CN109652816A - Tungsten does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride - Google Patents
Tungsten does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride Download PDFInfo
- Publication number
- CN109652816A CN109652816A CN201910015696.8A CN201910015696A CN109652816A CN 109652816 A CN109652816 A CN 109652816A CN 201910015696 A CN201910015696 A CN 201910015696A CN 109652816 A CN109652816 A CN 109652816A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- electrolysis
- anode
- tungsten hexafluoride
- fuse salt
- 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
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
It is preferred that tungsten plate does anode electrolytic cell, excellent to do electrolyte with raw material fluorinated lithium beryllium eutectic, melting range is suitble to electrolysis and fluoride-free hydrogen ingredient, pollution of the harmful components such as carbon tetrafluoride and hydrogen fluoride to finished product tungsten hexafluoride can be cut off from source.The fuse salt fugitive dust of the tungsten hexafluoride and entrainment that generate in electrolytic cell and the fluorine gas not reacted on a small quantity with tungsten enter purification for gas tank along cell gas outlet, with fugitive dust filter plate and the electrolyte micronic dust of fugitive dust adsorbent removal tungsten hexafluoride entrainment；Unreacted a small amount of fluorine gas is completely converted into tungsten hexafluoride with tungsten microballoon conversion zone, is all filtered the tungsten particle of entrainment with millipore filter, final output high-purity tungsten hexafluoride gas.The present invention realizes electrolysis method and directly synthesizes high-purity tungsten hexafluoride, has many advantages, such as that process route is succinct, finished product impurity is few, high income, the comprehensive great competitiveness of production cost.
Description
Technical field
The present invention relates to devices and technique that a kind of electrolyzing fused salt directly synthesizes high-purity tungsten hexafluoride.
Background technique
Tungsten hexafluoride (WF6) it is kind uniquely stable and by industrialized production in the fluoride of tungsten so far.It is important
There are many purposes；Tungsten/rhenium composite coating is such as made by the CVD technique of mixed metal, can be used for solar energy energy-absorbing material and X-ray
The manufacture of emission electrode；So that tungsten is generated hard tungsten carbide on steel, copper or other metal surfaces can be used to improve the table of metal
Face performance and for manufacturing various special-shaped tungsten part such as tungsten pipes, tungsten nozzle and tungsten crucible etc..WF6It is also extensive in electronics industry
As semi-conducting electrode and conductive paste raw material, especially with its manufactured tungsten silicide (WSi2), it is commonly used for microelectronics
The middle current divider as on electric shock material and polysilicon lines, because the electric conductivity and signal speed of polysilicon lines can be enhanced at high temperature
Degree, has become extremely important wiring material in large scale integrated circuit industry.
Synthesize WF6Method it is very much, conclude published report, industry mature at present is combined to WF6Technique main line just like
Lower three；
1, use Cl2The technique that 2HF mixture makees fluorization agent.Under the conditions of tungsten is existing for the no moisture and air with
Cl22HF mixture reaction preparation WF6, react and carried out in the usually autoclave made of monel metal, reaction equation is as follows: W+
3Cl2+ 6HF=WF6+6HCl.To ensure that product has good yield, Cl is needed2It is suitably excessive with HF, chlorine and tungsten hexafluoride
Theoretical molar ratio is 3: 1, uses 4~6: 1 in practice, and the theoretical molar ratio of hydrogen fluoride and tungsten hexafluoride is 6: 1, is used in practice
7~10: 1.Reaction temperature controls and improves progress (but the excessively high meeting of temperature that reaction temperature is conducive to reaction at 200~450 DEG C
Cause corrosion of equipment serious).For this technique greatest problem other than product tungsten hexafluoride purity is not high, yield is lower, pollution is tight
The reason of again and causing this process route that cannot be widely applied.
2, use fluorine gas as the technique of fluorization agent.Tungsten and fluorine gas directly react obtained WF6.Reaction equation is as follows: W+3F2
=WF6.Reaction is that fluidized bed containing tungsten or fixed bed are flowed through by fluorine gas to complete, reaction temperature control 350~
450 DEG C or so, quickly, high income, side reaction is also seldom for aggregate velocity, as long as finished product tungsten hexafluoride quality height depends on synthesis
Raw material fluorine gas purity and tungsten impurity content are the synthesis technologies of most mainstream in current world wide.Only it is limited to raw material
Fluorine gas purity limits that (industrial fluorine gas all is from medium temperature and is electrolysed fluorine processed, and the ingredients such as entrained with carbon tetrafluoride, hydrogen fluoride are for hexafluoro
It is very big to change tungsten qualitative effects), so this will put into before practical application or synthesis at the tungsten hexafluoride that route synthesizes to original
Material fluorine gas carries out numerous purification (and the more awkward things of step to tungsten hexafluoride finished product after being refined or being synthesized
Be in fact: fluorine gas entrainment hydrogen fluoride enters after finished product tungsten hexafluoride, since the two boiling point is close, wants the two to separate, is one
The thing that part is difficult).
