CN103146925B - Method of recycling rear earth from neodymium iron boron waste - Google Patents
Method of recycling rear earth from neodymium iron boron waste Download PDFInfo
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- CN103146925B CN103146925B CN201310096697.2A CN201310096697A CN103146925B CN 103146925 B CN103146925 B CN 103146925B CN 201310096697 A CN201310096697 A CN 201310096697A CN 103146925 B CN103146925 B CN 103146925B
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- rare earth
- filtered liquid
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- neodymium
- iron boron
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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
- 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
Abstract
The invention discloses a method of recycling rear earth from neodymium iron boron waste, wherein the method comprises such steps as calcination, acidolysis, separation and firing and the like, and modified attapulgite and hydrogen peroxide are used for treating the filtrate in the invention to greatly reduce the content of iron element in the filtrate and improve the purity of the rear earth metallic oxides, so that the quality is greatly improved.
Description
Technical field
The present invention relates to rare earth resources and reclaim and recycle utilization field, particularly relate to the method for Extraction of rare earth in a kind of neodymium iron boron waste material from being oxidized.
Background technology
Nd-Fe-B permanent magnet is a kind of permanent magnet material of superior performance, since within 1983, coming out, just from numerous permanent magnet materials, has shown one's talent, and is widely used in high-tech every field.Become the outstanding person in permanent magnet material because Nd-Fe-Bo permanent magnet material has high remanent magnetism, high-coercive force, high energy product, be acknowledged as " magnetic king ".China is beginning to take shape the industrial system of oneself aspect Nd-Fe-Bo permanent magnet material production, output accounts for 45% of global total value.In recent years, the output of Chinese sintered NdFeB is with 35% speed increment.
Producing in the process of Nd-Fe-B permanent magnetic element, by producing the waste material of many blanks, material cutting and abrasive material class, add underproof magnetic part, its waste material amount is about raw material weight approximately 30%.Wherein contain the rare earth element Dy of 30% left and right of having an appointment, Tb, Gd, Ho etc., 60% ~ 65% iron;
According to current existing bibliographical information and patent about neodymium iron boron waste material recoverying and utilizing method, its main method comprises: complete molten method, oxidizing roasting-dissolving with hydrochloric acid etc. that the fluorochemical precipitator method, sulfuric acid-double salt precipitation technique, employing hydrochloric acid are solvent; These methods are to comprising Nd, Pr, and Dy, Tb, Gd, the recovery of the different rare earth elements such as Ho lacks the specific aim measure of carrying out clear sub-prime.In concrete production implementation process, exist recovery utilization rate low, the large and not high situation of rare-earth products quality of solid, liquid generation of waste materials amount.
Summary of the invention
The object of this invention is to provide a kind of from neodymium iron boron waste material the method for recovering rare earth, adopt the excellent molten solvent extration of hydrochloric acid, by the pre-treatment to neodymium iron boron waste material, make to obtain rare earth oxide metal purity and be significantly smaller than, purity is greater than 99%.
The present invention is achieved by the following technical solutions.
A method for recovering rare earth from neodymium iron boron waste material, is characterized in that the method comprises the following steps:
(1), pre-treatment: neodymium iron boron waste material is carried out to pre-treatment, transformation efficiency >=99.5% of Fe cycling of elements in oxidizing roasting link control waste material system at 700-800 ℃;
(2), waste material carried out to ball milling obtain fine powder, then use dissolving with hydrochloric acid, adjusting pH value is 4.5-5, filters and obtains filtered liquid and residue;
(3), residue repeating step (2) again, the filtered liquid obtaining and step (2) filtered liquid merge;
(4) the concentration 20-25% hydrogen peroxide that, simultaneously adds attapulgite modified, the 10-15% of the 1-2% that is equivalent to filtrate weight in filtrate, stirs 30-45 minute, centrifugal, removes slag;
Described attapulgite makes by the following method:
Attapulgite is added in 10-15% hydrochloric acid soln and soaks 3-4 hour, then, pull out and drain, send into after 450-500 ℃ of kiln roasting 3-4 hour, put into concentration 12-15% hydrogen peroxide solution and soak 1-2 hour, drain, after repeatedly rinsing with deionized water, then add the gac that is equivalent to attapulgite quality 2-3%, mix, under 12000-15000 rev/min, stir 5-8 minute, take out oven dry and obtain;
(5), in filtered liquid, add P507 extraction system, carry out the separation of rare earth chloride metal; Obtain the single rare earth chloride metals such as praseodymium chloride, Neodymium trichloride and Dysprosium trichloride solution;
(6), in the rare earth chloride metallic solutions such as praseodymium chloride, Neodymium trichloride and Dysprosium trichloride solution, add oxalic acid or bicarbonate of ammonia as precipitation agent, obtain rare earth metal precipitation, calcination, obtains rare metal oxide Praseodymium trioxide neodymium and dysprosium oxide etc.
