CN105369042A - Method for efficiently extracting rare earths from fluoride system rare earth molten salt electrolysis slag - Google Patents
Method for efficiently extracting rare earths from fluoride system rare earth molten salt electrolysis slag Download PDFInfo
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- CN105369042A CN105369042A CN201510918314.4A CN201510918314A CN105369042A CN 105369042 A CN105369042 A CN 105369042A CN 201510918314 A CN201510918314 A CN 201510918314A CN 105369042 A CN105369042 A CN 105369042A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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Abstract
The invention specifically relates to a method for efficiently extracting rare earths from a fluoride system rare earth molten salt electrolysis slag. The method comprises the following steps: step 1, evenly mixing a silicate with the fluoride system rare earth molten salt electrolysis slag; step 2, roasting a mixture obtained in the step 1 in a high-temperature furnace; step 3, leaching a roasted product obtained in the step 2 by using water and then carrying out filtering to obtain a filter cake; and step 4, putting the filter cake in a hydrochloric acid solution for reacting, and then carrying out filtering to obtain a rare earth feed liquid. The method is capable of efficiently extracting rare earths in the fluoride system rare earth molten salt electrolysis slag, and the maximum leaching rate is higher than 99%, which is greatly superior to a treatment effect of an existing process; in addition, the method is simple in process, convenient to operate, and conductive to improve the production efficiency; furthermore, acidic gases such as HF and so on may not be produced in the production process, and the process is environment-friendly.
Description
Technical field
The invention belongs to industrial waste residue disposal technical field, be specifically related to the method for recovering rare earth from industrial residue.
Background technology
Fused salt electrolysis technique is the common method of producing low melting point rare earth metal, is divided into rare earth chloride molten salt system and rare earth fluorine molten salt system.When adopting rare earth fluorine molten salt system to produce rare earth metal, its solute is rare earth oxide, and ionogen is the mixture of lithium fluoride or lithium fluoride and barium fluoride.Along with the carrying out produced, various non-rare earth impurity is brought in electrolyzer, and such as, when adding rare earth oxide, impurity just enters in electrolysis system thereupon; Change the operations such as anode and equally also can bring non-rare earth impurity into, thus cause the continuous enrichment of the non-rare earth in system, make ionogen no longer meet normal demand of producing.Now, the ionogen that just must more renew, thus form rare earth molten-salt electrolysis slag.Slag Rare-Earth Content is higher, and content of rare earth, 10% ~ 80%, mainly exists with the form of rare earth fluoride.Therefore, the rare earth in the middle of reclaiming from rare earth molten-salt electrolysis slag, significant to the Sustainable development of the utilization ratio and rare-earth industry that improve rare earth resources.
Treatment process in currently available technology mainly contains concentrated sulfuric acid roasting method and alkali conversion method.
Concentrated sulfuric acid roasting method is as described in Chinese invention patent " a kind of method of Extraction of rare earth from rare earth chloride electrolytic slag " (application number: 94106756.4, application publication number: CN1114363A) formerly.
Long in the production cycle of above-mentioned concentrated sulfuric acid roasting technique, and produce the sour gas such as a large amount of HF, corrosive equipment and contaminate environment.
Alkali conversion method is as Chinese invention patent " method of a kind of environmental protection low cost recovering rare earth from rare earth fluorine fused salt electrolysis waste material " (application number: 201510147509.3 formerly, application publication number: CN104843761A) and " a kind of method of Separation and Recovery rare earth element from molten salt electrolysis wastes " (application number: 201010505807.2, application publication number: CN101956078A) described in.
Alkali conversion method mainly comprises sodium hydroxide roasting conversion and calcium hydroxide roasting transforms, wherein calcium hydroxide roasting transforms and generates rare earth oxide and Calcium Fluoride (Fluorspan), in this resultant acid dissolution, Calcium Fluoride (Fluorspan) creates fluorion and is easy to rare earth oxide and dissolves the rare earth ion produced and regenerate rare earth fluorine, thus causes Extraction of rare eart not thorough; And when adopting sodium hydroxide roasting to transform, can the invert point of 300 DEG C-500 DEG C thoroughly be converted into rare earth oxide or rare earth hydrate by rare earth fluoride, unknown.
Therefore, the extraction process of a kind of efficient, economy of exploitation and environmental protection is badly in need of.
Summary of the invention
The object of the present invention is to provide a kind of Extraction of rare earth method of efficient from fluoric-salt system rare earth molten-salt electrolysis slag, economy and environmental protection.
For achieving the above object, the invention provides a kind of method of high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag, comprise the steps:
Step one, mixes silicate with fluoride system rare earth molten-salt electrolysis slag;
Step 2, mixture step one obtained is placed in high temperature kiln roasting;
Step 3, product of roasting water logging step 2 obtained goes out, filters, and obtains filter cake;
Step 4, is placed in hydrochloric acid soln by filter cake and reacts, and then filters and obtains rare earth feed liquid.
