CN103408091B - Recovery method of rare earth oxalate precipitation wastewater - Google Patents
Recovery method of rare earth oxalate precipitation wastewater Download PDFInfo
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- CN103408091B CN103408091B CN201310304975.9A CN201310304975A CN103408091B CN 103408091 B CN103408091 B CN 103408091B CN 201310304975 A CN201310304975 A CN 201310304975A CN 103408091 B CN103408091 B CN 103408091B
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- rare earth
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- wastewater
- oxalate
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 65
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000001556 precipitation Methods 0.000 title claims abstract description 32
- -1 rare earth oxalate Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000011084 recovery Methods 0.000 title claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 abstract description 38
- 238000000605 extraction Methods 0.000 abstract description 27
- 235000006408 oxalic acid Nutrition 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 229910052771 Terbium Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 2
- RVNCZYOIAUWWCB-UHFFFAOYSA-N oxalic acid;terbium Chemical compound [Tb].OC(=O)C(O)=O RVNCZYOIAUWWCB-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a recovery method of rare earth oxalate precipitation wastewater. The method is characterized in that the rare earth oxalate precipitation wastewater and hydrochloric acid are prepared into a solution, wherein the concentration of oxalate is 0.01-10g/L, and the concentration of H<+> is 3.5-6mol/L. According to the method provided in the invention, the rare earth oxalate precipitation wastewater and hydrochloric acid are prepared into a solution for back extraction of rare earth from a rare earth loaded extraction solution. Therefore, the wastewater discharge problem is solved, and the acid needed by back extraction of rare earth and the oxalic acid required by final rare earth precipitation can also be saved.
Description
Technical field
The present invention relates to a kind of recovery method of rare earth oxalate precipitation wastewater.
Background technology
Since 20th century the mid-80s, China's rare-earth industry development is very rapid, and achieves huge achievement.But rare-earth smelting belongs to hydrometallurgy, wastewater flow rate is larger, and waste water has seriously polluted and administers the features such as difficulty, and rare-earth smelting will bring larger environmental problem.
Rare Earth Production mainly comprises dissolving, extraction, strips and the operation such as precipitation, and wherein rare earth oxide or carbonated rare earth dissolving with hydrochloric acid are mainly rare earth chloride by dissolution process.Extraction process utilizes extraction agent to the difference of extraction ability between rare earth element, enters in extraction agent, form the extraction agent of supported rare earth by easy extracting rare-earth extraction.Reextraction operation is stripped by the extraction agent of rare earth from supported rare earth with certain density hydrochloric acid.Precipitation operation adopts oxalic acid to be precipitated by the rare earth chloride of stripping.Precipitation operation produces a large amount of mother liquor of precipitation of ammonium and the waste water of washing precipitation, and such waste water is referred to as rare earth oxalate precipitation wastewater, and its main component is the mixing solutions of hydrochloric acid and oxalic acid and the rare earth oxalate of trace and impurity etc., and oxalate concentration is 0.5 ~ 30g/L, H
+concentration is 0.1 ~ 3mol/L, and rare earth ion concentration is 10 ~ 200mg/L.At present, this type of waste water of domestic process mainly adopts limestone vegetation method, although this method is simple to operate, low cost, operating environment is severe, and the quantity of slag is large and difficult, and the acid in water is not recycled, and wastes resource.In recent years, many Rare Earth Factories adopt multiple method to administer this kind of waste water all not reach satisfied effect, and therefore, the improvement of rare earth oxalate precipitation wastewater is one of rare-earth industry problem demanding prompt solution.In order to recycle oxalic acid precipitation RE waste water, investigator's major objective concentrates on and reclaims oxalic acid in rare earth oxalate precipitation wastewater and hydrochloric acid, at present, mainly contains two kinds for the treatment of processs: method of evaporation and extraction process.Method of evaporation utilizes the principle of hydrogenchloride and water azeotropic in the characteristic of oxalic acid and hydrochloric acid, and evaporation rare earth oxalate precipitation wastewater, evaporate hydrochloric acid and water, in evaporative process, oxalic acid is crystallization in mother liquid evaporation.The method energy consumption is high, and hydrochloric acid corrosion resistance is very strong at a higher temperature.Extraction process has extraction Oxalic Acid Method and extraction hydrochloric acid method, and wherein extracting Oxalic Acid Method, is extracted by the oxalic acid in waste water, wastewater reuse, is stripped by oxalic acid after extraction agent extraction oxalic acid again.Extraction hydrochloric acid method mainly utilizes amine extractant by the hcl as extraction agent in waste water in organic phase, then adopts water to strip hydrochloric acid, forms dilute hydrochloric acid, thus reclaim hydrochloric acid.Above-mentioned extraction process can reclaim hydrochloric acid or oxalic acid, but also creates waste water in removal process simultaneously, loses more than gain.
