CN100387524C - Method of preparing rare earth fluoride from rare earth oxide - Google Patents
Method of preparing rare earth fluoride from rare earth oxide Download PDFInfo
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- CN100387524C CN100387524C CNB2005100889562A CN200510088956A CN100387524C CN 100387524 C CN100387524 C CN 100387524C CN B2005100889562 A CNB2005100889562 A CN B2005100889562A CN 200510088956 A CN200510088956 A CN 200510088956A CN 100387524 C CN100387524 C CN 100387524C
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- rare earth
- earth oxide
- hydrofluoric acid
- fluorine
- oxide
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Abstract
A method for preparing rare earth oxide comprises adding water (with weight being 0.15-1 times rare earth oxide) into rare earth oxide and stirring, heating the mixture to 30-250DEG C and maintaining for 1-8 h to obtain rare earth hydroxide powders, adding 2-40% hydrofluoric acid into the mixture, carrying out fluorination reaction at 20-150DEG C with hydrofluoric acid amount between 100-200% times of its theoretical quantity, precipitating, filtering, washing, and drying at 50-250DEG C to obtain rare earth fluoride. As this invention carries out a direct reaction of rare earth oxide with water and solid-liquid reaction of rare earth hydroxide powders with hydrofluoric acid, it has the advantages of simple raw materials and prcoess, being easy for filtration and washing, low labor intensity, high yield, little fluorine-containing wastewater discharge, simple apparatus, lower requirements for corrosion protection, and low investment and cost.
Description
Technical field
The present invention relates to a kind of method for preparing rare earth fluorine, more particularly, the invention relates to rare earth oxide and hydrofluoric acid is the method for feedstock production rare earth fluorine.
Technical background
Rare earth fluorine is the important source material that electrolytic reduction is produced rare earth metal, and it also can be used as the additive of luminous agent, iron and steel and the non-ferrous alloy of carbon arc rods, the ionogen that electrolytic process prepares rare earth metal in addition.Utilize refining rare earth fluoride to develop fluoride fiber, crystal of fluoride and infrared region with new purposes such as fluorescent material in recent years.Along with the development and application of novel rare-earth functional materials, the consumption of rare earth fluorine, particularly high-purity rare earth fluoride will increase day by day.The production technique that with the rare earth oxide is the feedstock production rare earth fluorine at present is main:
(1) HF gas and RE
2O
3Carry out gas-solid reaction:
RE
2O
3+6HF＝＝3H
2O+2REF
3
(2) NH
4HF
2Gas and RE
2O
3Carry out gas-solid reaction:
RE
2O
3+6NH
4HF
2＝＝3H
2O+2REF
3+6NH
4F
Aforesaid method all is synthetic by gas-solid reaction under hot conditions, and is therefore airtight very high with requirement of shelter to body of heater; Fluoro-gas has severe corrosive, makes some metallic elements in the fluoridation equipment enter the fluorochemical product, can't prepare the high purity rare earth fluorine; In addition, because gas-solid reaction is incomplete, the fluoro-gas utilization ratio is low, will cause serious environmental to be polluted after the discharging.
For avoiding the shortcoming of above-mentioned gas-solid pyroreaction, also have and adopt other rare earth compound and hydrofluoric acid directly to carry out the method that liquid-solid or reactive liquid solution prepares rare earth fluorine:
Rare earths salt and hydrofluoric acid direct reaction, undertaken by following reaction:
RE
3++3HF＝＝3H
++REF
3
Because REF
3Solubility product constant very little, so the REF that generates
3Be colloid, granularity is little, the clarification filtration difficulty.For this reason, disclose a kind of ammoniacal liquor and hydrofluoric acid of adopting among the Chinese patent CN1337357A and be mixed with compound fluorinating, react the method that generates oarse-grained rare earth fluorine with rare earth salts again, produced ammonia nitrogen waste water in this method preparation process.