The present invention is based on existing hydrochloric acid solvent extration is improved, in acidolysis filtrate, add attapulgite modified, hydrogen peroxide, can adsorb on the one hand the metallic impurity elements such as iron that remains in filter, adopt hydrogen peroxide to be oxidized simultaneously, the residual quantity of iron in filtrate is controlled in 0.1%, greatly improves the purity of rare-earth oxide.
Embodiment
A method for recovering rare earth from neodymium iron boron waste material, the method comprises the following steps:
(1), pre-treatment: neodymium iron boron waste material is carried out to pre-treatment, oxidizing roasting 3-4 hour at 700-800 ℃, detecting in waste material system Fe cycling of elements, to become the transformation efficiency of oxide compound be 99.5%;
(2), waste material carried out to ball milling obtain fine powder, then use dissolving with hydrochloric acid, adjusting pH value is 4.5-5, filters and obtains filtered liquid and residue;
(3), residue repeating step (2) again, the filtered liquid obtaining and step (2) filtered liquid merge;
(4) add 1% attapulgite modified, 15% concentration 25% hydrogen peroxide that are equivalent to filtrate weight, simultaneously in filtrate, stir 30-45 minute, centrifugal, remove slag; Detecting iron content in filtrate is 0.06%;
Described attapulgite makes by the following method:
Attapulgite is added in 15% hydrochloric acid soln and soaked 4 hours, then, pull out and drain, send into 500 ℃ of kiln roastings after 3 hours, put into concentration 15% hydrogen peroxide solution and soak 2 hours, drain, after repeatedly rinsing with deionized water, then add the gac that is equivalent to attapulgite quality 2%, mix, under 12000-15000 rev/min, stir 5 minutes, take out oven dry and obtain;
(5), in filtered liquid, add P507 extraction system, carry out the separation of rare earth chloride metal; Obtain the single rare earth chloride metals such as praseodymium chloride, Neodymium trichloride, Dysprosium trichloride, gadolinium sesquioxide, terbium sesquioxide, Holmium trioxide solution;
(6), in the rare earth chloride metallic solutions such as praseodymium chloride, Neodymium trichloride and Dysprosium trichloride solution, add oxalic acid or bicarbonate of ammonia as precipitation agent, obtain rare earth metal precipitation, calcination, obtains rare metal oxide Praseodymium trioxide neodymium and dysprosium oxide, gadolinium sesquioxide, terbium sesquioxide, Holmium trioxide etc.
Detection gained Praseodymium trioxide neodymium, dysprosium oxide, gadolinium sesquioxide, terbium sesquioxide, Holmium trioxide purity are all more than 99.5%, and gained earth oxide product is all up to state standards and industry standard requirement.
According to calculating, the total recovery utilization rate of rare earth element including 5 products such as Praseodymium trioxide neodymium, dysprosium oxide, gadolinium sesquioxide, terbium sesquioxide, Holmium trioxide reaches 97.5.0% (weight ratio of neodymium iron boron waste material rare earth elements total amount relatively).
In the present invention, hydrochloric acid consumption is little, is only the 15%-20% of the complete molten solvent extration of hydrochloric acid.Because acid consumes less, factory effluent is just few.