In rare-earth trade, people generally believe: rare earth oxalate precipitation wastewater contains oxalate, waste water easily and rare earth produce and precipitate, cause waste water to utilize.But people often have ignored the increase along with solution acidic, the solubleness of rare-earth oxalate sharply increases.The present invention will utilize this principle, rare earth oxalate precipitation wastewater and hydrochloric acid are mixed with solution, for the anti-stripping agent of rare earth of stripping from the extraction agent of supported rare earth, both solve discharge of wastewater problem, again save the acid of reextraction rare earth needs and the oxalic acid needed for final precipitating rare earth.
Summary of the invention
Rare earth oxalate precipitation wastewater of the present invention is the waste water that rare-earth precipitation operation produces, and comprising: the waste water of mother liquor of precipitation of ammonium and washing precipitation, the oxalate concentration of rare earth oxalate precipitation wastewater is 0.5 ~ 30g/L, H
+concentration is 0.1 ~ 3mol/L, and rare earth ion concentration is 10 ~ 200mg/L.
The object of the present invention is to provide a kind of recovery method of rare earth oxalate precipitation wastewater.
Technical scheme of the present invention is; Rare earth oxalate precipitation wastewater and hydrochloric acid are mixed with solution, make its oxalate concentration be 0.01 ~ 10g/L, H
+concentration is 3.5 ~ 6mol/L.
The solubleness of rare-earth oxalate sharply increases along with the increase of solution acidic, and under certain acidity condition, when oxalate is below 10g/L, oxalate can not generate with rare earth and precipitate.The present invention is based on this principle, rare earth oxalate precipitation wastewater and hydrochloric acid are mixed with solution, for rare earth of stripping from the extraction solution of supported rare earth, both solve discharge of wastewater problem, again save the acid of reextraction rare earth needs and the oxalic acid needed for final precipitating rare earth.
Embodiment
Embodiment 1
The precipitation waste water of oxalic acid precipitation europium, the europium ion concentration of this solution is 45mg/L, H
+concentration is 1.82mol/L, C
2o
4 2-concentration be 30g/L; Industrial concentrated hydrochloric acid 122L that concentration is 30%wt is added and 78L water is mixed with H in above-mentioned waste water 100L
+concentration is 5.5mol/L, C
2o
4 2-concentration is the solution of 10g/L; For the rare earth in the supported rare earth extraction solution of stripping in divalent europium and other trivalent rare earth separating technology.
Embodiment 2
Oxalic acid terbium precipitation waste water, the terbium ion concentration of this solution is 75mg/L, H
+concentration is 1.95mol/L, C
2o
4 2-concentration be 15g/L; The dilute hydrochloric acid 512L that concentration is 15%wt will be added in above-mentioned waste water 100L; Be mixed with C
2o
4 2-concentration is 2.45g/L, H
+concentration is the solution of 4.5mol/L, for the rare earth in the supported rare earth extraction solution of stripping in pure terbium separating technology.
Embodiment 3
Yttrium oxalate precipitation waste water, the ruthenium ion concentration of this solution is 75mg/L, H
+concentration is 1.51mol/L, C
2o
4 2-concentration be 20g/L; By adding the dilute hydrochloric acid 400L that concentration is 10%wt in above-mentioned waste water 100L, be mixed with H
+concentration is 3.5mol/L, C
2o
4 2-concentration reduces to the solution of 4g/L, for the rare earth in the supported rare earth extraction solution of stripping in pure yttrium separating technology.
