CN1044499A - Recycle oxalic acid extracts the technology of rare earth - Google Patents
Recycle oxalic acid extracts the technology of rare earth Download PDFInfo
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- CN1044499A CN1044499A CN89106897A CN89106897A CN1044499A CN 1044499 A CN1044499 A CN 1044499A CN 89106897 A CN89106897 A CN 89106897A CN 89106897 A CN89106897 A CN 89106897A CN 1044499 A CN1044499 A CN 1044499A
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- 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
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Abstract
A kind of recycle oxalic acid extracts the technology of rare earth from ion type rareearth ore.This technology is to extract from ion type rareearth ore on the basis of rare-earth process at original oxalic acid that utilizes, and has mainly increased rare-earth oxalate precipitation to be carried out oxalic acid reclaims and oxalic acid utilizes operation.Whole technology is made up of rare earth leaching, oxalic acid precipitation, solid-liquid roughing out, oxalic acid recovery, solid-liquid separation, oxalic acid utilization and calcination operation.It is few that this technology has the oxalic acid consumption, saves oxalic acid about 50% than former technology; The technology simple possible need not increase equipment and device; Quality product easily guarantees, the low advantages such as (reducing more than 15% than former technology) of production cost.
Description
The technology, especially the recycle oxalic acid that the present invention relates to extraction rare earth in a kind of hydrometallurgy field extract the technology of rare earth from ion type rareearth ore.
At present, extracting rare earth from ion type rareearth ore mostly utilizes the rare earth in salt strong electrolyte and the rare-earth original ore to carry out the feed liquid that ion exchange reaction obtains containing rare earth, use the precipitation agent of oxalic acid then as rare earth, it and rare earth form insoluble rare-earth oxalate and separate from solution, and calcination is at high temperature at last removed the oxalic acid material and obtained rare earth oxide product [Chinese rare earth association " rare earth " 83.3].This technology has the product purity height, advantages such as technology is simple and easy to grasp, and throw out is easily separated, the problem of existence is that consumption of oxalic acid is more, 1 ton of rare earth oxide product of every production need exhaust 2 tons of left and right sides oxalic acid, and the expense that is used for oxalic acid accounts for about 60% of production raw materials cost.
In order to reduce the consumption of oxalic acid problem in the Rare Earth Production, someone once adopted by reducing the impurity in the feed liquid, reduce oxalic acid and impurity and form complex compound, thereby reduce the method for oxalic acid loss, also the someone adopts and soaks the ore deposit agent concentration by raising the rare earth concentration in the feed liquid is improved, thereby reduces the method [Chinese rare earth association " rare earth " 88.4] of the remaining loss amount of oxalic acid in surplus liquid.But the purpose of aforesaid method just reduces solubility oxalic acid amount in the solution (accounting for oxalic acid total amount about 25%), and for that part of oxalic acid that has formed rare-earth oxalate (account for oxalic acid total amount about 75%) in present extraction rare-earth process still at high temperature expense abandon.
Oxalic acid is reclaimed in the nitric acid and the rare-earth oxalate reaction that disclose a kind of usefulness 50～60% concentration in No. 783298, the russian patent, as the method for fertiliser production, nitric acid dosage is 4.6～8.6 times of rare earth content, complex process, the equipment requirements height is difficult to use among the existing extraction rare-earth process.
The objective of the invention is to overcome the big shortcoming of oxalic acid consumption that exists in the said extracted rare-earth process, provide a kind of processing unit simple, cost is low, and reusable edible oxalic acid extracts the technology of rare earth from ion type rareearth ore.
Task of the present invention realizes in the following manner: promptly utilize oxalic acid to make precipitation agent to extract on the basis of rare-earth process from ion type rareearth ore original, between oxalic acid precipitation and solid-liquid separation process, increased solid-liquid roughing out and oxalic acid recovery process, between solid-liquid separation and calcination operation, increased oxalic acid and utilized operation.
It is to utilize salt strong electrolyte (NaCl as 5～7%, 1～4% (NH that rare earth leaches operation
4)
2SO
4Or NH
4Cl etc.) agent is in return leached rare earth from ion type rareearth ore, liquid: Gu=0.5～0.8: 1.
