CN107385474B - A kind of chlorination calcium molten salt electrolysis calcium electrolyte and the electrolytic method using the electrolyte - Google Patents
A kind of chlorination calcium molten salt electrolysis calcium electrolyte and the electrolytic method using the electrolyte Download PDFInfo
- Publication number
- CN107385474B CN107385474B CN201710660046.XA CN201710660046A CN107385474B CN 107385474 B CN107385474 B CN 107385474B CN 201710660046 A CN201710660046 A CN 201710660046A CN 107385474 B CN107385474 B CN 107385474B
- Authority
- CN
- China
- Prior art keywords
- calcium
- electrolyte
- electrolysis
- fused salt
- calcium chloride
- 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.)
- Active
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
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- 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
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
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)
Abstract
The invention discloses the electrolytic method of a kind of chlorination calcium molten salt electrolysis calcium electrolyte and the use electrolyte, the molar percentage group of electrolyte of the present invention becomes：CaCl2It is 10%~20%KF for 5%~20%, LiCl, KF is 10%~20%, CaF2It is 5%~10%, surplus KCl.The density of electrolyte primary crystal temperature and electrolyte using said components formula can be substantially relatively low, it can be controlled in the density less than melting calcium, when being produced using above-mentioned electrolyte, the molten metal doped calcium that can obtain electrolysis is on the carbon cathode surface of electrolyte bottom.Fused salt calcium electrolysis production is carried out based on the electrolyte, the production model of existing calcium electrolysis can thoroughly be changed, obtained calcium metal collects in bottom of electrolytic tank, can very easily extract out, and no longer need to process, to realize the extensive of calcium electrolysis, serialization and production energy-saving.
Description
Technical field
The invention belongs to electrolysis tech field more particularly to a kind of chlorination calcium molten salt electrolysis calcium electrolyte and use should
The electrolytic method of electrolyte.
Background technology
The industrialized production main means of the high-purity calcium of metal are chlorination calcium molten salt electrolysis, and used method includes that contact is cloudy
Pole method and liquid cathode method.Traditional Contact cathod method proposed by W.Rathenau in 1904 first, the electrolyte used
For CaCl2And CaF2The mixture of composition.The density of the molten mixture is much larger than the density of fused salt calcium, therefore design of electrolysis cells
For cathode close to slot top, anode in slot lower part, electrolytic process, calcium is precipitated on cathode by electrochemical reaction, on anode
Chlorine is precipitated, and since the density of calcium is less than fused calcium chloride, and the surface of electrolyte is swum in, it is cold when with steel cathode contacts
It coagulates on cathode.Cathode is only capable of contacting and cannot being placed in electrolyte with bath surface, artificially to be poured on calcium pump surface
One layer of cold electrolyte of note, separates calcium and air, avoids the oxidizing fire of calcium.With the progress of electrolysis, cathode constantly accordingly carries
It rises, calcium forms the club of a carrot shape in cathode bottom.Electrolysis starts, the electrolysis bath ebullition below cathode, generates calcium
Pearl, calcium pearl is condensed once touching the cold surface of cathode, and is sticked to above anode.With the promotion of cathode, below cathode again
Generate new calcium pearl.
This method be most directly produce high pure metal calcium method, but consider used electrolyte system the reason of,
Calcium metal caused by causing swims in the top of electrolyte, and such as without specially treated, then the active metal calcium melted is quickly
It can be aoxidized, and even if the inherent shortcoming of this method can not be solved if using corresponding technology, that is, the calcium metal generated floats
Problem on electrolyte, thus also result in conventional contacts cathode method production calcium and have that consumption of raw materials is big, low output, electric current
Efficiency low (secondary oxidation of calcium is serious), labour and it is of high cost a series of problems, such as, or even gradually face by liquid cathode method
Electrolysis is replaced.
Therefore, to solve the problems, such as that conventional contacts method production calcium metal is faced, it is relatively molten that first choice must design a kind of density
Melt the low electrolyte system that can be completed calcium and be electrolysed of calcium metal, and then cell construction is designed again, to adapt to metal
Calcium is gathered in slot Inner electrolysis matter bottom this new phenomenon, to realize efficient, the large-scale continuous production of electrolysis of calcium metal.
