CN110344086A - A method of electrolyte components are separated and recovered from fluoric-salt system Rare Earth Electrolysis fused salt slag - Google Patents
A method of electrolyte components are separated and recovered from fluoric-salt system Rare Earth Electrolysis fused salt slag Download PDFInfo
- Publication number
- CN110344086A CN110344086A CN201910771676.3A CN201910771676A CN110344086A CN 110344086 A CN110344086 A CN 110344086A CN 201910771676 A CN201910771676 A CN 201910771676A CN 110344086 A CN110344086 A CN 110344086A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- fused salt
- slag
- electrolysis
- fluoric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of methods from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components, first Rare Earth Electrolysis fused salt slag is crushed, broken Rare Earth Electrolysis fused salt slag is evaporated in vacuo again, electrolysis of fluorides matter is collected after vacuum distillation, directly return Rare Earth Electrolysis process.The present invention directly recycles electrolysis of fluorides matter by vacuum distillation method, entire removal process does not generate secondary pollution, upright connect of electrolysis of fluorides after separation returns to Rare Earth Electrolysis process, further realizes the efficient comprehensive reutilization of rare earth in difficult Rare Earth Electrolysis fused salt slag, lithium, fluorine and graphite resource.
Description
Technical field
The present invention relates to metallurgy and environment protection fields, more particularly to one kind to separate and recover from fluoric-salt system Rare Earth Electrolysis fused salt slag
The method of electrolyte components.
Background technique
At present the preparation method of rare earth metal (alloy) mainly include fused salt electrolysis process, calciothermy, intermediate alloy process,
Direct-reduction-way of distillation of rare earth oxide etc..Wherein, fused salt electrolysis process is because it is with easy to operate, production cost is low, product
Ingredient is uniform, high-quality, process is easy to control and is easily achieved the advantages such as serialization and is widely used in scale industrial production
In.However, during rare earth fluoride-lithium fluoride-rare earth oxide system molten salt electrolysis production rare earth metal and rare earth alloy, meeting
Generate a large amount of Rare Earth Electrolysis fused salt slag.The generation of these molten Rare Earth Electrolysis fused salt slags causes in entire rare earth molten-salt electrolysis technique
Rare-earth yield is only in 91%-93% or so, and the rare earth overwhelming majority of loss is in Rare Earth Electrolysis fused salt slag.Rare Earth Electrolysis fused salt slag
In not only contain rare earth and lithium, but also contain many nonmetallic inclusions such as a large amount of graphite powders, calcirm-fluoride, aluminium oxide, iron oxide.This
Outside, the impurity content of generated Rare Earth Electrolysis fused salt slag in different rare earths and alloy process is produced, rare earth grade is also different, and
Otherness is larger, but belongs to the rare earth secondary resource of difficult difficult recycling.It is domestic at present golden using electrolysis process production rare earth
The annual output of category is at 35000-45000 tons or so, about 2200 tons or so every year of the Rare Earth Electrolysis fused salt slag of output.As can will electrolysis
Valuable constituent sufficiently recycles in slag, will generate huge economic benefit.
The main thought of processing Rare Earth Electrolysis fused salt slag at present are as follows: rare earth fluoride is converted into using a kind of efficient fluorine fixing material
Rare earth oxide is to realize the separation of rare earth and fluorine, and on this basis, take into account the miscellaneous leaching of suppression to produce qualified oxidation
Rare earth.As Research Thinking, sodium carbonate roasting, sodium hydroxide roasting, calcium hydroxide roasting, negative pressure heating caustic digestion are formd
The process routes such as method, sodium metasilicate roasting.But these techniques only focus on the recycling of rare earth, and not to stone in Rare Earth Electrolysis fused salt slag
Ink, fluorine and lithium resource carry out synthetical recovery, and be these processes more or less exist process route is long, secondary pollution is big,
The problems such as comprehensive resource utilization rate is low, at high cost.
Summary of the invention
For various problems existing for existing fluoric-salt system Rare Earth Electrolysis fused salt residues processing technique, the purpose of the present invention is
In provide it is a kind of from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components method, it is straight by vacuum distillation method
Take back and receive electrolysis of fluorides matter, entire removal process do not generate secondary pollution, the electrolysis of fluorides after separation is upright connect return it is dilute
Native electrowinning process further realizes efficiently integrating back for rare earth in difficult Rare Earth Electrolysis fused salt slag, lithium, fluorine and graphite resource
It receives and utilizes.