The oxalic acid precipitation operation is that to utilize concentration be 1～5%, the rare earth in the oxalic acid solution precipitation leach liquor of pH value 1～4, oxalic acid: RE
2O
3=1: 1.6～2.2(weight), obtain the solution that rare-earth oxalate precipitates and contain the part exchanger.
Solid-liquid roughing out operation is that rare-earth oxalate precipitation and the solution that contains the part exchanger are carried out roughing out with ordinary method, the solution that contains the part exchanger that obtains is handled (PH=4.5～5.0), add the rare earth that circulation is used for next time behind the exchanger and leach operation.
The oxalic acid recovery process is that isolated rare-earth oxalate material and one or more solubility inorganic carbonates are carried out permutoid reaction.
The solubility inorganic carbonate that uses in the present invention is bicarbonate of ammonia, volatile salt, sodium bicarbonate and yellow soda ash.
In the oxalic acid recovery process, rare-earth oxalate material and solubility inorganic carbonate are reacted by 1: 0.2～4.0 weight ratio, make liquid: Gu=5～40: 1, stirred 5～60 minutes, and promptly obtained containing the solution of oxalate material and contain rare earth carbonate and the unreacted mixed sediment of rare-earth oxalate completely.
Solid-liquid separation process is that the solution that will obtain in the oxalic acid recovery process separates with ordinary method with throw out.
It is the solution that contains the oxalate material (with sulfuric acid or hydrochloric acid) acidifying according to a conventional method that above-mentioned separation is obtained that oxalic acid utilizes operation, makes PH＜4, is used for next round-robin oxalic acid precipitation operation after adding an amount of oxalic acid.
The calcination operation be with obtain in the solid-liquid separation process contain rare earth carbonate and unreacted completely rare-earth oxalate mixed sediment through washing, dry after calcination 30～60 minutes under 800～850 ℃ high temperature, promptly obtain containing RE
2O
3Rare earth oxide product more than 92%.
The operation of the recovery oxalic acid among the present invention also can be used for separately reclaiming the oxalic acid material from rare-earth oxalate, as long as the solution that contains the oxalate material that will obtain carries out condensing crystal, can obtain corresponding oxalate material.
Process implementing of the present invention does not need special equipment and device, and except that the calcination operation, all the other all carry out at normal temperatures and pressures.
The technology that recycle oxalic acid of the present invention extracts rare earth has the following advantages: (1) oxalic acid consumption is few, produces 1 kilogram of rare earth oxide (RE
2O
3) only need 0.65～0.84 kilogram of oxalic acid, save oxalic acid about 50% than former technology; (2) technology simple possible need not increase equipment and device; (3) quality product guarantees that easily the rare-earth products after reclaiming oxalic acid can not increase impurity; (4) production cost is low, has reduced more than 15% than the cost of former rare earth production technology.
Fig. 1 is a process flow sheet of the present invention.
Below in conjunction with embodiment the present invention is described in more detail.
Embodiment:
Select heavy rare earths ore deposit in certain ionic of Ganzhou Prefecture, Jiangxi Province (grade 0.0506%) for use, carry out the test that four times recycle oxalic acid extracts rare earth.Test conditions, parameter and result are as shown in table-1.
From the table-1 as can be seen, extract in the 1st circulation of rare-earth process test in circulation, the oxalic acid add-on is 5.41 grams, and in the 2nd, 3,4 round-robin tests, owing to adopted oxalic acid recovery process and oxalic acid to utilize operation, the oxalic acid amount that needs to add in oxalic acid precipitation is reduced to 2.49 grams, 2.35 grams and 2.69 grams respectively.