Invention content
A kind of chlorination calcium molten salt electrolysis calcium electrolysis is provided it is an object of the invention to overcome the deficiencies in the prior art
Matter, not only liquidus temperature is low for the electrolyte, but also density is less than the density of melting calcium, utilizes the electrolytically generated metal of the electrolyte
Calcium can make molten metal doped calcium on the carbon cathode surface of electrolyte bottom, can thoroughly change the life of existing calcium electrolysis
Production pattern, obtained calcium metal collect in bottom of electrolytic tank, can very easily extract out, and no longer need to process, to real
Existing the extensive of calcium electrolysis, serialization and production energy-saving.
In order to solve the above technical problems, the molar percentage group of calcium chloride electrolyzing fused salt solution matter provided by the present invention
Become：CaCl2For 5%~20%, LiCl be 10%~20%, KF it is 10%~20%, CaF2It is 5%~10%, surplus is
KCl。
Preferably, the molar percentage group of the electrolyte becomes：CaCl2It is 14%~16% for 10%~15%, LiCl,
KF is 14%~16%, CaF2It is 6%~8%, surplus KCl.
Preferably, the molar percentage group of the electrolyte becomes：CaCl2For 12%, LiCl 15%, KF 15%, CaF2
It is 7%, surplus KCl.
Further, the electrolysis temperature of electrolyte is 550 DEG C~700 DEG C.
Further, the liquidus temperature of electrolyte is 530 DEG C~680 DEG C.
Further, the density of electrolyte is 1.38~1.58g/cm3。
Using the electrolytic method of above-mentioned calcium chloride fused salt electrolyte, this method passes through a set of chlorination calcium molten salt electrolysis system
Calcium device is implemented, which includes the electrolytic cell with heating device, the gas collection that is connected to above electrolytic cell and blanking system, setting
The several groups anode being correspondingly arranged in the cathode of bottom of electrolytic tank and above cathode and with cathode, includes the following steps：
(1) by the CaCl of specific quantity2、LiCl、KF、CaF2, KCl mixed, the mixture that will be obtained using heating device
It is maintained at molten state；
(2) melt in step (1) 550 DEG C~700 DEG C are warming up to be electrolysed.
Preferably, CaCl is quantitatively supplemented by gas collection and blanking system in electrolytic process2。
Preferably, the CaCl of supplement2Moisture content<0.01%.
Preferably, electrolytic process Anodic current density is 1.5~3.5A/cm2。
Further, ranging from 50~200kA of electric tank working electric current.
Compared with the prior art, the advantages of the present invention are as follows：
(1) electrolyte primary crystal temperature and density of the present invention are greatly reduced, and density is in 1.38~1.58g/cm3Between, primary crystal
For temperature between 530 DEG C~680 DEG C, conductivity is 2.5~4.5S.cm-1, prior so as to work at lower temperatures
It is to produce obtained calcium metal due to density variation, the bottom of electrolyte can be gathered in, to inherently change existing connect
The technique and production process of the method for touching electrolysis calcium, fundamentally avoid the calcium produced during volume traditional electrolyte because floating on electrolyte
Surface and the great drawback of secondary oxidation, can obtain high-purity calcium metal with Direct Electrolysis.
(2) the extensive clean manufacturing of calcium electrolysis may be implemented in the present invention.Since the calcium metal that present invention electrolysis obtains is poly-
Collection can very easily utilize vacuum precipitation, therefore electrolytic process is a continuous, efficient process in trench bottom, and due to
Single slot is 50kA or more, and single slot extension or the series connection of more slots extension can be carried out according to actual conditions, therefore large-scale industry
Change will also become very easy.
(3) quick, the high maintenance of electrolytic cell may be implemented in the electrolysis unit used in the present invention.Due in electrolysis unit
Anode be respectively independent, operation can very easily use for reference very ripe at present and efficient aluminium electroloysis with management
Slot management mode, the maintenance management of anode, the precipitation of calcium become very efficiently, and not consuming due to anode, electrolytic cell
Operation that can be steady in a long-term.
In conclusion the present invention, which is a kind of can realize, utilizes direct extensive, the continuous high-efficient production calcium metal of contact method
Electrolyte system and electrolytic method can be that the large-scale low-cost production of the high-purity calcium of industry provides safeguard.
Description of the drawings
Fig. 1 is chlorination calcium molten salt electrolysis calcium apparatus structure schematic diagram in the present invention.