3, with Nitrogen trifluoride (NF3) technique as fluorization agent.By NF3Import a reaction made of nickel or monel metal
In device, NF3It is directly reacted at 200~400 DEG C with tungsten, generates WF6.Reaction equation is as follows: W+2NF3=WF6+N2.The technique
Maximum feature is the shadow to tungsten hexafluoride quality such as carbon tetrafluoride, hydrogen fluoride of entrainment when avoiding industrial fluorine gas to make fluorization agent
It rings.But have to be pointed out that；Industrial production Nitrogen trifluoride, mature process route be exactly fluorine and ammonia the direct synthesis or
Fluorine gas and ammonium acid fluoride, fluorine gas and hydrogen fluoride process etc. are several.If saying that the quality of Nitrogen trifluoride production tungsten hexafluoride is more raw than fluorine gas
The quality for producing tungsten hexafluoride is high, real causes be exactly by the purification trouble of raw material fluorine gas, with the purification of Nitrogen trifluoride come instead of.
But what benefit still had: although equally also to be processed by subsequent purification with Nitrogen trifluoride production tungsten hexafluoride, finished product is lithium
The purity of tungsten is just able to satisfy requirement, but due to avoiding the carbon tetrafluoride directly with fluorine gas synthesis tungsten hexafluoride entrainment substantially
And the difficult removal ingredient such as hydrogen fluoride, so efficiency is obviously much higher in subsequent refinement treatment.
It, at least will be in 99.99% (being commonly called as 4 9) since tungsten hexafluoride is very high in electronic gas industrial application purity requirement
More than, and the tungsten hexafluoride purity that above-mentioned three kinds of process route commercial synthesis come out is about between 99~99.9%, it is necessary to
It can be really practical by various subsequent refinement treatments.Tungsten hexafluoride purity reaches 99.99% referred above to high-purity tungsten hexafluoride,
By especially refining processing, tungsten hexafluoride purity can be made to reach 99.9999% or more (referred to as ultrapure tungsten hexafluoride).
For the tungsten hexafluoride purity for improving commercial synthesis, a large amount of research and development works have been done by domestic and international scientific research institution and manufacturing enterprise
Make.
As U.S. U.S.P5324498 discloses a kind of purification process of tungsten hexafluoride；" tungsten hexafluoride is initially evaporated to remove
Nonvolatile residue, then the product of condensation evaporation are removed, the tungsten hexafluoride of condensation is frozen into solid form later, is evacuated thereon
Melt solid to remove volatile impurity and heat tungsten hexafluoride to its boiling temperature or more under reduced pressure, evacuate in portion space
Upper part space, therefrom removes volatile impurity, and above steps may be repeated multiple times, is finally reached tungsten hexafluoride purifying purpose ".Analysis
It can be seen that: overall process has conclusive effect to volatile impurity, such as nitrogen and oxygen is removed, but in removing tungsten hexafluoride
Hydrogen fluoride is invalid, because they are close on boiling point.Simultaneously because this method needs to be repeated several times thermal cycle, also very consumption energy consumption
When.
For another example U.S. U.S.P5328668 and 5348723 discloses the integrated approach of production semiconductor grade tungsten hexafluoride.This
A little methods use evaporation as the means for removing non-volatile impurities from product, but without providing any removing metal impurities
Means and the method for reducing hydrogen fluoride level.
A kind of method that patent CN1281823A discloses ultra-pure (UHP) tungsten hexafluoride of production, this method is first by thick six
Tungsten fluoride is distilled to isolate the non-volatile metal impurity in tungsten hexafluoride, then removes HF after villiaumite adsorbs, finally
Bubble systems through UHP helium isolate high-purity tungsten hexafluoride product, and there is no go to improve tungsten hexafluoride from source for this method
Purity, but the purity of tungsten hexafluoride is improved using cumbersome purification process, production cost is prohibitively expensive.
Summary of the invention
In order to overcome prior art disadvantage, the present invention provides a kind of device and method of directly synthesis high-purity tungsten hexafluoride.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following scheme: the electrolysis made of heat resisting steel (1)
Rectangle groove body (1), entire groove body outside are kept the temperature with light fire brick thermal insulation layer (2), and installation is integrated respectively in heat resisting steel slot cover (6)
Sensor (8), the copper conducting rod of anode (9) and gas outlet tube (18), slot cover are fixed on by mica temperature resistant encapsulation felt pad
Above electrolytic cell body, sensor, conducting rod and gas outlet tube pass through respectively temperature resistant encapsulation insulation sleeve (7), (10) and
(19) it is fixed in slot cover.Tungsten plate (4) is fixed below conducting rod by anode electrolytic cell conducting rod tungsten plate fixed frame, gold
Belong to nickel plate (3) together with electric tank cathode conducting rod (21) rivet clasp, cathode conducting rod is fixed by temperature resistant encapsulation insulation sleeve (20)
Below fusion electrolysis slot groove body.Initial electrolysis matter selects lithium fluoride (LiF) and beryllium fluoride (BeF2) two kinds of villiaumites according to mole
Than 2:1 mixing (carried out later with electrolysis, lithium fluoride only serves the eutectiferous effect of building, the only beryllium fluoride actually consumed at
Point), select medium-frequency electrical heating device (22) and (24) heating electrolyte to molten condition (400~500 DEG C), by electrolyzing fused
Salt mode applies 2.5~3V DC voltage to electrolytic cell anode and cathode, cathode precipitating metal beryllium (due to melting points, metallic beryllium with
Broken flakey (23) falls to cell bottom from metal nickel cathode).Anode generate fluorine gas immediately with tungsten anode reaction
Generate tungsten hexafluoride.The fuse salt fugitive dust and a small amount of fluorine gas not reacted with tungsten of tungsten hexafluoride and entrainment are along electrolysis
Slot gas outlet tube (18) enters purification for gas tank (11), the fugitive dust filter plate (12) sintered by alkali metal and fugitive dust absorption
Agent (17) filtering, absorption fuse salt are entrained with the electrolytic cell solids come with gas, pass through tungsten microballoon support bracket (13) and tungsten
Microballoon conversion zone (16), by unreacted a small amount of fluorine gas total overall reaction at tungsten hexafluoride, gas is sintered by sponge nickel later
Millipore filter (14), it would be possible to the tungsten particle of entrainment all filters, finally with high-purity tungsten hexafluoride gaseous state from
Tank delivery line (15) are purified to draw.