Claims (3)
1, a kind of recycle oxalic acid extracts the technology of rare earth, form by rare earth leaching, oxalic acid precipitation, solid-liquid separation and calcination operation, it is characterized in that: between oxalic acid precipitation and solid-liquid separation process, increase solid-liquid roughing out and oxalic acid recovery process, behind solid-liquid separation process, increase oxalic acid and utilize operation
A. the oxalic acid recovery process is that rare-earth oxalate material and one or more solubility inorganic carbonates that the solid-liquid roughing out obtains are carried out permutoid reaction,
B. to utilize operation be that the oxalate material that will obtain after the solid-liquid separation contains liquid (with sulfuric acid or hydrochloric acid) acidifying according to a conventional method to oxalic acid, is used for next round-robin oxalic acid precipitation operation after making PH＜4.
2, recycle oxalic acid according to claim 1 extracts the technology of rare earth, it is characterized in that: it is bicarbonate of ammonia, volatile salt, sodium bicarbonate or yellow soda ash that oxalic acid reclaims the solubility inorganic carbonate that uses.
3, recycle oxalic acid according to claim 1 extracts the technology of rare earth, it is characterized in that: in the oxalic acid recovery process, rare-earth oxalate and solubility inorganic carbonate are reacted by 1: 0.2～4.0 weight ratio, make liquid: Gu=5～40: 1, stirred 5～60 minutes, and isolated the solution that contains oxalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106897A CN1016679B (en) | 1989-12-23 | 1989-12-23 | Extraction of rare-earth elements by circulating oxalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106897A CN1016679B (en) | 1989-12-23 | 1989-12-23 | Extraction of rare-earth elements by circulating oxalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044499A true CN1044499A (en) | 1990-08-08 |
| CN1016679B CN1016679B (en) | 1992-05-20 |
Family
ID=4856963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89106897A Expired CN1016679B (en) | 1989-12-23 | 1989-12-23 | Extraction of rare-earth elements by circulating oxalic acid |
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| Country | Link |
|---|---|
| CN (1) | CN1016679B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976525A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for treating and recycling rare earth oxalate precipitation mother solution |
| CN103086440A (en) * | 2011-11-02 | 2013-05-08 | 深圳市环境友好金属材料工程技术研究开发中心 | Method for processing cobalt oxalate waste |
| CN103266224A (en) * | 2013-05-27 | 2013-08-28 | 江西理工大学 | Ion-adsorption-type rare earth extracting method |
| CN108218682A (en) * | 2017-12-13 | 2018-06-29 | 包头稀土研究院 | The method of calcium oxalate waste residue solid-solid conversion recycling oxalic acid |
| CN113387795A (en) * | 2021-06-09 | 2021-09-14 | 江苏南方永磁科技有限公司 | Method for extracting oxalic acid from rare earth waste liquid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1989
- 1989-12-23 CN CN89106897A patent/CN1016679B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086440A (en) * | 2011-11-02 | 2013-05-08 | 深圳市环境友好金属材料工程技术研究开发中心 | Method for processing cobalt oxalate waste |
| CN103086440B (en) * | 2011-11-02 | 2014-10-29 | 深圳市环境友好金属材料工程技术研究开发中心 | Method for processing cobalt oxalate waste |
| CN102976525A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for treating and recycling rare earth oxalate precipitation mother solution |
| CN103266224A (en) * | 2013-05-27 | 2013-08-28 | 江西理工大学 | Ion-adsorption-type rare earth extracting method |
| CN103266224B (en) * | 2013-05-27 | 2016-06-22 | 江西理工大学 | A kind of ion adsorption type re extracting method |
| CN108218682A (en) * | 2017-12-13 | 2018-06-29 | 包头稀土研究院 | The method of calcium oxalate waste residue solid-solid conversion recycling oxalic acid |
| CN108218682B (en) * | 2017-12-13 | 2020-10-30 | 包头稀土研究院 | Method for recovering oxalic acid by solid-solid conversion of calcium oxalate waste residue |
| CN113387795A (en) * | 2021-06-09 | 2021-09-14 | 江苏南方永磁科技有限公司 | Method for extracting oxalic acid from rare earth waste liquid |
| CN113387795B (en) * | 2021-06-09 | 2023-06-09 | 江苏南方永磁科技有限公司 | Method for extracting oxalic acid from rare earth waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1016679B (en) | 1992-05-20 |
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