Chinese patent CN1017985B discloses a kind of method, adopting rare earth solubility salt, oxide compound, oxalate, sulfuric acid rare earth double salt, subcarbonate is slurries, add oxalic acid, add hydrofluoric acid again, carry out solid-liquid separation, prepare and be easy to the filtering rare earth fluorine of sedimentation, the used oxalic acid of this method costs an arm and a leg, the preparation cost height, and the final fluoride ion oxalic acid corrosion that produces is strong, equipment anticorrosion is required high.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare the rare earth fluorine method with rare earth oxide, this method technical process is simple, filtration washing easily, and manipulation strength is low, production capacity is big, and the fluoride waste quantity discharged is few, handles easily, and synthesis device is simple, requirement for anticorrosion is low, less investment, and cost is low.
The present invention is achieved through the following technical solutions:
At first with rare earth oxide and water direct reaction, generate rare-earth hydroxide, again with the hydrofluoric acid direct reaction, after filtration, washing and oven dry generate rare earth fluorine.Its reaction is as follows:
RE
2O
3+3H
2O＝＝2RE(OH)
3
2RE(OH)
3+6HF＝＝6H
2O+2REF
3
The present invention prepares the method for rare earth fluorine, and its concrete steps are as follows:
(1) rare earth oxide directly and water mix, the water yield is extraordinarily gone into to 1 by 0.15 of rare earth oxide weight;
(2) mixture obtains the rare-earth hydroxide powder 30 ℃～250 ℃ following heat tracings 1 to 8 hour;
(3) hydrofluoric acid of concentration 2% to 40% adds in the rare-earth hydroxide and carries out fluoridation, consumption be theoretical amount 100% to 200% between, between 20 ℃ to 150 ℃, carry out fluoridation;
(4) after sedimentation is finished, throw out is filtered, washs, dry down at 50～250 ℃;
In the inventive method, for guaranteeing to react completely, reduce excessive moisture volatile quantity, save energy, the preferred amount of water in the described step (1) is 0.2 to 0.5 times of rare earth oxide weight.
In the inventive method, Heating temperature is preferably 100 ℃～170 ℃ in the described step (2), and preferred soaking time is 1 to 5 hour.
In the inventive method, for accelerating to fluoridize speed, hydrogen fluorine reaction acid concentration is preferably 10%～30% in the described step (3), simultaneously, can adopt in the fluorination process to stir and mix, and improves the liquid-solid reaction uniformity coefficient.
In the inventive method, for guaranteeing to fluoridize fully and reducing the hydrofluoric acid consumption, the preferred dosage of hydrofluoric acid adds by 105%～120% of theoretical addition in the described step (3).
In the inventive method, for avoiding in the fluorination process corrosion to conversion unit, in the anticorrosion life-span of improving equipment, the preferred temperature of fluoridation is between 30 ℃～90 ℃ in the described step (3).
In the inventive method, in the described step (4), the preferred temperature of described exsiccant is 120 ℃～200 ℃.
Rare earth oxide of the present invention is La
2O
3, Pr
7O
11, Ce
2O
3, Nd
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3, YO
3, and Sc
2O
3In one or more mixture.Described rare earth oxide is preferably La
2O
3, Nd
2O
3, and La
2O
3And Nd
2O
3Composite oxides.
The present invention has following advantage: because the present invention adopts the direct and water reaction generation rare-earth hydroxide powder of rare earth oxide, again rare-earth hydroxide powder and hydrofluoric acid are carried out solid-liquid reaction, make that chemical raw material of the present invention and technical process are simple, easily filtration washing, manipulation strength is low, production capacity is big, and the fluoride waste quantity discharged is few, handles easily, synthesis device is simple, requirement for anticorrosion is low, less investment, and cost is low.
Fig. 2 and Fig. 3 are intermediates lanthanum hydroxide and lanthanum fluoride product electronic scanning electromicroscopic photograph, and the lanthanum fluoride granularity through the lanthanum hydroxide preparation is bigger as seen from the figure, and its sedimentation strainability is good.
Description of drawings
Fig. 1 is the schema of the inventive method.