Specific implementation mode
Embodiment 1
The molar percentage group of electrolyte becomes in the present embodiment：12%CaCl2, 15%LiCl, 15%KF, 7%CaF2、
51%KCl.
The performance of electrolyte described in the present embodiment is measured, result is：The density of electrolyte in the present embodiment
For 1.48g/cm3, liquidus temperature is 600 DEG C, conductivity 3.25S.cm-1。
Embodiment 2
The molar percentage group of electrolyte becomes in the present embodiment：10%CaCl2, 10%LiCl, 20%KF, 6%CaF2、
54%KCl.
The performance of electrolyte described in the present embodiment is measured, result is：The density of electrolyte in the present embodiment
For 1.43g/cm3, liquidus temperature is 594 DEG C, conductivity 3.43S.cm-1。
Embodiment 3
The molar percentage group of electrolyte becomes in the present embodiment：15%CaCl2, 20%LiCl, 12%KF, 8%CaF2、
45%KCl.
The performance of electrolyte described in the present embodiment is measured, result is：The density of electrolyte in the present embodiment
For 1.54g/cm3, liquidus temperature is 608 DEG C, conductivity 3.12S.cm-1。
Embodiment 4
The molar percentage group of electrolyte becomes in the present embodiment：20%CaCl2, 15%LiCl, 12%KF, 8%CaF2、
45%KCl.
The performance of electrolyte described in the present embodiment is measured, result is：The density of electrolyte in the present embodiment
For 1.58g/cm3, liquidus temperature is 615 DEG C, conductivity 3.09S.cm-1。
Embodiment 5
The molar percentage group of electrolyte becomes in the present embodiment：6%CaCl2, 12%LiCl, 20%KF, 6%CaF2、
56%KCl.
The performance of electrolyte described in the present embodiment is measured, result is：The density of electrolyte in the present embodiment
For 1.38g/cm3, liquidus temperature is 538 DEG C, conductivity 3.63S.cm-1。
The chlorination calcium molten salt electrolysis calcium device used in the present invention is as shown in Figure 1, the device includes with heating device
Electrolytic cell 1, the gas collection and blanking system 2, graphite electrode for being connected to 1 top of electrolytic cell.
The working region of the electrolytic cell 1 is a rectangular area, length 18000mm, width 3000mm, electrolytic cell 1
It is made of with the insulating layer 4 being arranged in pot shell 3 pot shell 3 of outer layer.
Graphite electrode is arranged in pairs in electrolytic cell 1, and graphite electrode is acyclic type electrode, and the thickness of electrode is 200~
300mm, length are 2000~4000mm, and width is 300~500mm, and 6 spacing side by side of several groups cathode is arranged at 1 bottom of electrolytic cell
Portion, anode 5 are located at 6 top of cathode and are correspondingly arranged with cathode 6, and the top of anode 5 is connected with anode rod 7, the bottom of cathode 6
It is fitted with cathode steel bar 8.
Electrolytic method using electrolyte in the present embodiment 1 is：
(1) by the CaCl of above-mentioned amount2、LiCl、KF、CaF2, KCl mixed, the mixture that will be obtained using heating device
It is maintained at molten state；
(2) melt in step (1) is warming up to 610 DEG C to be electrolysed, passes through gas collection and blanking system in electrolytic process
System quantitatively supplements CaCl2Anodic gas chlorine caused by being collected simultaneously, electrolytic process Anodic current density are 2.5A/cm2,
Electric tank working electric current is 150kA.
Electrolytic method using electrolyte in the present embodiment 2 is：
(1) by the CaCl of above-mentioned amount2、LiCl、KF、CaF2, KCl mixed, the mixture that will be obtained using heating device
It is maintained at molten state；
(2) melt in step (1) is warming up to 604 DEG C to be electrolysed, passes through gas collection and blanking system in electrolytic process
System quantitatively supplements CaCl2Anodic gas chlorine caused by being collected simultaneously, electrolytic process Anodic current density are 1.6A/cm2,
Electric tank working electric current is 120kA.
Electrolytic method using electrolyte in the present embodiment 3 is：
(1) by the CaCl of above-mentioned amount2、LiCl、KF、CaF2, KCl mixed, the mixture that will be obtained using heating device
It is maintained at molten state；
(2) melt in step (1) is warming up to 615 DEG C to be electrolysed, passes through gas collection and blanking system in electrolytic process
System quantitatively supplements CaCl2Anodic gas chlorine caused by being collected simultaneously, electrolytic process Anodic current density are 1.65A/cm2,
Electric tank working electric current is 200kA.
