CN102337405B - Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate - Google Patents
Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate Download PDFInfo
- Publication number
- CN102337405B CN102337405B CN2011103445910A CN201110344591A CN102337405B CN 102337405 B CN102337405 B CN 102337405B CN 2011103445910 A CN2011103445910 A CN 2011103445910A CN 201110344591 A CN201110344591 A CN 201110344591A CN 102337405 B CN102337405 B CN 102337405B
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- Prior art keywords
- rare earth
- precipitation
- sulfate
- europium
- solution
- Prior art date
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Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract 11
- 238000001556 precipitation Methods 0.000 title claims abstract 9
- 239000002351 wastewater Substances 0.000 title claims abstract 8
- ONQORTHCHCYWSQ-UHFFFAOYSA-L europium(2+);sulfate Chemical compound [Eu+2].[O-]S([O-])(=O)=O ONQORTHCHCYWSQ-UHFFFAOYSA-L 0.000 title claims abstract 5
- 238000000034 method Methods 0.000 title claims abstract 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims abstract 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract 5
- 239000012141 concentrate Substances 0.000 claims abstract 4
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims abstract 3
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 claims abstract 3
- 238000005660 chlorination reaction Methods 0.000 claims 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- -1 rare earth carbonate Chemical class 0.000 claims 2
- TVYNCCPJWWBXRT-UHFFFAOYSA-N [Sm].[Gd] Chemical group [Sm].[Gd] TVYNCCPJWWBXRT-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000012065 filter cake Substances 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 229910052693 Europium Inorganic materials 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001940 europium oxide Inorganic materials 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000009854 hydrometallurgy Methods 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract 1
- 235000019341 magnesium sulphate Nutrition 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate, belonging to the field of rare earth hydrometallurgy. The method comprises the step of concentrating precipitation wastewater from production of mixed carbonate-rare earth by baking and decomposing rare earth baotite concentrate with concentrated sulfuric acid to obtain a concentrated mixed solution of ammonium sulfate and magnesium sulfate. The obtained concentrated mixed solution is used as a rich europium preparation reagent in europium oxide extraction process from Sm-Eu-Gd enrichment mineral to replace single magnesium sulfate heptahydrate to be used as europium (II) sulfate precipitant, thereby broadening the recycling ranges of precipitation wastewater from production of mixed carbonate-rare earth from rare earth baotite concentrate, lowering the energy consumption in concentration and crystallization of recovered wastewater, saving the production cost, and reducing the resource waste and environmental pollution.
Description
Technical field
The present invention relates to the method for a kind of baotite mixed rare earth carbonate precipitation waste water for the europous sulfate precipitation, belong to the rare-earth wet method field of metallurgy.
Background technology
From Sm Eu Gd concentrate, extract europium sesquioxide technique at present, one of its critical process is the preparation of rich europium, industry widespread use be, with zinc powder, the trivalent europium is reduced to divalent europium, the divalent europium generated reacts with sulfate radical and generates stable europous sulfate precipitation, realize europium and other Rare Earth Separation, in technique, sulfate radical is to join reaction system with magnesium sulfate heptahydrate, sal epsom as the europous sulfate precipitation agent in widespread use, and in fluorescence europium oxide production technique at present, be not widely used as precipitation agent with ammonium sulfate or ammonium sulfate and sal epsom mixture.
Produce mixed rare earth carbonate technique with vitriol oil decomposing Baotou rare earth ore concentrate, the a large amount of ammonium sulfate and the sal epsom waste water that produce, produce 1 ton of baotite mixed rare earth carbonate and produce 13 tons of mother liquor waste waters, obtain ammonium sulfate and magnesium sulfate heptahydrate mixed crystal 1110kg, wherein liquid containing ammonium sulfate 480kg, magnesium sulfate heptahydrate 630kg through concentrated, crystallization.This mixture application facet can only be fertile for agriculture, ion adsorption type rare earth ore soak the less demanding sector application such as ore deposit reagent, as obtained purer ammonium sulfate and the higher production cost of magnesium sulfate heptahydrate product needed, enterprise is difficult to bear, so be restricted in other field application, the a large amount of crystal that reclaim exist and overstock, and will cause waste and the environmental pollution of resource as precipitated discharge of wastewater.
Summary of the invention
The purpose of this invention is to provide the method for a kind of baotite mixed rare earth carbonate precipitation waste water for the europous sulfate precipitation, the method is produced mixed rare earth carbonate precipitation Waste water concentrating by the concentrated sulfuric acid roasting decomposing Baotou rare earth ore concentrate, ammonium sulfate after being concentrated and sal epsom mixing solutions, get for single magnesium sulfate heptahydrate as the europous sulfate precipitation agent, save production cost, reduce waste and the environmental pollution of resource.
Technical solution:
Baotite mixed rare earth carbonate precipitation waste water of the present invention is for the method for europous sulfate precipitation.The Baotou rare earth ore concentrate mixed rare earth carbonate precipitates liquid containing ammonium sulfate 0.28mol/L in waste water, contains magnesium sulfate heptahydrate 0.2mol/L, by concentrated 5 times of this wastewater volume, in solution after concentrated, ammonium sulfate and magnesium sulfate heptahydrate all do not produce crystallization, obtain concentrated solution after concentrated, liquid containing ammonium sulfate 1.4mol/L in concentrated solution, containing magnesium sulfate heptahydrate 1mol/L, cooling stand-by; Raw material chlorination sm-eu-gd solution is squeezed in setting tank to europium sesquioxide content Eu in the raw material sm-eu-gd
2o
3/ REO is 6～15%, and rare earth concentration is 0.5～1.5mol/L, and feed acidity pH=4 adds respectively zinc powder, and the weight ratio containing the europium sesquioxide amount in zinc powder add-on and Sm Eu Gd concentrate is 0.35: 1; Add concentrated rear ammonium sulfate and sal epsom mixing solutions, add-on is the solution after adding 4.73 liters to concentrate containing the 1kg europium sesquioxide in sm-eu-gd; Open stirring reaction 2 hours, clarify 4 hours, filter, obtaining filter cake is the europous sulfate precipitation, europium sesquioxide content Eu
2o
3/ REO>92%, filtrate is samarium gadolinium enriched substance solution, europium sesquioxide content Eu in the samarium gadolinium
2o
3/ REO<0.1%.
Sulfate radical after the present invention is concentrated in solution and divalent europium generate the europous sulfate precipitation, ammonium ion, magnesium ion and excessive sulfate radical enter in samarium gadolinium solution, after extracting and separating purification samarium gadolinium, ammonium ion, magnesium ion and excessive sulfate radical are drained into the wastewater treatment operation with extracting and separating waste water.
It is crucial controlling the Waste water concentrating amount in the present invention, and control Waste water concentrating amount is conducive to ammonium sulfate and sal epsom is constant in concentrated rear weight ratio, is convenient to determine concentrated rear waste water add-on.
Advantage of the present invention
(1) contain micro-rare earth element in waste water in rare earth carbonate precipitation, can not affect zinc powder reduction europous sulfate preparation technology after waste water recycling, more can not affect fluorescence europium oxide purity, can improve the rare earth yield, reduce the wasting of resources simultaneously.
(2) precipitation waste water does not need to concentrate fully and is prepared into crystal, and the solution after concentrated can dilute the raw material rare earth concentration, reduces energy consumption concentrated, crystallization.
Embodiment
Embodiment 1
Liquid containing ammonium sulfate 0.28mol/L, magnesium sulfate heptahydrate 0.2mol/L in Baotou rare earth ore concentrate mixed rare earth carbonate precipitation waste water, by concentrated 5 times of this wastewater volume, liquid containing ammonium sulfate 1.4mol/L in the solution after concentrated, containing magnesium sulfate heptahydrate 1mol/L, cooling stand-by.
At 3M
3in retort, add 2M
3the Sm Eu Gd concentrate feed liquid, the feed liquid rare earth concentration is 1mol/L, feed acidity pH=4, europium sesquioxide content Eu in feed liquid
2o
3/ REO is 10%, adds the 12.32kg zinc powder, adds 166.5 liters of ammonium sulfate after concentrated and sal epsom mixing solutionss, opens stirring reaction 2 hours, clarifies 4 hours, filters, and obtaining filter cake is the europous sulfate precipitation, europium sesquioxide content Eu
2o
3/ REO=92.6%, filtrate is samarium gadolinium enriched substance solution, europium sesquioxide content Eu in the samarium gadolinium
2o
3/ REO<0.08%.
Embodiment 2
Liquid containing ammonium sulfate 0.28mol/L, magnesium sulfate heptahydrate 0.2mol/L in Baotou rare earth ore concentrate mixed rare earth carbonate precipitation waste water, by concentrated 5 times of this wastewater volume, liquid containing ammonium sulfate 1.4mol/L in the solution after concentrated, containing magnesium sulfate heptahydrate 1mol/L, cooling stand-by.
At 3M
3in retort, add 2M
3the Sm Eu Gd concentrate feed liquid, the feed liquid rare earth concentration is 1.2mol/L, feed acidity pH=4, europium sesquioxide content Eu in feed liquid
2o
3/ REO is 8%, adds the 11.83kg zinc powder, adds 160 liters of ammonium sulfate after concentrated and sal epsom mixing solutionss, opens stirring reaction 2 hours, clarifies 4 hours, filters, and obtaining filter cake is the europous sulfate precipitation, europium sesquioxide content Eu
2o
3/ REO=92.8%, filtrate is samarium gadolinium enriched substance solution, europium sesquioxide content Eu in the samarium gadolinium
2o
3/ REO<0.05%.
Claims (1)
1. baotite mixed rare earth carbonate precipitation waste water is for the method for europous sulfate precipitation, it is characterized in that, the Baotou rare earth ore concentrate mixed rare earth carbonate precipitates liquid containing ammonium sulfate 0.28mol/L in waste water, contains magnesium sulfate heptahydrate 0.2mol/L, this waste water is concentrated, obtain concentrated solution, liquid containing ammonium sulfate 1.4mol/L in concentrated solution, containing magnesium sulfate heptahydrate 1mol/L, cooling stand-by; Raw material chlorination sm-eu-gd solution is squeezed in setting tank to europium sesquioxide content Eu in this solution
2o
3/ REO is 6～15%, and rare earth concentration is 0.5～1.5mol/L, and feed acidity pH=4 adds respectively zinc powder, concentrated rear ammonium sulfate and sal epsom mixing solutions, and the weight ratio containing the europium sesquioxide amount in zinc powder add-on and chlorination sm-eu-gd is 0.35: 1; The amount that adds concentrated rear ammonium sulfate and sal epsom mixing solutions is the solution after adding 4.73 liters to concentrate containing the 1kg europium sesquioxide in the chlorination sm-eu-gd; Open stirring reaction 2 hours, clarify 4 hours, filter, obtaining filter cake is the europous sulfate precipitation, europium sesquioxide content Eu
2o
3/ REO>92%, filtrate is samarium gadolinium enriched substance solution, europium sesquioxide content Eu in this solution
2o
3/ REO<0.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103445910A CN102337405B (en) | 2011-10-28 | 2011-10-28 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103445910A CN102337405B (en) | 2011-10-28 | 2011-10-28 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
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| Publication Number | Publication Date |
|---|---|
| CN102337405A CN102337405A (en) | 2012-02-01 |
| CN102337405B true CN102337405B (en) | 2013-12-11 |
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| CN2011103445910A Expired - Fee Related CN102337405B (en) | 2011-10-28 | 2011-10-28 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
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| CN107326200B (en) * | 2017-05-25 | 2019-05-31 | 广东省稀有金属研究所 | A method of it being enriched with europium from sm-eu-gd chloride solution |
| CN109735719B (en) * | 2019-03-19 | 2020-07-14 | 王柯娜 | Method for processing waste television fluorescent powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1017419B (en) * | 1989-06-13 | 1992-07-15 | 甘肃稀土公司 | Preparation process of europium sulfate |
| CN100485056C (en) * | 2004-06-12 | 2009-05-06 | 包头市京瑞新材料有限公司 | Zinc powder reduction process of preparing europium-enriched solution |
| CN102190325B (en) * | 2010-03-17 | 2014-07-16 | 有研稀土新材料股份有限公司 | Method for recovering rare earth from ionic type rare earth crude ore |
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