CN101851000A - Method for preparing rare-earth oxide - Google Patents
Method for preparing rare-earth oxide Download PDFInfo
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- CN101851000A CN101851000A CN 201010168397 CN201010168397A CN101851000A CN 101851000 A CN101851000 A CN 101851000A CN 201010168397 CN201010168397 CN 201010168397 CN 201010168397 A CN201010168397 A CN 201010168397A CN 101851000 A CN101851000 A CN 101851000A
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Abstract
The invention discloses a method for preparing a rare-earth oxide by using electrochemical fluorination residues generated by electrolyzing rare-earth metals. The method comprises the steps of treating, calcining, crushing, leaching and filtering raw materials, preparing the rare-earth oxide and the like. Compared with an alkaline method, the method has the advantages of simple process, short flow, easily controlled manufacture operation, low cost, small wastewater drainage and over 95 percent of recovery rate; and meanwhile, the method has strong adaptability to raw materials, can treat the electrochemical fluorination residues, rare-earth catalyst waste, waste battery scarp and the like, and can treat phosphor-containing xenotime and monazite.
Description
Technical field:
The present invention relates to a kind of preparation method of rare earth oxide, the preparation method that particularly a kind of electrofluorination slag that utilizes the electrolysis rare earth metal to generate is produced rare earth oxide.
Background technology:
Rare earth occupies critical role as Chinese special mineral resources and process for processing technology in world's rare earth Application Areas, control rare earth market, the world substantially.Chinese rare earth outlet in 2009 surpasses 60,000 tons of oxide compounds, and global rare earth consumption surpasses 100,000 tons of oxide compounds.Along with global economic integration, world economy and science and technology development, the range of application and the demand of rare earth enlarge day by day, expect 2012, whole world rare earth consumption will be above 180,000 tons of oxide compounds, and still, whole world rare earth Mineral resources are limited, and ore grade also adopts lower and lower, so be difficult to satisfy human wants.The end product of rare-earth products is a rare earth metal, as neodymium metal, metal dysprosium, terbium metal etc., generally by the electrolysis high melt, is processed into rare earth metal.In electrochemical machining process, produce a certain amount of electrofluorination slag.This fluoridizes slag, contains rare earth 30%50%, fluoride ion (F
-), silicon (si), calcium (ca), iron 50%-70% such as (Fe), be insoluble to acid, water insoluble, also be insoluble to alkali, manufacturer abandoned it or was used to pave the way etc. the past, wasted valuable rare earth resources.
Summary of the invention:
The purpose of this invention is to provide the preparation method that a kind of electrofluorination slag that utilizes the electrolysis rare earth metal to generate is produced rare earth oxide.
The present invention adopts following technical scheme to realize its goal of the invention, a kind of preparation method of rare earth oxide, and it may further comprise the steps:
(1) raw material is handled: with vibromill raw material is milled to 250 orders～350 orders;
(2) roasting: step (1) gained abrasive material is put into stoving oven, and by weight, adding concentration by 1: 1.2～1.5 is 98% the vitriol oil, stirs and heats to 150 ℃～800 ℃ roasting time 3 hours～6 hours;
(3) fragmentation: will join in the crusher through the good raw material of step (2) roasting, be crushed to 50 orders～100 orders;
(4) leach: will put into leaching vat through the raw material after step (3) fragmentation, and by weight, add entry by 1: 4～8, and stir and make rare earth be dissolved in water, and leach, and clarify then, and 24 hours～36 hours time, make feed liquid limpid;
(5) filter: will squeeze in the sheet frame through the leach liquor after step (4) leaches, filter rare earth feed liquid;
(6) rare earth oxide preparation: rare earth feed liquid is made rare-earth oxalate after rare earth oxide is made in roasting.
Raw material of the present invention is for fluoridizing slag or xenotime or solitary stone ore.
Because adopt technique scheme, the present invention has realized goal of the invention preferably, compares with alkali process, its technology is simple, flow process is short, and production operation is easy to control, and cost is low, discharge of wastewater is few, the rate of recovery can reach more than 95%, and is simultaneously, strong to the adaptability of raw material, can handle such as electrofluorination slag, rare earth catalyst waste material, refuse battery waste material etc., also can handle phosphorated xenotime, solitary stone ore.