Electrolytic method using electrolyte in the present embodiment 4 is：
(1) by the CaCl of above-mentioned amount2、LiCl、KF、CaF2, KCl mixed, the mixture that will be obtained using heating device
It is maintained at molten state；
(2) melt in step (1) is warming up to 620 DEG C to be electrolysed, passes through gas collection and blanking system in electrolytic process
System quantitatively supplements CaCl2Anodic gas chlorine caused by being collected simultaneously, electrolytic process Anodic current density are 1.75A/cm2,
Electric tank working electric current is 250kA.
Electrolytic method using electrolyte in the present embodiment 5 is：
(1) by the CaCl of above-mentioned amount2、LiCl、KF、CaF2, KCl mixed, the mixture that will be obtained using heating device
It is maintained at molten state；
(2) melt in step (1) is warming up to 548 DEG C to be electrolysed, passes through gas collection and blanking system in electrolytic process
System quantitatively supplements CaCl2Anodic gas chlorine caused by being collected simultaneously, electrolytic process Anodic current density are 1.5A/cm2,
Electric tank working electric current is 120kA.
Above-described embodiment is elaborated the particular content of the present invention, and those skilled in the art should be bright
In vain, it is claimed that the variation in any type of improvement done on the basis of the present invention and details belongs to the present invention
Content.
Claims (10)
1. a kind of calcium chloride electrolyzing fused salt solution matter, it is characterised in that the molar percentage group of the electrolyte becomes：CaCl2For
5%~20%, LiCl are that 10%~20%, KF is 10%~20%, CaF2It is 5%~10%, surplus KCl.
2. calcium chloride electrolyzing fused salt solution matter according to claim 1, it is characterised in that：The Mole percent of the electrolyte
Become than group：CaCl2For 10%~15%, LiCl be 14%~16%, KF it is 14%~16%, CaF2It is 6%~8%, surplus
For KCl.
3. calcium chloride electrolyzing fused salt solution matter according to claim 2, it is characterised in that：The Mole percent of the electrolyte
Become than group：CaCl2For 12%, LiCl 15%, KF 15%, CaF2It is 7%, surplus KCl.
4. calcium chloride electrolyzing fused salt solution matter according to claim 1, it is characterised in that：The electrolysis temperature of the electrolyte
Degree is 550 DEG C~700 DEG C.
5. calcium chloride electrolyzing fused salt solution matter according to claim 1, it is characterised in that：The primary crystal temperature of the electrolyte
Degree is 530 DEG C~680 DEG C.
6. calcium chloride electrolyzing fused salt solution matter according to claim 1, it is characterised in that：The density of the electrolyte is
1.38~1.58g/cm3。
7. using the electrolytic method of claim 1-6 any one of them calcium chloride electrolyzing fused salt solution matter, pass through a set of chlorine
Change calcium molten salt electrolysis calcium device to implement, which is characterized in that include the following steps：
(1) by the CaCl of specific quantity2、LiCl、KF、CaF2, KCl mixed, using chlorination calcium molten salt electrolysis calcium device will
To mixture be maintained at molten state；
(2) melt in step (1) 550 DEG C~700 DEG C are warming up to be electrolysed.
8. the electrolytic method of the calcium chloride electrolyzing fused salt solution matter according to right 7, it is characterised in that：Calcium chloride fused salt electricity
The gas collection and blanking system, setting that solution calcium device includes the electrolytic cell with heating device, is connected to above electrolytic cell are being electrolysed
The cathode of trench bottom and the several groups anode being correspondingly arranged above cathode and with cathode.