According to known electrochemistry law, in an electrolytic cell, when applying DC voltage to electrolyte, electrolytic cell is just
The oxidation reaction of betatopic occurs respectively and obtains the reduction reaction of electronics for cathode.Important active metal such as sodium, potassium, lithium, aluminium etc.
None is not to be obtained by electrolyzing fused salt at electric tank cathode position.The product visual fusion at anode position melt salt anionic ingredient and
Fixed, if fuse salt is chloride, then anode generates chlorine, and if fuse salt is fluoride, then anode generates fluorine gas.
The electrolyte that the present invention selects is that beryllium fluoride and lithium fluoride are formed by low-melting-point eutectic.With chemical equation table
Show i.e. are as follows: 2LiF+BeF2→Li2BeF4(lithium fluoride beryllium eutectic).Not only fusing point is low for this kind of eutectiferous feature of lithium fluoride beryllium
(lower 400 DEG C of normal pressure or more are presented molten state), and steam forces down, heats high, eutectic formation wide (the two kinds of fluoride ratios of range
For example between 1:1 to 10:1, co-crystal structures are all very stable, and fusing point increases also seldom).It has been widely used in such as solar energy storage
It deposits, the heat-exchange fluid in fission reactor and fusion reactor and the electrochemical production for beryllium metal.
DC voltage is applied to lithium fluoride beryllium electrolyte, two kinds of metals (metallic beryllium and metals can be generated in cathode by seeming
Lithium), but according to the two electrode potential data；Li++ e → Li, E=-3.040V；Be++ e → Be, E=-1.847V is obtained electric
Both sub- abilities are compared, and beryllium is easy more than lithium.Actual production result is also fully consistent with electrode potential theory, normal DC voltage
(within 3V) electrolyzing fused state lithium fluoride beryllium, the metal that cathode generates only have beryllium to be precipitated without lithium.
DC voltage is applied to lithium fluoride beryllium electrolyte, if the electrolysate on anode does not select tungsten to do anode
Words are no any objections, entirely fluorine gas (anion of fuse salt lithium fluoride beryllium only has a kind of fluorine).But tungsten is selected
As anode, this has just achieved significance of the invention: tungsten lithium fluoride beryllium molten condition at a temperature of (400~500
DEG C), reactivity increases very much, once the fluorine gas in its Surface Creation is encountered, reaction, generation tungsten hexafluoride rapidly immediately.Institute
Anode electrolysis lithium fluoride beryllium fuse salt is done with tungsten plate, in anode surface, the final product for stablizing output is tungsten hexafluoride gas
Body.
Since melting salt component determines, present invention can assure that eliminating from the root most troublesome miscellaneous in tungsten hexafluoride
Matter carbon tetrafluoride and hydrogen fluoride etc. (it is well known that prepare industrial fluorine gas no matter senior middle school's low temperature electrolytic cell, electrolyte all contains fluorination
Hydrogen ingredient, the anode overwhelming majority used is carbon materials, and in the environment, hydrogen fluoride and carbon tetrafluoride harmful components can not be kept away
Exempt from).
Tungsten plate does anode electrolysis lithium fluoride beryllium fuse salt, can be because of electricity while anode output tungsten hexafluoride
The reasons such as stream transient fluctuation or Faradaic current are excessive lead to carry secretly fuse salt fugitive dust in the tungsten hexafluoride generated (at once
The electrolyte droplet being commonly called as) and it is not in time for the fluorine gas reacted with tungsten on a small quantity.In response to this, the present invention is in fuse salt
A set of gas purification apparatus is devised on cell gas outlet.Set in device sintering alkali metal material fugitive dust filter plate and
Fugitive dust adsorbent, it can be ensured that block electrolyte droplet these solia particles and pass through.Pass through the tungsten microballoon support of heat resisting steel material
The tiny tungsten ball (tungsten bulb diameter preferably 5~10mm) that frame and metal tungsten powder high pressure are pressed into, tungsten hexafluoride are pressed from both sides from electrolytic cell
The a small amount of fluorine gas taken out of, total overall reaction is fallen under the conditions of tiny tungsten ball is large excess of, generates tungsten hexafluoride.Gas passes through later
Tungsten ball is filtered out because reacting issuable powder dust, can finally be obtained by the millipore filter that sponge nickel sinters into
Obtain high-purity tungsten hexafluoride gas.
The invention has the following advantages that
1, the tooling device that electrolyzing fused salt prepares all kinds of important meals is mature and stable, Core equipment electrolytic cell and electrolysis
The auxiliary equipments such as slot heating, sealing, insulation have all formed standard system series, and the device that the present invention designs is not powerful and unconstrained style formula
Fantasy, the not instead of design of laboratory small beaker flask scale have solid reliable industrialization basis.