In order to achieve the above technical purposes, the present invention provides one kind separates and recovers from fluoric-salt system Rare Earth Electrolysis fused salt slag
Rare Earth Electrolysis fused salt slag is first crushed by the method for electrolyte components, and broken Rare Earth Electrolysis fused salt slag carries out vacuum again
Electrolysis of fluorides matter is collected in distillation after vacuum distillation, directly return Rare Earth Electrolysis process.
Preferably, the fluoric-salt system Rare Earth Electrolysis fused salt slag is rare earth fluoride-lithium fluoride-rare earth oxide system fused salt
The Rare Earth Electrolysis fused salt slag generated during electrolysis production rare earth metal and rare earth alloy.
Preferably, it is 50-500 mesh, preferably 50-100 mesh that the Rare Earth Electrolysis fused salt slag, which is crushed to partial size,.
Preferably, the condition of the vacuum distillation are as follows: vapo(u)rizing temperature is 700-1600 DEG C, preferably 1000-1100 DEG C；It steams
Evaporating the time is 1-12h, preferably 3-8h；Vacuum degree is 1-100Pa, preferably 1-10Pa.
Preferably, Rare Earth Electrolysis fused salt slag residue after being evaporated in vacuo has distillation slag, treatment process are as follows: distillation slag
Through hydrochloric acid it is excellent it is molten obtain re dip solution and kish slag, re dip solution can be obtained by further removal of impurities, precipitating, calcination
Rare earth oxide product, kish slag can arrive graphite powder by the further molten removal of impurities of acid.
Compared with prior art, present invention has an advantage that
This technique by vacuum distillation in the form of rare earth fluoride and lithium fluoride recovering rare earth be electrolysed fused salt slag in fluorine, rare earth and
Lithium resource (rare earth fluoride in slag is converted rare earth oxide, then the recovering rare earth in the form of rare earth oxide by prior art) is realized
The high-value-use of rare earth, fluorine, lithium resource in Rare Earth Electrolysis fused salt slag avoids in slag fluorine recycle work during to the two of environment
Secondary pollution (prior art can generate a large amount of fluorine-containing waste residue and waste water), have process flow it is short (save ingredient, alkali turn roasting and
Broken process), easy to operate, acid and alkali consumption is low, environmentally protective, production cost is low, comprehensive resource utilization rate is high, synthetical recovery valence
It is worth high advantage.
Handle Rare Earth Electrolysis fused salt slag through the invention, it can be achieved that electrolysis of fluorides matter and rare earth oxide, graphite and other
The clean separation of impurity breaches the conventional thought of Rare Earth Electrolysis fused salt slag only recovering rare earth, is realizing that fluoride of the present invention is electric
On the basis of solving matter recycling purpose, the efficient of rare earth in Rare Earth Electrolysis fused salt slag, lithium, fluorine and graphite resource can be further realized
Comprehensive reutilization.Present invention process is environmentally protective, process flow is short, at low cost, comprehensive resource utilization rate is high, synthetical recovery valence
Value is high, is very suitable to industrially large-scale promotion application.
Detailed description of the invention
Fig. 1 is Rare Earth Electrolysis fused salt slag process for separating and recovering flow chart of the present invention.
Fig. 2 is that front and back XRD comparative analysis figure is evaporated in vacuo in Rare Earth Electrolysis fused salt slag.
Specific embodiment
Below with reference to embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than it is right
Of the invention further limits.
The main component and content of Rare Earth Electrolysis fused salt slag used in the embodiment of the present invention are as follows: REO-38.76%, Li2O-
5.73%, F-20.40%, C-30.12%, Fe2O3- 4.21%, SiO2- 0.7%, Al2O3- 1.61%, CaO-2.49%.
Electrolysis of fluorides matter is recycled by vacuum distillation method, uses fluoride recovery as the evaluation criterion of separating effect.