Fig. 2 is an intermediates lanthanum hydroxide electronic scanning electromicroscopic photograph.
Fig. 3 is a lanthanum fluoride product electronic scanning electromicroscopic photograph.
Embodiment
By the following example the present invention is further set forth, but be not that scope of the present invention is limited.Comparative Examples:
Adopting the commodity lanthanum trioxide is raw material, adding concentration by 200% of theoretical amount is 5%, 10%, 15%, 20%, 25%, 30% and 35% hydrofluoric acid, 100 ℃ of following isothermal reactions 5 hours, sedimentation, filtration, use the deionized water wash filter cake, under 130 ℃ with filtration cakes torrefaction after, carry out chemical ingredients and detect, the proof composition is still based on lanthanum trioxide, and transformation efficiency is all less than 5%.
Hydrofluoric acid concentration and transformation efficiency relation in table 1 lanthanum trioxide and the hydrofluoric acid direct reaction process
| Hydrofluoric acid concentration | 5％ | 10％ | 15％ | 20％ | 25％ | 30％ | 35％ |
| Transformation efficiency (%) | 2.35 | 2.75 | 2.88 | 4.08 | 3.66 | 3.69 | 3.45 |
This example shows, the direct and rare earth oxide reaction with hydrofluoric acid, and the transformation efficiency of rare earth oxide is very low, can't obtain rare earth fluorine.
Embodiment 1:
Adopting the commodity lanthanum trioxide is raw material, by 0.2 extraordinarily entry of its weight, after mixing is stirred, in 8 hours 120 ℃ of heat tracing reaction times, obtains the lanthanum hydroxide powder; Get 1 kilogram of lanthanum hydroxide, adding concentration by 185% of theoretical amount is 5% hydrofluoric acid, and 150 ℃ of following isothermal reactions 2 hours, the deionized water wash filter cake was used in sedimentation, filtration, under 130 ℃ with filtration cakes torrefaction.Detect through XRD, products therefrom is a lanthanum fluoride, and transformation efficiency is greater than 99% after testing.
Embodiment 2:
Adopting the commodity Neodymium trioxide is raw material, by 0.9 extraordinarily entry of its weight, after mixing is stirred, in 2 hours 250 ℃ of reacting by heating times, obtains the neodymium hydroxide Neodymium trihydroxide powder; The hydrofluoric acid of getting 1 kilogram of neodymium hydroxide Neodymium trihydroxide and concentration 35% is by theoretical amount 120% reaction, and in 40 ℃ of isothermal reactions 2 hours, the clear water washing leaching cake was used in sedimentation, filtration, and filter cake is in 250 ℃ of oven dry.Detect through XRD, products therefrom is a neodymium fluoride, and through chemical detection, transformation efficiency is greater than 99%.
Embodiment 3:
Adopting Neodymium trioxide and lanthanum trioxide is raw material by each mixed thing of 50%, by 0.5 extraordinarily entry of its weight, after mixing is stirred, in 5 hours 50 ℃ of heat tracing times, obtains lanthanum hydroxide neodymium powder; The hydrofluoric acid of getting lanthanum hydroxide neodymium and concentration 15% is by theoretical amount 105% reaction, and in 40 ℃ of isothermal reactions 2 hours, the clear water washing leaching cake was used in sedimentation, filtration, and filter cake is in 130 ℃ of oven dry.Through chemical detection, transformation efficiency is greater than 99%.
Claims (8)
1. one kind prepares the method for rare earth fluorine from rare earth oxide, and it is characterized in that: it may further comprise the steps:
(1) adding weight in rare upward oxide compound is 0.15 to 1 times water of rare earth oxide weight, and mixes;
(2) with mixture heating up to 30 ℃ between 250 ℃, and be incubated 1 to 8 hour, obtain the rare-earth hydroxide powder;
(3) adding concentration in mixture is 2% to 40% hydrofluoric acid, carries out fluoridation between 20 ℃ to 150 ℃, the amount of hydrofluoric acid theoretical amount 100% to 200% between;
(4) with throw out sedimentation, filtration, washing, dry under 50～250 ℃, obtain rare earth fluorine.