Wherein, rare earth fluorine and rare earth metal is comprised in described fluoride system rare earth molten-salt electrolysis slag.
Wherein, in step one, described silicate is water glass or potassium silicate solid.
Wherein, in step one, the mass ratio of described fluoride system rare earth molten-salt electrolysis slag and silicate is: 1:0.5 ~ 1:4.
Wherein, in described step 2, temperature of reaction is 400 ~ 1000 DEG C, and roasting time is 0.5 ~ 3.5h.
Wherein, in described step 4, the concentration of hydrochloric acid soln is 0.5 ~ 6mol/L, and liquid volume is 15:1 ~ 3:1 with the ratio of solid masses; The temperature of reaction of product of roasting and hydrochloric acid soln is room temperature ~ 90 DEG C, and the reaction times is 0.5 ~ 4h.
The invention has the beneficial effects as follows: the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag provided by the invention, rare earth in high efficiency extraction fluoride system rare earth molten-salt electrolysis slag, the highest leaching yield, more than 99%, is better than the treatment effect of current technology greatly; And technique is simple, and convenient operation, is conducive to enhancing productivity; In addition, the sour gas such as HF can not be produced in process of production, technique environmental protection.
Accompanying drawing explanation
Fig. 1 is the schema of the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag provided by the invention.
Embodiment
In order to more clearly state the present invention, below in conjunction with accompanying drawing, the present invention is further described.
Consult Fig. 1, the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag provided by the invention, comprises the steps:
Step one, mixes for 1:0.5 ~ 1:4 with silicate in mass ratio by fluoride system rare earth molten-salt electrolysis slag;
Step 2, mixture step one obtained is placed in high temperature kiln roasting; Controlling temperature of reaction is 400 ~ 1000 DEG C, and roasting time is 0.5 ~ 3.5h; In this step, the chemical reaction occurred is:
10REF
3+15Na
2SiO
3＝RE
10(SiO
4)
6O
3+30NaF+9SiO
2；
Step 3, product of roasting water logging step 2 obtained goes out, and then filters and obtains filter cake; Wherein filter cake is mainly containing RE
10(SiO
4)
6o
3;
Step 4, is placed in hydrochloric acid soln by the filter cake after oven dry and leaches, obtain rare earth feed liquid after filtration; Wherein, the concentration of hydrochloric acid soln is 0.5 ~ 6mol/L, and liquid volume is 15:1 ~ 3:1 with the ratio of solid masses; The temperature of reaction of filter cake and hydrochloric acid soln is room temperature ~ 90 DEG C, and the reaction times is 0.5 ~ 4h.
Be specific embodiment explanation below.
Embodiment 1:
Get fluoride system rare earth molten-salt electrolysis slag 10kg, wherein the content of REO is 69.4%, water glass and rare earth molten-salt electrolysis slag mass ratio are 2.5:1, maturing temperature 900 DEG C, take out after roasting 3.5h, filter after water logging product of roasting, filter cake leaches 3h in concentration of hydrochloric acid 4mol/L, liquid-solid ratio 10:1, temperature of reaction under being the condition of 90 DEG C, it is 1.21% that filtering drying records slag Rare-Earth Content, and the leaching yield of rare earth is 99.37%.
Embodiment 2:
Get fluoride system rare earth molten-salt electrolysis slag 5kg, wherein the content of REO is 45.2%, water glass and rare earth molten-salt electrolysis slag mass ratio are 0.5:1, maturing temperature 400 DEG C, take out after roasting 2h, filter after water logging fired slags, filter cake leaches 0.5h in concentration of hydrochloric acid 0.5mol/L, liquid-solid ratio 3:1, temperature of reaction under being the condition of room temperature, recording slag Rare-Earth Content after filtering drying is 38.91%, and the leaching yield of rare earth is 28.76%.
Embodiment 3:
Get fluoride system rare earth molten-salt electrolysis slag 12kg, wherein the content of REO is 61.2%, potassium silicate and rare earth molten-salt electrolysis slag mass ratio are 2:1, maturing temperature 700 DEG C, take out after roasting 4h, filter after water logging fired slags, filter cake leaches 4h in concentration of hydrochloric acid 6mol/L, liquid-solid ratio 15:1, temperature of reaction under being the condition of room temperature, recording slag Rare-Earth Content after filtering drying is 1.43%, and the leaching yield of rare earth is 99.25%.