Embodiment:
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
Present embodiment adopts electrofluorination slag that the electrolysis rare earth metal generates as raw material, and electrofluorination slag middle-weight rare earths content 50% (being mainly praseodymium, neodymium) is fluorine-containing 20%, non-rare earth impurity 30%.
A kind of preparation method of rare earth oxide, it may further comprise the steps:
(1) raw material is handled: with vibromill raw material is milled to 250 orders～350 orders (present embodiment is 350 orders);
(2) roasting: step (1) gained abrasive material is put into stoving oven, by weight, adding concentration by 1: 1.2～1.5 (present embodiment is 1.5) is 98% the vitriol oil, stirring is heated to 150 ℃～800 ℃ (present embodiment is 700 ℃), roasting time 3 hours～6 hours (present embodiment is 6 hours) makes fluorine and Rare Earth Separation;
(3) fragmentation: will join in the crusher through the good raw material of step (2) roasting, be crushed to 50 orders～100 orders (present embodiment is 80 orders);
(4) leach: will put into dissolving tank, by weight through the raw material after step (3) fragmentation, add entry by 1: 4～8 (present embodiment is 6), stirring makes rare earth be dissolved in water, leaches, settling time 24 hours～36 hours (present embodiment is 32 hours) makes feed liquid limpid;
(5) filter: will squeeze in the sheet frame through the leach liquor after step (4) leaches, filter rare earth feed liquid;
(6) rare earth oxide preparation: earlier rare earth feed liquid is made rare-earth oxalate, make rare earth oxide through high temperature (1100 ℃) roasting again.
The rare earth oxide of preparation is praseodymium, neodymium oxides, content praseodymium 25, neodymium 75.
Embodiment 2:
Present embodiment adopts xenotime as raw material, and content of rare earth 55% (yttrium, cerium, gadolinium, dysprosium, erbium, ytterbium) is phosphorous 30%, non-rare earth impurity 15%.A kind of preparation method of rare earth oxide, it may further comprise the steps:
(1) raw material is handled: with vibromill raw material is milled to 300 orders;
(2) roasting: step (1) gained abrasive material is put into stoving oven, by weight, is 98% the vitriol oil by adding concentration at 1: 1.4, stirs and heats to 450 ℃, and roasting time 4 hours makes phosphorus and Rare Earth Separation;
(3) fragmentation: will join in the crusher through the good raw material of step (2) roasting, be crushed to 50 orders;
(4) leach: will put into dissolving tank through the raw material after step (3) fragmentation, and by weight, add entry by 1: 4, stirring makes rare earth be dissolved in water, leaches, and settling time 30 hours makes feed liquid limpid;
(5) filter: will squeeze in the sheet frame through the leach liquor after step (4) leaches, filter rare earth feed liquid;
(6) rare earth oxide preparation: earlier rare earth feed liquid is made rare-earth oxalate, make rare earth oxide through high temperature (1100 ℃) roasting again.
The rare earth oxide of preparation is mixed rare-earth oxide (being mainly yttrium 62.97, cerium 3.63, gadolinium 3.02, dysprosium 7.63, erbium 6.34, ytterbium 6.79).
Embodiment 3:
Present embodiment adopts solitary stone ore as raw material, and content of rare earth 60% (yttrium, cerium, gadolinium, neodymium, lanthanum, praseodymium) is phosphorous 20%, non-rare earth impurity 20%.A kind of preparation method of rare earth oxide, it may further comprise the steps:
(1) raw material is handled: with vibromill raw material is milled to 250 orders;
(2) roasting: step (1) gained abrasive material is put into stoving oven, by weight, is 98% the vitriol oil by adding concentration at 1: 1.2, stirs and heats to 150 ℃, and roasting time 3 hours makes phosphorus and Rare Earth Separation;
(3) fragmentation: will join in the crusher through the good raw material of step (2) roasting, be crushed to 50 orders;
(4) leach: will put into dissolving tank through the raw material after step (3) fragmentation, and by weight, add entry by 1: 5, stirring makes rare earth be dissolved in water, leaches, and settling time 24 hours makes feed liquid limpid;
(5) filter: will squeeze in the sheet frame through the leach liquor after step (4) leaches, filter rare earth feed liquid;
(6) rare earth oxide preparation: earlier rare earth feed liquid is made rare-earth oxalate, make rare earth oxide through high temperature (1100 ℃) roasting again.