Electrolysis of fluorides matter total amount × 100% in the rate of recovery=fluoride volatile quantity/electrolytic slag
Embodiment 1
Rare Earth Electrolysis fused salt slag is put into vacuum distillation tank, is 1100 DEG C in vacuum distillation temperature, material size 50
Mesh investigates influence of the vacuum degree to the electrolysis of fluorides matter rate of recovery in furnace, result such as 1 institute of table under the conditions of distillation time is 4h
Show.
Influence of 1 vacuum degree of table to the electrolysis of fluorides matter rate of recovery
Embodiment 2
Rare Earth Electrolysis fused salt slag is put into vacuum distillation tank, is 5Pa in vacuum degree, material size is 50 mesh, when distillation
Between under the conditions of 4h, to investigate influence of the vapo(u)rizing temperature to the electrolysis of fluorides matter rate of recovery, the results are shown in Table 2.
Influence of 2 vapo(u)rizing temperature of table to the electrolysis of fluorides matter rate of recovery
Embodiment 3
Rare Earth Electrolysis fused salt slag is put into vacuum distillation tank, is 1100 DEG C in vacuum distillation temperature, material size 50
Mesh under the conditions of vacuum degree is 5Pa, investigates influence of the distillation time to the electrolysis of fluorides matter rate of recovery, the results are shown in Table 3.
Influence of 3 distillation time of table to the electrolysis of fluorides matter rate of recovery
Embodiment 4
Rare Earth Electrolysis fused salt slag is put into vacuum distillation tank, is 1100 DEG C, distillation time 6h in vacuum distillation temperature,
Under the conditions of vacuum degree is 5Pa, influence of the material size to the electrolysis of fluorides matter rate of recovery is investigated, the results are shown in Table 4.
Influence of 4 material size of table to the electrolysis of fluorides matter rate of recovery
Embodiment 5
Vacuum distillation:
Rare Earth Electrolysis fused salt slag is put into vacuum distillation tank, is 1100 DEG C, distillation time 6h in vacuum distillation temperature,
100 mesh of material size, vacuum degree are tested under the conditions of being 5Pa, and the electrolysis of fluorides matter rate of recovery is up to 95.3%, obtained fluorination
Object electrolyte directly returns to the use of Rare Earth Electrolysis process.Electrolytic slag and product of distillation are carried out shown in XRD comparative analysis Fig. 2.By
Fig. 2 it is found that electrolytic slag mainly with NdF3、PrOF、NdF2、NdOF、Nd2Ce2O3F3, LiF, C-shaped formula exist, through vacuum distillation just
After step vacuum distillation, condensation distillation is mainly NdF3、LiF、PrF3, have no the miscellaneous cutting edge of a knife or a sword of other substances, and NdF in distillation3、
LiF、PrF3Diffraction maximum it is more sharp, illustrate NdF3、LiF、PrF3It is enriched with.
Distill Slag treatment:
Distillation slag progress hydrochloric acid is excellent molten, at 80 DEG C of acidleach temperature, under the conditions of leaching time 1h, acidleach terminal pH are 4.0,
Up to 99.3%, obtained rare earth leaches rare earth leaching rate, in 1.2 times that oxalic acid additional amount is rare earth quality, 80 DEG C of precipitation temperature,
Precipitating rare earth is carried out under the conditions of precipitating terminal pH=2.0, obtains rare earth oxalate after filtering drying, calcination 2h is obtained at 850 DEG C
To rare earth oxide.The excellent molten obtained kish slag of hydrochloric acid cleans under the conditions of acid solution pH=0.5, acid dissolution time 2h, insoluble
Solid is filtered, washed, dry after obtain graphite powder.Entire technique rare earth total recovery is up to 98.21%, and the lithium rate of recovery is up to
95%, the fluorine rate of recovery >=95%, recycling graphite rate >=98%.
Claims (7)
1. a kind of method from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components, it is characterised in that: first will be dilute
Soil electrolysis fused salt slag is crushed, and broken Rare Earth Electrolysis fused salt slag is evaporated in vacuo again, is collected after vacuum distillation
Electrolysis of fluorides matter, directly return Rare Earth Electrolysis process.
2. a kind of side from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components according to claim 1
Method, it is characterised in that: the fluoric-salt system Rare Earth Electrolysis fused salt slag is rare earth fluoride-lithium fluoride-rare earth oxide system fused salt
The Rare Earth Electrolysis fused salt slag generated during electrolysis production rare earth metal and rare earth alloy.