Embodiment 4
Yttrium oxalate precipitation waste water, the ruthenium ion concentration of this solution is 75mg/L, H
+concentration is 1.51mol/L, C
2o
4 2-concentration be 20g/L; Be that 15%wt technical hydrochloric acid 241L and 58.5L water are mixed with H by adding concentration in above-mentioned waste water 100L
+concentration is 4.0mol/L, C
2o
4 2-concentration reduces to the solution of 5g/L, for the rare earth in the supported rare earth extraction solution of stripping in pure yttrium separating technology.
Embodiment 5
Oxalic acid terbium washing of precipitate water, the terbium ion concentration of this solution is 75mg/L, H
+concentration is 0.12mol/L, C
2o
4 2-concentration be 0.8g/L; 30%wt technical hydrochloric acid 3999L and 3901L pure water is added by above-mentioned waste water 100L; Be mixed with 8000LC
2o
4 2-concentration is 0.01g/L, H
+concentration is the solution of 6.0mol/L, for the rare earth in the supported rare earth extraction solution of stripping in pure terbium separating technology.
Claims (1)
1. a recovery method for rare earth oxalate precipitation wastewater, it is characterized in that rare earth oxalate precipitation wastewater and hydrochloric acid to be mixed with solution, its oxalate concentration is 0.01 ~ 10g/L, H
+concentration is 3.5 ~ 6mol/L.
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| CN201310304975.9A CN103408091B (en) | 2013-07-19 | 2013-07-19 | Recovery method of rare earth oxalate precipitation wastewater |
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| CN103408091B true CN103408091B (en) | 2015-02-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105624403B (en) * | 2014-11-24 | 2018-08-24 | 赣州力赛科新技术有限公司 | A kind of method of comprehensive utilization of spent acid |
| CN106222419A (en) * | 2016-08-16 | 2016-12-14 | 南京格洛特环境工程股份有限公司 | Rare-earth oxidation europium extraction wastewater is except weight, except putting and resource recovery process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650652A (en) * | 1984-01-31 | 1987-03-17 | Kasei Optonix, Ltd. | Process for recovering highly pure rare earth oxides from a waste rare earth phosphor |
| CN101935762A (en) * | 2010-08-25 | 2011-01-05 | 江西明达功能材料有限责任公司 | Method for comprehensively recycling rare earth oxalate precipitate waste liquid |
| CN102676853A (en) * | 2012-05-28 | 2012-09-19 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN102976525A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for treating and recycling rare earth oxalate precipitation mother solution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979336B (en) * | 2010-09-03 | 2012-03-28 | 江西明达功能材料有限责任公司 | Method for simultaneously treating waste water and recovering rare earth of rare earth separation plant |
| CN102312098B (en) * | 2011-09-28 | 2013-08-14 | 武汉理工大学 | Method for separation and purification of fluorescent grade yttrium oxide and europium oxide from waste phosphor powder |
-
2013
- 2013-07-19 CN CN201310304975.9A patent/CN103408091B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650652A (en) * | 1984-01-31 | 1987-03-17 | Kasei Optonix, Ltd. | Process for recovering highly pure rare earth oxides from a waste rare earth phosphor |
| CN101935762A (en) * | 2010-08-25 | 2011-01-05 | 江西明达功能材料有限责任公司 | Method for comprehensively recycling rare earth oxalate precipitate waste liquid |
| CN102676853A (en) * | 2012-05-28 | 2012-09-19 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN102976525A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for treating and recycling rare earth oxalate precipitation mother solution |
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Effective date of registration: 20171227 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: GUANGDONG INSTITUTE OF RARE METALS Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee before: GUANGZHOU Research Institute OF NON FERROUS METALS |
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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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Application publication date: 20131127 Assignee: DONGGUAN QINGLIU NEW MATERIAL Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980037903 Denomination of invention: A Recovery Method for Rare Earth Oxalate Precipitation Wastewater Granted publication date: 20150204 License type: Common License Record date: 20230713 |
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Application publication date: 20131127 Assignee: Foshan shangxiaoyun Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980041338 Denomination of invention: A Recovery Method for Rare Earth Oxalate Precipitation Wastewater Granted publication date: 20150204 License type: Common License Record date: 20230907 Application publication date: 20131127 Assignee: FOSHAN ZHENGRONG TECHNOLOGY Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980041273 Denomination of invention: A Recovery Method for Rare Earth Oxalate Precipitation Wastewater Granted publication date: 20150204 License type: Common License Record date: 20230906 |
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