europium direct yield is 94%.
Claims (6)
1. being enriched with the method for europium in a kind of chloride solution from sm-eu-gd, the sm-eu-gd chloride solution separates for rare earth extraction
Intermediate product or sm-eu-gd oxide lysate, wherein [Eu3+] concentration is 3 ~ 50g/L, Σ REO are 70 ~ 300g/L, and pH is
3 ~ 5, containing a small amount of aluminium ion, it is characterized in that comprising the steps of successively：
1）Dispensing: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, regulation pH value to 1.5 ~ 3；
2）Reduction:At room temperature, in step 1）Solution in add magnesium sulfate, stir 30 ~ 60 minutes；Then zinc powder is added, is stirred
Mix 30 ~ 120 minutes；Filter residue containing europium and the chloride filtrate of gadolinium containing samarium are filtrated to get, concentration is used for 0.5 ~ 2mol/L watery hydrochloric acid
Filter residue containing europium is washed, washings are used to allocate above-mentioned sm-eu-gd chloride solution；
3）Decompose:At room temperature, in step 2）Filter residue containing europium in add hydrochloric acid solution, stir 30 ~ 60 minutes；Add dioxygen
Water, is stirred 1 ~ 5 hour；By 0.5 ~ 4 times of above-mentioned hydrochloric acid solution addition, it is diluted with water；Stir, to be filtrated to get trivalent europium molten
Liquid, filter residue returns to resolution process again.
2. the method for europium is enriched with the chloride solution according to claim 1 from sm-eu-gd, it is characterized in that the glacial acetic acid
Addition be glacial acetic acid:Sm-eu-gd chloride solution volume ratio 5 ~ 15:1000.
3. the method for europium is enriched with the chloride solution according to claim 1 from sm-eu-gd, it is characterized in that the magnesium sulfate
Addition be magnesium sulfate:Sm-eu-gd chloride solution mass ratio 5 ~ 15:100.
4. the method for europium is enriched with the chloride solution according to claim 1 from sm-eu-gd, it is characterized in that the zinc powder
Addition is zinc powder:The mass ratio 0.5 ~ 2 of europium in sm-eu-gd chloride solution:1.
5. the method for europium is enriched with the chloride solution according to claim 1 from sm-eu-gd, it is characterized in that the hydrochloric acid is molten
The addition of liquid is filter residue containing europium:Hydrochloric acid solution mass ratio 1:2 ~ 6, concentration of hydrochloric acid solution is 4 ~ 10mol/L.
6. the method for europium is enriched with the chloride solution according to claim 1 from sm-eu-gd, it is characterized in that the hydrogen peroxide
Addition 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680167A (en) * | 2019-01-17 | 2019-04-26 | 广东省稀有金属研究所 | A method of the continuously Separation Europium from rare-earth liquid |
| CN115784291A (en) * | 2022-11-18 | 2023-03-14 | 吉水金诚新材料加工有限公司 | Device for removing europium oxide from high-purity gadolinium oxide |
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 |
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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 |
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| CN109680167A (en) * | 2019-01-17 | 2019-04-26 | 广东省稀有金属研究所 | A method of the continuously Separation Europium from rare-earth liquid |
| CN115784291A (en) * | 2022-11-18 | 2023-03-14 | 吉水金诚新材料加工有限公司 | Device for removing europium oxide from high-purity gadolinium oxide |
| CN115784291B (en) * | 2022-11-18 | 2024-01-30 | 吉水金诚新材料加工有限公司 | Device for removing europium oxide from high-purity gadolinium oxide |
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Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of rare metals, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: GUANGDONG INSTITUTE OF RARE METALS |
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Effective date of registration: 20231101 Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: Institute of rare metals, Guangdong Academy of Sciences |