3. a kind of side from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components according to claim 1
Method, it is characterised in that: it is 50-500 mesh that the Rare Earth Electrolysis fused salt slag, which is crushed to partial size,.
4. a kind of side from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components according to claim 3
Method, it is characterised in that: it is 50-100 mesh that the Rare Earth Electrolysis fused salt slag, which is crushed to partial size,.
5. a kind of side from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components according to claim 1
Method, it is characterised in that: the condition of the vacuum distillation are as follows: vapo(u)rizing temperature is 700-1600 DEG C；Distillation time is 1-12h；Vacuum
Degree is 1-100Pa.
6. a kind of side from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte components according to claim 5
Method, it is characterised in that: the condition of the vacuum distillation are as follows: vapo(u)rizing temperature is 1000-1100 DEG C；Distillation time is 3-8h；Vacuum
Degree is 1-10Pa.
7. according to claim 1-6 a kind of from fluoric-salt system Rare Earth Electrolysis fused salt slag separation and recovery electrolyte group
The method divided, it is characterised in that: Rare Earth Electrolysis fused salt slag residue after being evaporated in vacuo has distillation slag, treatment process are as follows:
Distillation slag through hydrochloric acid it is excellent it is molten obtain re dip solution and kish slag, re dip solution is by further removal of impurities, precipitating, calcination
Rare earth oxide product can be obtained, kish slag can arrive graphite powder by the further molten removal of impurities of acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910771676.3A CN110344086B (en) | 2019-08-21 | 2019-08-21 | Method for separating and recovering electrolyte components from fluoride system rare earth electrolysis molten salt slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910771676.3A CN110344086B (en) | 2019-08-21 | 2019-08-21 | Method for separating and recovering electrolyte components from fluoride system rare earth electrolysis molten salt slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110344086A true CN110344086A (en) | 2019-10-18 |
| CN110344086B CN110344086B (en) | 2021-03-30 |
Family
ID=68180878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910771676.3A Active CN110344086B (en) | 2019-08-21 | 2019-08-21 | Method for separating and recovering electrolyte components from fluoride system rare earth electrolysis molten salt slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110344086B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519020A (en) * | 2020-05-08 | 2020-08-11 | 赣州有色冶金研究所 | Method for recovering valuable elements from rare earth electrolytic molten salt slag |
| CN111534701A (en) * | 2020-06-03 | 2020-08-14 | 赣州有色冶金研究所 | Method for efficiently recovering valuable elements from rare earth molten salt electrolytic slag |
| CN111876795A (en) * | 2020-07-28 | 2020-11-03 | 江苏金石稀土有限公司 | Method for recovering electrolyte in rare earth molten salt slag |
| CN114134543A (en) * | 2021-12-16 | 2022-03-04 | 中国铝业股份有限公司 | Method and device for recovering rare earth electrolyte |
| CN114380320A (en) * | 2021-12-03 | 2022-04-22 | 东北大学 | Method for recycling valuable resources in rare earth molten salt electrolytic slag through fluorination conversion and vacuum distillation |
| CN115852163A (en) * | 2022-11-23 | 2023-03-28 | 包头稀土研究院 | Separation method of rare earth zinc alloy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102046820A (en) * | 2008-03-26 | 2011-05-04 | 财团法人生产技术研究奖励会 | Method and apparatus for collection of rare earth element |
| CN104894600A (en) * | 2015-05-25 | 2015-09-09 | 东北大学 | Method for separating and recovering carbon and electrolytic constituents from aluminum molten salt electrolysis carbon-containing solid wastes |
| CN105567985A (en) * | 2015-12-28 | 2016-05-11 | 江苏金石稀土有限公司 | Recovery method of rare earth metal electrolysis fused salt slag |
-
2019
- 2019-08-21 CN CN201910771676.3A patent/CN110344086B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102046820A (en) * | 2008-03-26 | 2011-05-04 | 财团法人生产技术研究奖励会 | Method and apparatus for collection of rare earth element |