Claims (1)
1. a method for recovering rare earth from neodymium iron boron waste material, is characterized in that the method comprises the following steps:
(1), pre-treatment: neodymium iron boron waste material is carried out to pre-treatment, transformation efficiency >=99.5% of Fe cycling of elements in oxidizing roasting link control waste material system at 700-800 ℃;
(2), waste material carried out to ball milling obtain fine powder, then use dissolving with hydrochloric acid, regulating pH value is 4.5-5, filtration obtains filtered liquid and residue;
(3), residue repeating step (2) again, the filtered liquid obtaining and step (2) filtered liquid merge;
(4) the concentration 20-25% hydrogen peroxide that, simultaneously adds attapulgite modified, the 10-15% of the 1-2% that is equivalent to filtered liquid weight in filtered liquid, stirs 30-45 minute, centrifugal, removes slag;
Described attapulgite makes by the following method:
Attapulgite is added in 10-15% hydrochloric acid soln and soaks 3-4 hour, then, pull out and drain, send into after 450-500 ℃ of kiln roasting 3-4 hour, put into concentration 12-15% hydrogen peroxide solution and soak 1-2 hour, drain, after repeatedly rinsing with deionized water, then add the gac that is equivalent to attapulgite quality 2-3%, mix, under 12000-15000 rev/min, stir 5-8 minute, take out oven dry and obtain;
(5), in filtered liquid, add P507 extraction system, carry out the separation of rare earth chloride metal; Obtain the single rare earth chloride metal of praseodymium chloride, Neodymium trichloride and Dysprosium trichloride solution;
(6), in the rare earth chloride metallic solution of praseodymium chloride, Neodymium trichloride and Dysprosium trichloride solution, add oxalic acid or bicarbonate of ammonia as precipitation agent, obtain rare earth metal precipitation, calcination, obtains rare metal oxide Praseodymium trioxide neodymium and dysprosium oxide.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103343234B (en) * | 2013-07-19 | 2015-01-14 | 北京工业大学 | Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation |
| CN103911516B (en) * | 2014-03-27 | 2015-10-28 | 全南晶环科技有限责任公司 | A kind of technique extracting neodymium from waste electronic ceramics powder |
| CN106119523A (en) * | 2016-07-27 | 2016-11-16 | 信丰县包钢新利稀土有限责任公司 | A kind of efficiently self-heating autoxidation roasting neodymium iron boron waste material technology |
| CN110306071A (en) * | 2018-07-26 | 2019-10-08 | 安徽金三隆再生资源有限公司 | A kind of method for extraction and purification of dysprosia |
| CN111187927A (en) * | 2020-02-18 | 2020-05-22 | 内蒙古科技大学 | Method for selectively sulfating and recovering rare earth in neodymium iron boron waste |
| CN111549230B (en) * | 2020-05-22 | 2022-04-01 | 包头稀土研究院 | Treatment method of neodymium iron boron waste |
| CN115466859B (en) * | 2022-09-07 | 2023-06-30 | 中国科学院赣江创新研究院 | Method for selectively leaching rare earth and cobalt from iron tailings obtained by neodymium-iron-boron waste material hydrochloric acid eutectoid method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605638A (en) * | 2004-06-28 | 2005-04-13 | 辽宁美宝稀土材料有限公司 | Process for recovering rare earth from neodymium-ion-boron waste materials |
| CN102011020A (en) * | 2009-12-14 | 2011-04-13 | 包头市玺骏稀土有限责任公司 | Method for recovering rare earth elements from neodymium-iron-boron wastes |
| CN102912134A (en) * | 2012-09-27 | 2013-02-06 | 信丰县包钢新利稀土有限责任公司 | Neodymium, iron and boron waste recycling process with approximately zero wastewater discharge |
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| KR100578712B1 (en) * | 2004-11-04 | 2006-05-12 | 한국지질자원연구원 | Recovery of Neodymium from NdFeB Oxidation-Roasted Scrap by Acetic Acid Leaching |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605638A (en) * | 2004-06-28 | 2005-04-13 | 辽宁美宝稀土材料有限公司 | Process for recovering rare earth from neodymium-ion-boron waste materials |
| CN102011020A (en) * | 2009-12-14 | 2011-04-13 | 包头市玺骏稀土有限责任公司 | Method for recovering rare earth elements from neodymium-iron-boron wastes |
| CN102912134A (en) * | 2012-09-27 | 2013-02-06 | 信丰县包钢新利稀土有限责任公司 | Neodymium, iron and boron waste recycling process with approximately zero wastewater discharge |
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