9. the electrolytic method of calcium chloride electrolyzing fused salt solution matter according to claim 8, it is characterised in that：It had been electrolysed
CaCl is quantitatively supplemented by gas collection and blanking system in journey2。
10. the electrolytic method of the calcium chloride electrolyzing fused salt solution matter according to right 7, it is characterised in that：In electrolytic process
Anodic current density is 1.5~3.5A/cm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710660046.XA CN107385474B (en) | 2017-08-04 | 2017-08-04 | A kind of chlorination calcium molten salt electrolysis calcium electrolyte and the electrolytic method using the electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710660046.XA CN107385474B (en) | 2017-08-04 | 2017-08-04 | A kind of chlorination calcium molten salt electrolysis calcium electrolyte and the electrolytic method using the electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107385474A CN107385474A (en) | 2017-11-24 |
| CN107385474B true CN107385474B (en) | 2018-10-12 |
Family
ID=60344697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710660046.XA Active CN107385474B (en) | 2017-08-04 | 2017-08-04 | A kind of chlorination calcium molten salt electrolysis calcium electrolyte and the electrolytic method using the electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107385474B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4738759A (en) * | 1984-10-05 | 1988-04-19 | Extramet S.A. Zone Industrielle | Method for producing calcium or calcium alloys and silicon of high purity |
| JPH02259092A (en) * | 1989-03-31 | 1990-10-19 | Nippon Steel Corp | Production of calcium |
| US5225051A (en) * | 1991-09-24 | 1993-07-06 | The United States Of America As Represented By The United States Department Of Energy | Electrowinning process with electrode compartment to avoid contamination of electrolyte |
| US7410562B2 (en) * | 2003-08-20 | 2008-08-12 | Materials & Electrochemical Research Corp. | Thermal and electrochemical process for metal production |
| AU2005258596A1 (en) * | 2004-06-30 | 2006-01-12 | Toho Titanium Co., Ltd. | Method and apparatus for producing metal by electrolysis of molten salt |
| CN101148773B (en) * | 2007-07-24 | 2010-07-07 | 哈尔滨工程大学 | Method for producing magnesium-lithium-calcium alloy by fused salt electrolytic ion eutectoid method |
| JP5138465B2 (en) * | 2008-05-27 | 2013-02-06 | 東邦チタニウム株式会社 | Method and apparatus for producing metallic calcium |
| CN102071434B (en) * | 2010-12-08 | 2012-11-14 | 华东理工大学 | Method for removing impurity CaCl2 from lithium electrolyte KCl-LiCl |
-
2017
- 2017-08-04 CN CN201710660046.XA patent/CN107385474B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107385474A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102121117B (en) | Cathode boss structure of aluminum electrolysis cell | |
| WO2016082726A1 (en) | Electrolysis furnace | |
| CN205062204U (en) | Electrolytic furnace | |
| CN105088284B (en) | A kind of electrolytic furnace | |
| CN104818499B (en) | A kind of electrolysis is bench of burners | |
| WO2008106849A1 (en) | Electrolytic cells for aluminum having cathode carbon blocks with heterotypic structure | |
| CN101805914B (en) | Bottom cathode diversion type rare earth electrolysis cell | |
| CN105256337B (en) | A kind of novel rare-earth electrolytic cell | |
| CN207672137U (en) | Anode steel claw strainer | |
| CN1201034C (en) | Electrolytic cell for production of aluminium and a method for maintaining crust on sidewall and for recovering electricty | |
| CN108950604A (en) | A kind of aluminum electrolysis technology | |
| CN102534663A (en) | Device for generating metal magnesium by electrolyzing magnesium chloride | |
| CN204661841U (en) | A kind of electrolytic furnace group | |
| CN102154661A (en) | Method for preparing aluminum ingot by low-temperature electrolysis of metal monocrystal surface electrodes | |
| CN107385474B (en) | A kind of chlorination calcium molten salt electrolysis calcium electrolyte and the electrolytic method using the electrolyte | |
| CN104213152A (en) | Aluminum electrolysis cell with center joint material blocking partition plate | |
| CN107881531B (en) | A kind of composite anode of aluminium cell | |
| CN101984143B (en) | External heated aluminum electrolytic cell | |
| CN205556801U (en) | Pre -baked aluminum reduction cells positive pole group structure | |
| CN101845641B (en) | Immersion-type rare earth electrolyzer | |
| WO2004018736A1 (en) | Utilisation of oxygen evolving anode for hall-heroult cells and design thereof | |
| CN201722432U (en) | Bottom cathode diversion-type rare-earth electrolytic bath | |
| CN213680931U (en) | Closed type rare earth chloride system electrolytic cell | |
| CN102925931B (en) | Negative electrode rare earth molten salt electrolytic under submergence type is inserted in side | |
| CN105780053B (en) | A kind of aluminum electrolysis method using aluminium as cathode |
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 |