2, tungsten of the present invention does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device and current existing synthesis work
Skill and equipment are compared, and have breakthrough in synthesis tungsten hexafluoride technique: existing synthesis tungsten hexafluoride technique, in raw material rank
Control of the section to most harmful impurity carbon tetrafluoride, hydrogen fluoride equal size all seems many and diverse incomparable: or before reactions, it will
Rectifying is multiple under Cryogenic Conditions or simply gives up fluorine gas for fluorine gas, then makees fluorization agent (if not with Nitrogen trifluoride is refining to obtain
The impurity such as objectionable impurities carbon tetrafluoride and hydrogen fluoride are controlled in feed stage, then after synthesis tungsten hexafluoride crude product, subsequent fine
Treatment process processed is more troublesome).The method that the present invention selects electrolyzing fused salt synthesizes tungsten hexafluoride, and raw material fluorinated lithium beryllium is not fluorine-containing
Change hydrogen, pollution of the hydrogen fluoride to finished product tungsten hexafluoride, fluorine gas cryogenic rectification or Nitrogen trifluoride have thus been cut off from source
Many and diverse processing such as purification can avoid.
3, the electrolyzing fused salt synthesis high-purity tungsten hexafluoride device important innovations of the present invention also reside in anode electrolytic cell material
It selects；All fluorine cells, either low temperature, medium temperature or high temperature slot are currently known, the anode overwhelming majority selects carbon material
Expect (low temperature, medium temperature flowing current separation amorphous carbon, high temperature flowing current separation graphite), only a few selects metal nickel plate.It is good to be electrolysed flowing current separation carbon materials
It is in durable, at low cost, disadvantage is also apparent；Carbon does anode, the unavoidable oxidation reaction for participating in betatopic, final result
It is exactly in anodic gas, carbon tetrafluoride etc carbon fluoride impurities are difficult to avoid.Just because of this, extremely individual enterprises are free of to produce
The gas of carbon fluoride impurities can select metallic nickel to do anode material.Although metallic nickel, which does anode benefit, obviously (will not generate fluorine carbon
Impurity), but drawback is also very headachy；It, cannot be as carbon tetrafluoride after anode metal nickel betatopic in addition to cost is high
Or tungsten hexafluoride equally generates gaseous compound, can only enter in electrolyte.It is excessive that nickel ion enters electrolyte, can bring electrolysis
A series of problems, such as fluid viscosity rises, current efficiency is low.It selects tungsten to do anode when electrolyzing fused salt of the invention, and passes through
Careful consideration；Even if general fluorine cell anode selects tungsten, anodic gas entrainment hydrogen fluoride also can't resolve
Problem (because the electrolyte of standard configuration centainly contains hydrogen fluoride ingredient).If electrolyzing fused salt is using general graphite anode, certainly
Tungsten hexafluoride can be smoothly produced, is also avoided that hydrogen fluoride ingredient.But it is unavoidable to carry fluorocarbons secretly.Comprehensively consider,
Electrolyzing fused salt selects tungsten to do anode, and the fluorine gas reaction generated at any time with anode surface generates high-purity six of impurity seldom
Tungsten fluoride, and avoid other materials and do many disadvantages brought by anode, really and truly be an innovation.
4, tungsten of the present invention does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride and also has much spy in electrolyte selection
Color；It is thought through, selects lithium fluoride and beryllium fluoride to be formed by lithium fluoride beryllium eutectic and do electrolyte.This kind of eutectic is prominent
Feature is exactly that fusing point is low, and (lower 400 DEG C of normal pressure or more are presented molten state), (such as lithium fluoride fusing point exists other opposite villiaumite fusing points
842 DEG C, potassium fluoride fusing point is at 846 DEG C, and sodium fluoride fusing point is at 995 DEG C, and magnesium fluoride fusing point is at 1270 DEG C, and calcium fluoride melting point is 1478
DEG C etc.).Just because selecting lithium fluoride beryllium eutectic, is possible to realization and is electrolysed in 400~500 DEG C of temperature ranges, no
But energy consumption substantially reduces, it is even more important that device reliability, durability can all greatly improve, and mass production just becomes can
Energy.
5, tungsten of the present invention does the relatively general at present synthesis technology of anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride
Route, equivalents quality are compared, and production cost is very competitive；Because not only output tungsten hexafluoride on anode, but also in yin
On extremely, at the same the very high broken flakey metallic beryllium of generating value (about broken flakey metallic beryllium recycling, refine, on metallurgy
There is special chapter to describe, herein few superfluous words).
Detailed description of the invention
Fig. 1 is that tungsten does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride process units total figure.
Fig. 2 is fusion electrolysis slot trough body structure schematic diagram in process units.
Fig. 3 is purification for gas jar structure schematic diagram in process units.
Fig. 4 is fusion electrolysis slot anode construction schematic diagram in process units
Fig. 5 is fusion electrolysis slot cathode construction schematic diagram in process units
Symbol description
1 fusion electrolysis slot heat resisting steel groove body
2 fusion electrolysis slot light fire brick thermal insulation layers
3 fusion electrolysis slot nickel plate cathodes
4 fusion electrolysis slot tungsten plate anodes
5 fusion electrolysis slot slot cover temperature resistant encapsulation felt pads
6 fusion electrolysis slot heat resisting steel upper covers
7 fusion electrolysis slot integrated sensor temperature resistant encapsulation insulation sleeves
8 fusion electrolysis slot integrated sensors
9 fusion electrolysis slot conductive anode rods
10 conductive anode rod tungsten plate fixed frame temperature resistant encapsulation insulation sleeves
11 purification for gas tank fusion electrolysis slot gas eduction tubes
12 purification for gas tanks are sintered alkali metal material fugitive dust filter plate
13 purification for gas tank tungsten microballoon support brackets
14 purification for gas tanks are sintered sponge nickel material millipore filter
15 purification for gas tank gas vents
16 purification for gas tank tungsten microballoon conversion zones
17 purification for gas tank electrolyte are sintered alkali metal material fugitive dust adsorbent
18 fusion electrolysis slot gas eduction tubes (electrolyte inlets are also served as when feeding intake)
19 fusion electrolysis slot gas eduction tube temperature resistant encapsulation insulation sleeves
20 fusion electrolysis slot cathode conducting rod temperature resistant encapsulation insulation sleeves
21 fusion electrolysis slot cathode conducting rods
22 fusion electrolysis slot medium-frequency electrical heating coils
Broken flakey metallic beryllium is precipitated in 23 fusion electrolysis slot cathodes
24 medium-frequency electrical heating Setup Controllers
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings, but the present invention is not limited to the implementations
Example.
Embodiment:
Tungsten does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride, comprising the following steps:
Selecting DYD-100-0.5 type beryllium electrolytic cell is core equipment prototype (basic parameter: electrolytic cell volume 0.8M3, intermediate frequency
Heating device power 100Kw, 3010 heat-resistance stainless steel of electrolytic cell overall material, slot cover plate thickness 30mm, groove body plate thickness 18mm, groove body
Outer light fire brick insulation thickness 200mm, electrolytic cell normal working temperature: heat-resisting 800 DEG C of short time interval highest, long-term work
Within 600 DEG C, electric tank cathode nickel plate size: 400*300*6*9, anode electrolytic cell tungsten board size: 400*300*20*8).
By components such as tooling requirement cleaning, oil removing, assembling cathode and anode, assembling electrolytic cell, assembling purification for gas tanks, feed intake
Preceding sealing groove vacuumizes pressure testing to electrolysis by gas outlet tube, and light condition opens medium-frequency electrical heating, is tested by integrated sensor
Whether device is normal.
The assembling attention sequence of purification for gas tank, purifying tank upper cover open the assembly since bottommost.Successively are as follows: sintering alkali
Fugitive dust filter plate, the spherical fugitive dust adsorbent of sintering alkali metal material, heat resisting steel material tungsten microballoon support bracket, the tungsten of metal material are micro-
Ball conversion zone, sintering sponge nickel material millipore filter.Finally seal tank body upper cover, by gas eduction tube be added, extract out it is lazy
Property gas test purifying tank vapour lock (normal pressure drop is between 0.01~0.012Mpa).
Molten state lithium fluoride beryllium 600Kg (initial electrolysis matter fluorination is transferred to from cell gas outlet with Special feeding container
Lithium: 2:1's beryllium fluoride feeds intake in molar ratio, maintains the two molar ratio to be no more than 10:1 before being electrolysed terminal), charging finishes gas is pure
Change tank reset to install.
- 0.098Mpa or more is evacuated to electrolytic cell using purification for gas tank conduit, according to integrated sensor data control
Bath temperature processed is between 460~480 DEG C.
It connects external dc and is electrolysed power supply, select constant current transformation mode, operation in first 1 hour rises to 1000A, subsequent electricity from 100A
Time current stabilization is solved in 1100~1200A.
Electrolysis start first hour, in slot gas do not do finished product collect (single slot amount is small, can be vented to eluting column decomposition
After harmful components, exhaust gas emptying up to standard, waste liquid centralized recovery).On-line checking product quality, stabilization reach simultaneously for subsequent stable electrolysis
Tungsten hexafluoride is collected to after requiring (to continue to guide external hexafluoro into from purification for gas tank by tungsten hexafluoride in electrolytic cell
Change tungsten liquefied pot).
During normal electrolysis, since tungsten hexafluoride synthesis is exothermic reaction, so medium-frequency electrical heating device will be according to setting
Bath temperature enter the warm mode of dimension.Meanwhile as tungsten hexafluoride is continuously generated, tungsten plate anode also (presses farad in continuous consumption
Electrolysis law simple computation consumes tungsten anode 11.4Kg it is found that 10000 ampere-hours of every energization, can output tungsten hexafluoride 18.5Kg,
The broken flakey metallic beryllium 1.69Kg of cathode output simultaneously).
In the present embodiment, the total installation of anode tungsten plate is according to pure tungsten density 19.25g/cm3It is calculated as 369.6Kg.Theoretically
When the quality of anode tungsten plate can be with 32 Wan An of continued electrolysis, electrolytic efficiency is taken into account in practice, is generally energized to the 75% of theoretical amount
When 25 Wan An (i.e. turn on angle to) considers replacement anode.
When actual production, it is very simple that electrolytic cell replaces anode；It is whole in the spare good spare anode of electrolytic cell slot cover over-assemble
Body lifting replacement (hang out slot cover between dismantling by rule cleaning after, remove anode residual tungsten plate, the metallurgical unit of profession handed over to re-work
At conjunction scale cun tungsten plate).
In the present embodiment, when being energized to 25 Wan An, adds up to and collect high-purity tungsten hexafluoride 420.8Kg, calculated by theoretical amount, received
Rate is 91%.
In the present embodiment, when being energized to 25 Wan An, bottom of electrolytic tank is total to collect broken flakey metallic beryllium 40.5Kg, according to reason
Stoichiometric calculates, yield 95.7%.
In the present embodiment, when being energized to 25 Wan An, electrolyte lithium fluoride beryllium molar ratio becomes most from the 2:1 at the initial stage of feeding intake
(according to lithium fluoride beryllium eutectic volume property, fusing point rises to 454 DEG C from 400 DEG C to whole 8.9:1, still in the normal setting slot of electrolytic cell
It is very safe under temperature).When being powered up to 25 Wan An, after replacing anode, pulling broken flakey metallic beryllium out, mended by electrolytic cell
Expect program, puts into powdered fluorinated beryllium 219Kg to electrolytic cell, close slot cover, normal heating melts completely to powdered fluorinated beryllium, again
Revert to lithium fluoride with original electrolyte: beryllium fluoride molar ratio is 2:1.
By surveying according to GB/T32386-2015 Electronic Gases tungsten hexafluoride standard, tungsten of the present invention does sun
Device tungsten hexafluoride (the WF produced of extremely electrolyzing fused salt synthesis high-purity tungsten hexafluoride6) purity [(volume fraction/10-2)]≥
99.99；Major impurity hydrogen fluoride (HF) standard limitation [(volume fraction)/10-6] it is 5, measured value is less than 1；Carbon tetrafluoride (CF4)
Standard limitation [(volume fraction)/10-6] it is 0.5, measured value is not detected.Specific aim eliminate the main objectionable impurities of tungsten hexafluoride this
In one key problem, conclusion is very satisfactory.
Claims (27)
1. a kind of tungsten does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device and method, wherein described device includes:
Light fire brick thermal insulation layer (2) are used outside electrolysis rectangle groove body (1) made of heat resisting steel and entire groove body, heat resisting steel slot cover (6)
And integrated sensor (8), the copper conducting rod of anode (9) and the gas outlet tube (18) of configuration, slot cover pass through mica temperature resistant encapsulation
Felt pad is fixed on above electrolytic cell body, and sensor, conducting rod and gas outlet tube pass through temperature resistant encapsulation insulation sleeve respectively
(7), (10) and (19) are fixed in slot cover, and metal tungsten electrode (4) is fixed on by anode electrolytic cell conducting rod tungsten plate fixed frame and is led
Below electric pole, metal nickel plate (3) is connected with electric tank cathode conducting rod (21) rivet clasp, solid by temperature resistant encapsulation insulation sleeve (20)
It is scheduled below fusion electrolysis slot groove body, medium-frequency electrical heating device (22), (24) are used as fusion electrolysis slot heat source, on electrolytic cell
Purification for gas tank (11) are arranged in portion's gas outlet tube (18), purify and are Down-Up set gradually inside tank by being sintered alkali metal material
Matter fugitive dust filter plate (12) and sintering alkali metal material spherical shape fugitive dust adsorbent (17), tungsten microballoon support bracket (13) and tungsten microballoon are anti-
Layer (16), sintering sponge nickel material millipore filter (14) are answered, gas eduction tube (15) are arranged in purification for gas tank highest point.
2. a kind of tungsten according to claim 1 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device, special
Sign is fusion electrolysis slot anode plate material selection tungsten.
3. a kind of tungsten according to claim 2 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device, special
Sign is that metal tungsten electrode is fixed by bolts to below conductive anode rod.
4. a kind of tungsten according to claim 3 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device, special
Sign is that fusion electrolysis slot conductive anode rod selects fine copper material.
5. a kind of metal tungsten electrode according to claim 1 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that metal nickel plate is selected to do fusion electrolysis slot cathode.
6. a kind of metal tungsten electrode according to claim 5 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that metal nickel plate by riveting on cathode conducting rod.
7. a kind of metal tungsten electrode according to claim 6 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that fusion electrolysis slot cathode conducting rod selects heat resisting steel material.
8. a kind of metal tungsten electrode according to claim 1 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that fusion electrolysis slot groove body selects the production of heat resisting steel material.
9. a kind of metal tungsten electrode according to claim 1 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that fusion electrolysis slot groove body insulating layer selects lightweight silicate refractory brick material.
10. a kind of metal tungsten electrode according to claim 1 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that fusion electrolysis slot heat source selects medium-frequency electrical heating device.
11. a kind of metal tungsten electrode according to claim 1 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that purification for gas tank is arranged on fusion electrolysis slot slot cover gas outlet tube.
12. a kind of metal tungsten electrode according to claim 11 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that purification for gas tank selects stainless steel material production (preferably 316L).
13. a kind of metal tungsten electrode according to claim 11 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that integrated gas purifying part is arranged in purification for gas tank.
14. a kind of metal tungsten electrode according to claim 13 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that purification for gas component sequence (Down-Up) fugitive dust filter plate, fugitive dust adsorbent, tungsten microballoon support in purifying tank
Frame, tungsten microballoon conversion zone and millipore filter.
15. a kind of metal tungsten electrode according to claim 14 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device,
It is characterized in that fugitive dust filter plate and fugitive dust adsorbent select sintering alkali metal material in purifying tank in integrated gas purifying part
Matter, tungsten microballoon support bracket select heat resisting steel material, and tungsten microballoon conversion zone selects the compacting of metal tungsten powder high pressure, millipore filter choosing
With sintering sponge nickel material.
16. a kind of metal tungsten electrode does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride device and method, the described method includes:
Apolegamy has the fusion electrolysis slot of frequency heating device, cleans as required, assembles each component such as cathode and anode and purification for gas tank,
Sealing groove before feeding intake vacuumizes pressure testing to electrolysis by gas outlet tube, and light condition opens medium-frequency electrical heating, passes through integrated sensor
Whether test device is normal, is transferred to (the initial electrolysis matter fluorination of molten state lithium fluoride beryllium electrolyte with Special feeding container before production
Lithium: 2:1's beryllium fluoride feeds intake in molar ratio, maintains the two molar ratio to be no more than 10:1 before being electrolysed terminal), charging finishes gas is pure
To change tank to reset, between 0.01~0.012Mpa, electrolytic cell is evacuated to -0.098Mpa or more for purifying tank vapour lock control pressure drop,
According to integrated sensor data control flume preferably between 460~480 DEG C, connects external dc and be electrolysed power supply, select constant current transformation
Mode, from 100A to 1000A, gradient rises electric current for operation in first 1 hour, and subsequent electrolysis time current stabilization is in 1100~1200A, electrolysis
First hour started, gas does not do finished product collection in slot, after gas is vented to eluting column decomposition harmful components, exhaust gas row up to standard
Empty, waste liquid centralized recovery, subsequent stable electrolysis while on-line checking product quality, stably reach and collect tungsten hexafluoride after requiring
Gas (continues to guide external tungsten hexafluoride liquefied pot into from purification for gas tank by tungsten hexafluoride in electrolytic cell).
17. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that selecting lithium fluoride beryllium eutectic as fusion electrolysis slot electrolyte.
18. a kind of metal tungsten electrode according to claim 17 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that selecting lithium fluoride beryllium eutectic, villiaumite molar ratio is initially controlled in lithium fluoride: beryllium fluoride=2:1, electrolysis termination
Keep the two molar ratio without departing from 10:1.
19. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that selecting fusion electrolysis slot operating temperature whole-process control between 400~500 DEG C (preferably 460~480 DEG C).
20. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that electrosynthesis glyoxal tungsten hexafluoride DC power supply selects constant current transformation mode, it is (excellent that Faradaic current controls 1000~1500A
Select 1100~1200A) between.
21. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that it is pure to select the tungsten hexafluoride of fusion electrolysis slot synthesis to pass through the purification for gas tank being arranged on outlet
Change purification.
22. a kind of metal tungsten electrode according to claim 21 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that control purifying tank pressure drop is between 0.01~0.012Mpa when purification for gas tank purifying purification tungsten hexafluoride.
23. a kind of metal tungsten electrode according to claim 21 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that replacing fugitive dust filter plate and millipore filter in purification for gas tank when electrolysis electricity is up to 50 Wan An.
24. a kind of metal tungsten electrode according to claim 21 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that adding spherical fugitive dust adsorbent and tungsten microballoon conversion zone in purification for gas tank when electrolysis electricity is up to 100 Wan An.
25. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that determining replacement metal tungsten electrode time according to electrolysis electricity (preferably tungsten plate loss degree is replaced 75% or so).
26. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that collecting the broken flakey metallic beryllium of fusion electrolysis slot slot bottom when replacement anode electrolytic cell tungsten plate.
27. a kind of metal tungsten electrode according to claim 16 does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride method,
It is characterized in that except electrolyte ingredient for the first time is according to molar ratio lithium fluoride: in addition to beryllium fluoride=2:1, subsequent electrolyte ingredient is
Beryllium fluoride is added, beryllium fluoride additional amount is determined according to electrolysis electricity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910015696.8A CN109652816B (en) | 2019-01-08 | 2019-01-08 | Synthesis of high-purity tungsten hexafluoride by using metal tungsten as anode to electrolyze molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910015696.8A CN109652816B (en) | 2019-01-08 | 2019-01-08 | Synthesis of high-purity tungsten hexafluoride by using metal tungsten as anode to electrolyze molten salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109652816A true CN109652816A (en) | 2019-04-19 |
| CN109652816B CN109652816B (en) | 2021-04-06 |
Family
ID=66119520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910015696.8A Active CN109652816B (en) | 2019-01-08 | 2019-01-08 | Synthesis of high-purity tungsten hexafluoride by using metal tungsten as anode to electrolyze molten salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109652816B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020619A (en) * | 2019-12-31 | 2020-04-17 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for preparing tungsten hexafluoride gas |
| CN116618190A (en) * | 2023-07-21 | 2023-08-22 | 福建德尔科技股份有限公司 | Centrifugal control system and control method for preparing tungsten hexafluoride |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2359221A1 (en) * | 1976-07-23 | 1978-02-17 | Anvar | Titanium mfr. by electrolytic redn. of titanium tri:halide - gives high purity titanium with low iron content |
| US6361679B1 (en) * | 1999-02-10 | 2002-03-26 | Mitsui Chemicals, Inc. | Process for producing high-purity nitrogen trifluoride gas |
| CN101428858A (en) * | 2008-11-07 | 2009-05-13 | 黎明化工研究院 | Method for producing high-purity tungsten hexafluoride with fluidized bed and equipment thereof |
| CN201330282Y (en) * | 2008-12-19 | 2009-10-21 | 四川红华实业有限公司 | Medium-temperature fluorine-making electrolytic cell |
| CN202390544U (en) * | 2011-11-21 | 2012-08-22 | 上海塑泰新材料科技有限公司 | Capacity-expandable fluorine-making electrolytic bath |
| CN105926004A (en) * | 2016-07-07 | 2016-09-07 | 洛阳高昌机电科技有限公司 | Efficient fluorine preparation device |
| CN107459062A (en) * | 2016-06-03 | 2017-12-12 | 和立气体（上海）有限公司 | The production method and process units of a kind of high-purity tungsten hexafluoride |
-
2019
- 2019-01-08 CN CN201910015696.8A patent/CN109652816B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2359221A1 (en) * | 1976-07-23 | 1978-02-17 | Anvar | Titanium mfr. by electrolytic redn. of titanium tri:halide - gives high purity titanium with low iron content |
| US6361679B1 (en) * | 1999-02-10 | 2002-03-26 | Mitsui Chemicals, Inc. | Process for producing high-purity nitrogen trifluoride gas |
| CN101428858A (en) * | 2008-11-07 | 2009-05-13 | 黎明化工研究院 | Method for producing high-purity tungsten hexafluoride with fluidized bed and equipment thereof |
| CN201330282Y (en) * | 2008-12-19 | 2009-10-21 | 四川红华实业有限公司 | Medium-temperature fluorine-making electrolytic cell |
| CN202390544U (en) * | 2011-11-21 | 2012-08-22 | 上海塑泰新材料科技有限公司 | Capacity-expandable fluorine-making electrolytic bath |
| CN107459062A (en) * | 2016-06-03 | 2017-12-12 | 和立气体（上海）有限公司 | The production method and process units of a kind of high-purity tungsten hexafluoride |
| CN105926004A (en) * | 2016-07-07 | 2016-09-07 | 洛阳高昌机电科技有限公司 | Efficient fluorine preparation device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020619A (en) * | 2019-12-31 | 2020-04-17 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for preparing tungsten hexafluoride gas |
| CN111020619B (en) * | 2019-12-31 | 2023-10-17 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for preparing tungsten hexafluoride gas |
| CN116618190A (en) * | 2023-07-21 | 2023-08-22 | 福建德尔科技股份有限公司 | Centrifugal control system and control method for preparing tungsten hexafluoride |
| CN116618190B (en) * | 2023-07-21 | 2023-10-03 | 福建德尔科技股份有限公司 | Centrifugal control system and control method for preparing tungsten hexafluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109652816B (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100415940C (en) | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis | |
| CN112941567B (en) | Electrochemical method and device for high-temperature molten salt electrolysis in humid atmosphere | |
| CN106835203B (en) | A kind of purification device and method of fused salt | |
| JP6839719B2 (en) | Conversion of used uranium oxide fuel to molten salt reactor fuel | |
| CN105088274A (en) | Device for treating and recycling aluminum electrolysis solid waste | |
| CN109652816A (en) | Tungsten does anode electrolysis fuse salt synthesis high-purity tungsten hexafluoride | |
| CN109825854A (en) | A kind of molten-salt electrolysis-high temperature distillation prepares the device and method of high-purity titanium | |
| CN102583422A (en) | Cyclic preparation method for producing titanium boride by taking potassium-based titanium boron villiaumite mixture as intermediate raw material and synchronously producing potassium cryolite | |
| CN110526249A (en) | A kind of reactor assembly producing silane mixture | |
| CN109267100A (en) | A kind of device and method of electrolysis-pure titanium of chlorination-electrolytic preparation | |
| CN104313643A (en) | High-purity antimony producing method by two-section fused salt electrolysis method | |
| JP4462839B2 (en) | Silicon manufacturing apparatus and manufacturing method | |
| CN101967567A (en) | Method for preparing metal vanadium | |
| CN102703929A (en) | Method for preparing Ti-Fe alloy by direct reduction of ilmenite | |
| US3453187A (en) | Apparatus and process for reduction of hydrogen chloride | |
| CN102121123A (en) | Vanadium metal smelting process | |
| CN101759187B (en) | Preparation method and device for solar-grade polycrystalline silicon | |
| CN204959051U (en) | Aluminium electroloysis solid waste material's device is handled and retrieved | |
| JP2011098861A (en) | Method and apparatus for producing solar cell silicon | |
| CN209024654U (en) | A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation | |
| CN101812703B (en) | Method for preparing metallic titanium by electrolyzing sodium titanate-sodium hydroxide melt | |
| CN104611728B (en) | Preparation apparatus of chloride composite electrolyte used for molten salt electrolysis | |
| JP2023517841A (en) | Liquid Anode Based Molten Oxide Electrolysis/Oxygen Production from Electrolysis of Molten Oxide | |
| CN206319069U (en) | A kind of purifier for being used to remove metal impurities in fused salt | |
| CN110144598A (en) | A kind of preparation method and applications of uranium trichloride |
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 |