Embodiment 4:
Get fluoride system rare earth molten-salt electrolysis slag 25kg, wherein the content of REO is 65.7%, water glass and rare earth molten-salt electrolysis slag mass ratio are 4:1, maturing temperature 1000 DEG C, take out after roasting .05h, filter after water logging fired slags, filter cake leaches 2.5h in concentration of hydrochloric acid 3mol/L, liquid-solid ratio 8:1, temperature of reaction under being the condition of 80 DEG C, recording slag Rare-Earth Content after filtering drying is 1.01%, and the leaching yield of rare earth is 99.45%.
From every testing data of above-described embodiment, the method of high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag provided by the invention, rare earth in high efficiency extraction fluoride system rare earth molten-salt electrolysis slag, the highest leaching yield, more than 99%, is better than the treatment effect of current technology greatly; And technique is simple, and convenient operation, is conducive to enhancing productivity; In addition, the sour gas such as HF can not be produced in process of production, can not etching apparatus, do not pollute the environment yet, can extension device work-ing life, environmental protection more simultaneously.
These are only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag, is characterized in that, comprise the steps:
Step one, mixes silicate with fluoride system rare earth molten-salt electrolysis slag;
Step 2, mixture step one obtained is placed in high temperature kiln roasting;
Step 3, product of roasting water logging step 2 obtained goes out, filters, and obtains filter cake;
Step 4, filter cake step 3 obtained is placed in hydrochloric acid soln and reacts, and then filters and obtains rare earth feed liquid.
2. the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag according to claim 1, is characterized in that, comprises rare earth fluorine and rare earth metal in described fluoride system rare earth molten-salt electrolysis slag.
3. the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag according to claim 1 and 2, is characterized in that, in step one, described silicate is water glass or potassium silicate solid.
4. the method for high efficiency extraction rare earth from fluoric-salt system rare earth molten-salt electrolysis slag according to claim 1 and 2, is characterized in that, in step one, the mass ratio of described fluoride system rare earth molten-salt electrolysis slag and silicate is: 1:0.5 ~ 1:4.
5. the method for Extraction of rare earth from fluoride system rare earth molten-salt electrolysis slag according to claim 1 and 2, is characterized in that, in described step 2, temperature of reaction is 400 ~ 1000 DEG C, and roasting time is 0.5 ~ 3.5h.
6. the method for Extraction of rare earth from fluoride system rare earth molten-salt electrolysis slag according to claim 1 and 2, is characterized in that, in described step 4, the concentration of hydrochloric acid soln is 0.5 ~ 6mol/L, and liquid volume is 15:1 ~ 3:1 with the ratio of solid masses; The temperature of reaction of product of roasting and hydrochloric acid soln is room temperature ~ 90 DEG C, and the reaction times is 0.5 ~ 4h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107630143A (en) * | 2017-09-26 | 2018-01-26 | 赣南师范大学 | Method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue |
| CN109785986A (en) * | 2019-01-31 | 2019-05-21 | 中国科学院上海应用物理研究所 | The minimizing technology of rare earth element in spentnuclear fuel abraum salt |
| CN113025835A (en) * | 2020-07-28 | 2021-06-25 | 江西理工大学 | Method for efficiently extracting rare earth from bastnaesite |
| CN114226058A (en) * | 2021-11-25 | 2022-03-25 | 郑州大学 | Method for recovering rare earth molten salt from rare earth waste graphite |
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| CN101824531A (en) * | 2010-03-12 | 2010-09-08 | 包头稀土研究院 | Liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates |
| CN102212674A (en) * | 2011-05-12 | 2011-10-12 | 包头稀土研究院 | Process for comprehensively recovering liquid alkali roasting resource of mixed rare earth concentrate |
| RU2487185C1 (en) * | 2011-11-24 | 2013-07-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" | Method of extracting rare-earth metals from phosphogypsum |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107630143A (en) * | 2017-09-26 | 2018-01-26 | 赣南师范大学 | Method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue |
| CN107630143B (en) * | 2017-09-26 | 2019-10-25 | 赣南师范大学 | Method for extracting rare earth from rare earth fluorescent powder waste and fluorine-containing rare earth electrolysis waste residue |
| CN109785986A (en) * | 2019-01-31 | 2019-05-21 | 中国科学院上海应用物理研究所 | The minimizing technology of rare earth element in spentnuclear fuel abraum salt |
| CN109785986B (en) * | 2019-01-31 | 2020-12-25 | 中国科学院上海应用物理研究所 | Method for removing rare earth elements in spent fuel salt |
| CN113025835A (en) * | 2020-07-28 | 2021-06-25 | 江西理工大学 | Method for efficiently extracting rare earth from bastnaesite |
| CN114226058A (en) * | 2021-11-25 | 2022-03-25 | 郑州大学 | Method for recovering rare earth molten salt from rare earth waste graphite |
| CN114226058B (en) * | 2021-11-25 | 2023-10-17 | 郑州大学 | Method for recovering rare earth molten salt from rare earth waste graphite |
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