The rare earth oxide of preparation is mixed rare-earth oxide (being mainly yttrium 4, cerium 43, gadolinium 3.5, neodymium 17, lanthanum 25, praseodymium 6).
Claims (2)
1. the preparation method of a rare earth oxide is characterized in that it may further comprise the steps:
(1) raw material is handled: with vibromill raw material is milled to 250 orders～350 orders;
(2) roasting: step (1) gained abrasive material is put into stoving oven, and by weight, adding concentration by 1: 1.2～1.5 is 98% the vitriol oil, stirs and heats to 150 ℃～800 ℃ roasting time 3 hours～6 hours;
(3) fragmentation: will join in the crusher through the good raw material of step (2) roasting, be crushed to 50 orders～100 orders;
(4) leach: will put into leaching vat through the raw material after step (3) fragmentation, and by weight, add entry by 1: 4～8, and stir and make rare earth be dissolved in water, and leach, and clarify then, and 24 hours～36 hours time, make feed liquid limpid;
(5) filter: will squeeze in the sheet frame through the leach liquor after step (4) leaches, filter rare earth feed liquid;
(6) rare earth oxide preparation: rare earth feed liquid is made rare-earth oxalate after rare earth oxide is made in roasting.
2. the preparation method of a kind of rare earth oxide according to claim 1 is characterized in that the raw material described in the step (1) is for fluoridizing slag or xenotime or solitary stone ore.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010168397 CN101851000A (en) | 2010-05-08 | 2010-05-08 | Method for preparing rare-earth oxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010168397 CN101851000A (en) | 2010-05-08 | 2010-05-08 | Method for preparing rare-earth oxide |
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| CN101851000A true CN101851000A (en) | 2010-10-06 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534269A (en) * | 2012-03-26 | 2012-07-04 | 乐山盛和稀土股份有限公司 | Method for comprehensively recycling various rare earth from rare earth materials containing fluorine |
| CN104805292A (en) * | 2015-04-17 | 2015-07-29 | 益阳鸿源稀土有限责任公司 | Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste |
| CN106044833A (en) * | 2016-06-07 | 2016-10-26 | 福建省长汀金龙稀土有限公司 | Method for recovering rare earth fluoride from electrode scrap reclaimed material and slag of rare earth |
| CN106145176A (en) * | 2015-04-21 | 2016-11-23 | 永州市湘江稀土有限责任公司 | The technique that a kind of alkaline process processes monazite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS539298A (en) * | 1976-07-15 | 1978-01-27 | Kenichi Fukuo | Method of separating and recovering rearearth element and thorium from rearearth phosphate ore |
| CN1103111A (en) * | 1993-11-26 | 1995-05-31 | 北京有色金属研究总院 | Making rare-earth material liquid from bastnae site |
-
2010
- 2010-05-08 CN CN 201010168397 patent/CN101851000A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS539298A (en) * | 1976-07-15 | 1978-01-27 | Kenichi Fukuo | Method of separating and recovering rearearth element and thorium from rearearth phosphate ore |
| CN1103111A (en) * | 1993-11-26 | 1995-05-31 | 北京有色金属研究总院 | Making rare-earth material liquid from bastnae site |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534269A (en) * | 2012-03-26 | 2012-07-04 | 乐山盛和稀土股份有限公司 | Method for comprehensively recycling various rare earth from rare earth materials containing fluorine |
| CN104805292A (en) * | 2015-04-17 | 2015-07-29 | 益阳鸿源稀土有限责任公司 | Method for separating and recovering valuable components from rare earth praseodymium-neodymium fused salt electrolysis waste |
| CN106145176A (en) * | 2015-04-21 | 2016-11-23 | 永州市湘江稀土有限责任公司 | The technique that a kind of alkaline process processes monazite |
| CN106145176B (en) * | 2015-04-21 | 2019-07-16 | 永州市湘江稀土有限责任公司 | A kind of technique of alkaline process processing monazite |
| CN106044833A (en) * | 2016-06-07 | 2016-10-26 | 福建省长汀金龙稀土有限公司 | Method for recovering rare earth fluoride from electrode scrap reclaimed material and slag of rare earth |
| CN106044833B (en) * | 2016-06-07 | 2017-10-27 | 福建省长汀金龙稀土有限公司 | A kind of method of the recovering rare earth fluoride from rare earth electrode scrap reclaimed materials and clinker |
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Open date: 20101006 |