2. according to claim 1ly a kind ofly prepare the method for rare earth fluorine from rare earth oxide, it is characterized in that: the weight that adds entry is 0.2 to 0.5 times of rare earth oxide weight.
3. according to claim 1ly a kind ofly prepare the method for rare earth fluorine from rare earth oxide, it is characterized in that: with the mixture heating up temperature of rare earth oxide and water is 100 ℃ to 170 ℃, and soaking time is 1 hour to 5 hours.
4. according to claim 1ly a kind ofly prepare the method for rare earth fluorine, it is characterized in that: in mixture, add hydrofluoric acid concentration between 10% to 30% from rare earth oxide.
5. according to claim 1ly a kind ofly prepare the method for rare earth fluorine from rare earth oxide, it is characterized in that: the hydrofluoric acid add-on is 105% to 120% of a theoretical amount.
6. according to claim 1ly a kind ofly prepare the method for rare earth fluorine from rare earth oxide, it is characterized in that: the temperature of reaction when fluoridizing is preferably between 30 ℃ to 90 ℃.
7. according to claim 1ly a kind ofly prepare the method for rare earth fluorine from rare earth oxide, it is characterized in that: described exsiccant temperature is 120 ℃～200 ℃.
8. according to claim 1ly a kind ofly prepare the method for rare earth fluorine from rare earth oxide, it is characterized in that: described rare earth oxide is La
2O
3Or Nd
2O
3Or La
2O
3And Nd
2O
3Composite oxides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100889562A CN100387524C (en) | 2005-08-03 | 2005-08-03 | Method of preparing rare earth fluoride from rare earth oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100889562A CN100387524C (en) | 2005-08-03 | 2005-08-03 | Method of preparing rare earth fluoride from rare earth oxide |
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|---|---|
| CN1907859A CN1907859A (en) | 2007-02-07 |
| CN100387524C true CN100387524C (en) | 2008-05-14 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086418B (en) * | 2013-01-30 | 2014-07-16 | 东北师范大学 | Synthesis methods of fluoride and europium-doped fluoride luminescent material |
| CN105776307B (en) * | 2016-02-05 | 2018-05-01 | 四川省新材料研究中心 | The pre-treating method that a kind of rare earth oxide isolates and purifies |
| CN110494393A (en) * | 2017-02-03 | 2019-11-22 | 南非核能源国营有限公司 | The preparation method of rare earth metal fluoride |
| CN111170352B (en) * | 2020-01-21 | 2022-11-29 | 包头稀土研究院 | Method for preparing rare earth fluoride particles by using fluorine-containing waste acid |
| CN115124065A (en) * | 2021-03-25 | 2022-09-30 | 有研稀土新材料股份有限公司 | Green combined preparation method of rare earth fluoride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048531A (en) * | 1989-07-07 | 1991-01-16 | 甘肃稀土公司 | Preparation method of rare earth fluoride |
| CN1337357A (en) * | 2000-08-08 | 2002-02-27 | 赣州有色冶金研究所 | Method of preparing rare earth fluoride |
-
2005
- 2005-08-03 CN CNB2005100889562A patent/CN100387524C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048531A (en) * | 1989-07-07 | 1991-01-16 | 甘肃稀土公司 | Preparation method of rare earth fluoride |
| CN1337357A (en) * | 2000-08-08 | 2002-02-27 | 赣州有色冶金研究所 | Method of preparing rare earth fluoride |
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Owner name: GRIREM ADVANCED MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING CENTRAL INST.OF THE NONFERROUS METAL Effective date: 20130802 Free format text: FORMER OWNER: GRIREM ADVANCED MATERIALS CO., LTD. Effective date: 20130802 |
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Effective date of registration: 20130802 Address after: 100088, 2, Xinjie street, Beijing Patentee after: Grirem Advanced Materials Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals Patentee before: Grirem Advanced Materials Co., Ltd. |
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