| CN104894600A (en) * | 2015-05-25 | 2015-09-09 | 东北大学 | Method for separating and recovering carbon and electrolytic constituents from aluminum molten salt electrolysis carbon-containing solid wastes |
| CN105567985A (en) * | 2015-12-28 | 2016-05-11 | 江苏金石稀土有限公司 | Recovery method of rare earth metal electrolysis fused salt slag |
Non-Patent Citations (1)
| Title |
|---|
| 黄丹丹 等: "氧化物沉淀-减压蒸馏耦合分离FLiNaK熔盐中的NdF3", 《核技术》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519020A (en) * | 2020-05-08 | 2020-08-11 | 赣州有色冶金研究所 | Method for recovering valuable elements from rare earth electrolytic molten salt slag |
| CN111534701A (en) * | 2020-06-03 | 2020-08-14 | 赣州有色冶金研究所 | Method for efficiently recovering valuable elements from rare earth molten salt electrolytic slag |
| CN111876795A (en) * | 2020-07-28 | 2020-11-03 | 江苏金石稀土有限公司 | Method for recovering electrolyte in rare earth molten salt slag |
| CN111876795B (en) * | 2020-07-28 | 2022-12-06 | 江苏金石稀土有限公司 | Method for recovering electrolyte in rare earth molten salt slag |
| CN114380320A (en) * | 2021-12-03 | 2022-04-22 | 东北大学 | Method for recycling valuable resources in rare earth molten salt electrolytic slag through fluorination conversion and vacuum distillation |
| CN114134543A (en) * | 2021-12-16 | 2022-03-04 | 中国铝业股份有限公司 | Method and device for recovering rare earth electrolyte |
| CN115852163A (en) * | 2022-11-23 | 2023-03-28 | 包头稀土研究院 | Separation method of rare earth zinc alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110344086B (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110344086A (en) | A method of electrolyte components are separated and recovered from fluoric-salt system Rare Earth Electrolysis fused salt slag | |
| CN103849775B (en) | A kind of method reclaiming nickel and cobalt from high-temperature alloy waste material | |
| CN105886767B (en) | A kind of recovery method of copper indium gallium selenide waste material | |
| CN107282598A (en) | A kind of aluminium cell discards the recoverying and utilizing method of cathode carbon pieces | |
| CN108470951A (en) | The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium ion battery | |
| CN111519020B (en) | Method for recovering valuable elements from rare earth electrolytic molten salt slag | |
| WO1994023073A1 (en) | Method for collecting valuable metal from nickel-hydrogen secondary cell | |
| CN107827089A (en) | Method for separating and recovering tellurium dioxide in cuprous telluride compound waste | |
| CN106048231A (en) | Method for recovering tantalum, silver, nickel and iron from waste tantalum capacitor | |
| CN111321302B (en) | Method for recovering lithium and potassium from high lithium potassium anode carbon residue or high lithium potassium electrolyte | |
| CN103449523A (en) | Preparation method of extracted high-purity molybdenum trioxide | |
| CN116334410A (en) | Method for separating lithium from lithium-containing electrolyte waste residues in aluminum electrolysis | |
| CN104164567A (en) | Method for enriching and recycling niobium and tantalum from waste high-temperature alloy | |
| CN102952951A (en) | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag | |
| CN106757156B (en) | A method of from recycling Re in high-temperature alloy waste material containing Re | |
| CN110357126A (en) | The recovery method of fluorine-containing molten-salt electrolysis slag | |
| CN102628105B (en) | Method for comprehensively recycling and using baric waste slag in refined aluminum production process | |
| CN111348653B (en) | Method for preparing high-purity silicon, titanium white and high-purity fluoride by using titanium-containing slag and low-purity silicon material | |
| CN109536715A (en) | A kind of zinc lixiviating solution Cobalt Purification method | |
| CN109136996B (en) | Method for preparing Mg-Nd base intermediate alloy by using neodymium iron boron waste | |
| CN108441637B (en) | The method of valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell | |
| CN116536514A (en) | Method for extracting lithium from lithium-containing electrolytic aluminum electrolyte by using organic acid | |
| CN109536992A (en) | A kind of method of two de- two products purifying copper electrolytes | |
| CN110735155A (en) | Method for producing electrolytic manganese metal and co-producing manganese dioxide | |
| JP5482461B2 (en) | Method for recovering copper from copper electrolysis waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |