CN206319068U - A kind of preparation system of molten salt electrolyte - Google Patents

Abstract

The utility model discloses a kind of preparation system of molten salt electrolyte, the preparation system includes reactor, feed conduit, the first conduit, sampler, the first vacuum-pumping tube, the second conduit and heating furnace；Reactor includes lid and housing on first；Lid and housing seal connection on first；The madial wall lower end of housing is fixedly connected abacus；The lower end of first conduit is through covering on first and extend under orifice plate, for by TiCl₄The bottom of reactor is imported with inert gas；Feed conduit, sampler, the first vacuum-pumping tube and the second conduit both pass through on first lid and are connected with institute reactor, reactor are fed respectively, molten salt electrolyte samples, vacuumizes and be filled with inert gas；Heating furnace is used to heat reactor.The utility model can be used for produce low chemical valence titanium ion molten salt electrolyte, with it is simple to operate, can be continuously produced, stable production process, titanium ion are evenly distributed, the features such as electrolyte oxygen content is low pure.

Description

A kind of preparation system of molten salt electrolyte

Technical field

The utility model is related to simulation technical field, more particularly to a kind of preparation system of molten salt electrolyte.

Background technology

In common metal, titanium is one of content most abundant element in the earth's crust, and abundance accounts for the 4th in structural metal, It is only second to aluminium, iron, magnesium.Titanium is a kind of Rare Metals Materials of superior performance, except superior strength/weight ratio, is suitable as Beyond space flight spare part, the purposes of many non-space flight is have now been developed, in people such as oil, the energy, traffic, chemical industry, raw doctors Certain application has also been obtained with field, and its application field is also constantly extending.In recent years, with semiconductor technology, information The fast development of the high-tech areas such as technology, biomaterial, their purity requirements to used titanium also more and more higher, Demand to high purity titanium is also increasing.

The production method of high purity titanium mainly has fused-salt electrolytic refining method, iodide process, electron-beam process.Refined with iodide process When, speed of separating out is slow, and is intermittent operation, therefore productivity ratio is low.Electron-beam process is to general low-melting-point metal impurity Element and nonmetalloid C, N, H can remove, but oxygen and heavy metal must use fused salt electrolysis process or iodine before electronic torch melting Change method is removed.Using fused salt electrolysis process refine titanium not only can effectively remove cause integrated circuit error radioactive element uranium and Thorium, and produce and can be carried out continuously, productivity ratio is high, and the energy of consumption is small, and production cost is low.

Fused-salt electrolytic refining method is to make anode with thick titanium, raw material titanium is dissolved in electrolyte under certain deposition potential, and Titanium is separated out in negative electrode.Impurity in electrolytic process in raw material titanium (anode), the impurity not dissolution higher than titanium of its dissolution current potential and Stay in the anode, stayed in the electrolytic solution after the impurity dissolution lower than titanium of dissolution current potential, what it is so in negative electrode precipitation is just pure titanium, from And reached the purpose of purification.

Fused-salt electrolytic refining prepares high purity titanium technique and typically uses NaCl, KCl, MgCl₂、LiCl、CaCl₂、NaF、LiF、 KF、Na₂TiF₆、K₂TiF₆Make to need in electrolyte, initial electrolysis matter containing appropriate titanium ion Deng halide molten salt system, to avoid Alkali metal is separated out during electrolysis, while avoiding the electrolysate efflorescence caused by titanium ion concentration polarization.Titanium ion in molten salt electrolyte With Ti²⁺、Ti³⁺、Ti⁴⁺Form is present.Higher titanium ion average valence can cause current efficiency to reduce, while can also be notable Reduce electrolytic titanium crystal size.Electrolytic titanium particle is smaller, and surface area is bigger, with high surfaces activity, easily in follow-up acidleach It is oxidized in processing procedure, causes electrolytic titanium oxygen content to raise.Therefore, titanium ion average valence is reduced, is conducive to being caused Close, bulky grain titanium crystal and higher current efficiency.

Utility model content

In view of above-mentioned analysis, the purpose of this utility model is to provide a kind of preparation system of molten salt electrolyte, this is System can be used for the titanium ion molten salt electrolyte for preparing titanium ion average valence ＜ 2.2.

In order to achieve the above object, the utility model adopts the following technical scheme that realization：

A kind of preparation system of molten salt electrolyte, the preparation system includes reactor 23, feed conduit 8, the first conduit 9th, sampler 11, the first vacuum-pumping tube 12, the second conduit 13 and heating furnace 22；

The reactor 23 includes lid 15 and housing 17 on first；Lid 15 and housing 17 are tightly connected on described first；Institute The madial wall lower end for stating housing 17 is fixedly connected abacus 20；

The lower end of first conduit 9 is through lid 15 on described first and extends under the orifice plate 20, for by TiCl₄ The bottom of the reactor 23 is imported with inert gas；

The feed conduit 8, sampler 11, the first vacuum-pumping tube 12 and the second conduit 13 both pass through lid 1 on described first It is connected, the reactor 23 is fed respectively, molten salt electrolyte samples, vacuumizes and be filled with the reactor 23 Inert gas；

The heating furnace 22 is used to heat the reactor 23.

Further, the preparation system also includes the first vacuum meter 14 and salt discharge pipeline 16；

First vacuum meter 14 is connected with lid 15 on described first, for measuring the pressure in the reactor 23 Power；

The lower end of the salt discharge pipeline 16 is through lid 15 on described first and extends under the orifice plate 20, for from described Export molten salt electrolyte 18 in reactor 23.

Further, the preparation system also includes lid 4 in feed supplement storehouse 6 and second；

Lid 4 is tightly connected with the feed supplement storehouse 6 on described second；The feed supplement storehouse 6 by the feed conduit 8 with it is described The connection connection of reactor 23.

Further, it is tightly connected between the feed supplement storehouse 6 and feed conduit 8 by push-pull valve 7, formation 2 is relatively only Vertical confined space.

Further, the second vacuum-pumping tube 2 and the 3rd conduit 3 are provided with lid 4 on described second；

Second vacuum-pumping tube 2 is used to vacuumize the feed supplement storehouse 6；3rd conduit 3 is used for inert gas It is filled into the feed supplement storehouse 6.

Further, the second vacuum meter 1 is additionally provided with lid 4 on described second, for measuring the pressure in the feed supplement storehouse 6 Power.

Further, the lower end of first conduit 9 is connected with jet pipe 21.

Further, the material of the orifice plate 20 is nickel, and aperture is 1~10mm.

The utility model beneficial effect：

1st, the utility model uses the first conduit and sampler, realizes Gas Stirring and titanium ion concentration analysis, so that It ensure that titanium ion is evenly distributed, it is therefore prevented that titanium ion concentration skewness in electrolytic process and the concentration polarization technology that causes are asked Topic, it is to avoid sampling titanium ion concentration analysis result has a relatively large deviation, thus available for producing low chemical valence titanium ion fused salt Electrolyte.

2nd, the utility model is using the reactor and feed supplement storehouse sealed, and the vacuum dehydration and titanium sponge for realizing halide salt are washed Gas, effectively removes the vapor and air of halide salt and titanium sponge absorption, reduces the oxygen content in molten salt electrolyte.

3rd, the utility model realizes whole closed state in electrolyte preparation process, thus prevented electrolyte by The possibility polluted to outside air.

4th, the utility model have it is simple to operate, can be continuously produced, stable production process, titanium ion are evenly distributed, electricity Solve the low feature of matter oxygen content.

Brief description of the drawings

Accompanying drawing is only used for showing the purpose of specific embodiment, and is not considered as to limitation of the present utility model, whole In accompanying drawing, identical reference symbol represents identical part.

Fig. 1 is the preparation system structural representation of molten salt electrolyte of the present utility model；

In figure：The vacuum meters of 1- second；The vacuum-pumping tubes of 2- second；The conduits of 3- the 3rd；Covered on 4- second；5- arched bolts；6- Feed supplement storehouse；7- push-pull valves；8- feed conduits；The conduits of 9- first；10- fused salt conduits；11- samplers；The vacuum-pumping tubes of 12- first； The conduits of 13- second；The vacuum meters of 14- first；Covered on 15- first；16- salt discharge pipelines；17- housings；18- molten salt electrolytes；19- seas Continuous titanium；20- orifice plates；21- jet pipes；22- heating furnaces；23- reactors.

Embodiment

Preferred embodiment of the present utility model is specifically described below in conjunction with the accompanying drawings, wherein, accompanying drawing constitutes the application one Point, and for explaining principle of the present utility model together with embodiment of the present utility model.

As shown in figure 1, this gives a kind of preparation system of molten salt electrolyte, the preparation system includes anti- Answer device 23, the first vacuum meter 14, feed conduit 8, the first conduit 9, sampler 11, the first vacuum-pumping tube 12, the second conduit 13, row Salt pipeline 16 and heating furnace 22, with reference to Fig. 1.

The reactor 23 of the present embodiment includes lid 15 and housing 17 on first.Lid 15 and the equal band of the upper flange of housing 17 on first There are lid 15 and the upper flange of housing 17 on cooling jacket, and first to be tightly connected, the vacuum dehydration of halide salt can be achieved.Housing 17 The lower end of madial wall is fixedly connected abacus 20.The material of the orifice plate 20 is nickel, and aperture typically takes 1~10mm, preferably 5mm, Both it can prevent that titanium sponge from leaking, and while being conducive to the inert gas that the first conduit 9 is filled with, realize and halide salt is entered by bubble Row stirring.The lower end of first conduit 9 and salt discharge pipeline 16 both passes through on first lid 15 and extended under orifice plate 20, and lower end is connected with Jet pipe 21 with nozzle.Feed conduit 8, sampler 11, the first vacuum-pumping tube 12, the second conduit 13 and the first vacuum meter 14 are all provided with Put on first on lid 15.

The feed conduit 8 of the present embodiment is used to salt and titanium sponge being added in reactor 23.First conduit 9 is used for will TiCl₄Imported with inert gas in reactor 23, realize fully reaction and Gas Stirring.Sampler 11 is used for molten salt electrolyte It is sampled.First vacuum-pumping tube 12 is used to vacuumize reactor 23.Second conduit 13 is used to inert gas being filled with reaction In device 23.First vacuum meter 14 is used to measure the pressure in the reactor 23.Salt discharge pipeline 16 is used for molten salt electrolyte 18 Exported in from reactor 23.

The heating furnace 22 of the present embodiment typically selects Resistant heating stove, for being heated to reactor 23.

In order to effectively remove the oxygen content in the vapor and air in halide salt and titanium sponge, reduction electrolyte.This reality Apply example and feed supplement and gas washing are carried out using the feed supplement storehouse 6 of sealing state, concrete structure includes lid 4 in feed supplement storehouse 6 and second.On second Lid 4 is tightly connected with feed supplement storehouse 6, is provided with the second vacuum meter 1, the second vacuum-pumping tube 2 and the 3rd conduit 3 on second on lid 4.Mend Feed bin 6 is connected by feed conduit 8 with reactor 23.Sealed and connected by push-pull valve 7 between feed supplement storehouse 6 and feed conduit 8 Connect, form 2 relatively independent sealing spaces, it is ensured that carry out titanium sponge gas washing and feed supplement in the closed state, it is therefore prevented that wash Titanium sponge after gas is polluted by outside air.The high-purity argon gas of preferred purity >=99.999% of inert gas in the present embodiment.

Second vacuum meter 1 of the present embodiment is used to measure the pressure in feed supplement storehouse 6, and the second vacuum-pumping tube 2 is used for feed supplement Storehouse 6 is vacuumized, and the 3rd conduit 3 is used to inert gas being filled into feed supplement storehouse 6.

The specific operation process of the present embodiment is as follows：

(1) feed

Lid 15 on first is opened, lid 15 on first is covered after powdered halide salt is imported in reactor 23, then uses Arched bolt compresses sealing, finally closes all valves.Powdered halide salt in the present embodiment is NaCl, KCl, LiCl, MgCl₂And CaCl₂In one or more.

(2) vacuum dehydration of halide salt

Vacuumized after the valve for first opening the first vacuum-pumping tube 12 so that absolute pressure≤100Pa in reactor 23；Again Start heating furnace 22 (such as Resistant heating stove), be warming up to 450~550 DEG C with 3~5 DEG C/min speed, and be incubated 40~55 Hour, maintenance reaction device inner vacuum state, absolute pressure≤100Pa in temperature-rise period.

(3) addition of titanium sponge and gas washing：

Gas washing after lid 4 is sealed on second is compressed using arched bolt 5, the detailed process of gas washing is：

Feed supplement storehouse 6 and reactor 23 are vacuumized simultaneously respectively by the second vacuum-pumping tube 2 and the first vacuum-pumping tube 12, absolutely Pressure is respectively less than and is equal to 100Pa, is maintained 20~40 minutes, the gas adsorbed in titanium sponge is fully removed；

By the 3rd conduit 3 and the second conduit 13 respectively to feed supplement storehouse 6 and the applying argon gas of reactor 23；

Circulate 2 times and vacuumize applying argon gas operation, complete to make to be full of argon gas in feed supplement storehouse 6 and reactor 23 after gas washing, and tie up Hold pressure-fired (400~600Pa of superatmospheric).

By the vacuum dehydration of halide salt and titanium sponge and gas washing, can be effectively except desalting and the vapor in titanium sponge And air, so as to reduce the oxygen content in electrolyte.

(4) blanking

Slow to open push-pull valve 7, sea is treated in the halide salt upper surface for making titanium sponge be fallen into along feed conduit 8 in reactor 23 Continuous titanium fully enters closing push-pull valve 7 after reactor 23.

Push-pull valve 7 can make feed supplement storehouse 6 and the 2 relatively independent confined spaces of formation of reactor 23, to ensure in charging During do not receive outside air pollution.

(5) molten electrolyte

Open the valve of the second conduit 13, supplement argon gas, until the pressure in reactor 23 for malleation (1500~ 2000Pa), then heating to 700~900 DEG C, (temperature can determine according to electrolyte fusing point, generally greater than electrolyte fusing point 100 DEG C), it is incubated 1~3 hour so that halide salt is able to fully melt-blended.

After being melted due to titanium sponge density higher than the halide salt in fused salt, thus reactor 23, titanium sponge will fall into reaction On the orifice plate 20 of the bottom of device 23.

(6) vacuumize

Open the valve of the first vacuum-pumping tube 12, vacuumized, until the vacuum in reactor 23 for 0.015~ 0.025MPa, closes the valve.

(7) TiCl is led to₄Carry out chlorination reaction

The valve of the first conduit 9 is opened, passes through the aperture regulation TiCl of control valve₄Flow.Its reaction is as follows：

3TiCl₄+ Ti=4TiCl₃； (1)

TiCl₄+ Ti=2TiCl₂； (2)

In electrolyte system, based on chemical reaction (2), titanium ion average valence 2.1~2.2.

In order to both can guarantee that higher reaction speed, TiCl can be made again₄Fully absorbed.TiCl in the present embodiment₄It is filled with Speed is：Per 100kg salt, every TiCl for being passed through 15~30kg for 1 hour₄, preferably 25kg.

(8) Gas Stirring

Work as TiCl₄When intake reaches aim parameter, high-purity argon gas (purity >=99.999%) is passed through along the first conduit 9, according to Fused salt is stirred by bubble, the internal pressure of reactor 23 closes valve when returning to atmospheric pressure, stops ventilation.

In order to ensure that titanium ion is evenly distributed, the concentration polarization caused by titanium ion concentration skewness when preventing from being electrolysed, together When preventing sampling analysis, in sample there is relatively large deviation in titanium ion concentration with titanium ion concentration in electrolyte body.This implementation Example is stirred using gas, and the process of implementing is：Work as TiCl₄When intake reaches aim parameter, height is passed through along the first conduit 9 Pure argon (purity >=99.999%), is stirred by bubble to fused salt, until the pressure in reactor 23 returns to air Valve is closed during pressure, stops ventilation.

(9) sampling analysis

Work as TiCl₄After being reacted 30~60 minutes with titanium sponge, decentralization sampler 11 is sampled analysis.

TiCl in this step₄It it is preferably 50 minutes with the titanium sponge reaction time.

Because the charge and reacting dose of titanium tetrachloride can not be extremely precisely controlled, titanium ion concentration control it is possible that Deviation, in order to ensure to obtain low chemical valence titanium ion molten salt electrolyte, the present embodiment passes through to the titanium ion in molten salt electrolyte Concentration is sampled analysis to realize.Detailed process is：

Titanium ion concentration in sampling analysis molten salt electrolyte；

When titanium ion concentration is equal to titanium ion concentration threshold value, low chemical valence titanium ion molten salt electrolyte is obtained；When fused salt electricity When solving the titanium ion concentration in matter less than titanium ion concentration threshold value, then supplement adds TiCl₄, until titanium ion concentration be equal to titanium from Untill sub- concentration threshold, so as to improve the titanium ion concentration in molten salt electrolyte；When the titanium ion concentration in molten salt electrolyte Higher than titanium ion concentration threshold value, then supplement and add halide salt, untill titanium ion concentration is equal to titanium ion concentration threshold value, so that Reduce the titanium ion concentration in molten salt electrolyte, it is to avoid the generation of the titanium ion of high chemical valence.This ensure that fused salt is electric Titanium ion concentration in solution matter can maintain zone of reasonableness (i.e. titanium ion concentration threshold value).The titanium ion concentration of the present embodiment is two Valency titanium ion concentration and trivalent titanium ion concentration sum.

Titanium ion chemical valence has the elevated trend with titanium ion concentration rise, therefore titanium ion concentration can not be too high, together When ensure divalence titanium ion mass transfer speed in electrolytic process again, titanium ion concentration can not be too low.Melted in the present embodiment Titanium ion concentration threshold value in salt electrolyte is generally 3~6wt%, preferably 4wt% and 5wt%, can so obtain relatively low Chemical valence titanium ion, is conducive to obtaining the fine and close titanium crystal of bulky grain in electrorefining processes, obtains higher current efficiency.

(10) electrolyte is discharged

The valve of the second conduit 13 is opened, applying argon gas are carried out, it is 0.06~0.08MPa, the row of opening to keep reactor malleation Salt pipeline 16,, can be by the low chemical valence titanium ion fused salt prepared electricity by the malleation in reactor 23 by fused salt conduit 10 Solution matter, which is discharged in inert gas environment electrolytic cell, to be carried out electrolysis operation or is discharged in inert gas environment holding vessel to store.

The present embodiment can be used for produce low chemical valence titanium ion molten salt electrolyte, with it is simple to operate, can be continuously produced, Stable production process, titanium ion are evenly distributed, the features such as electrolyte oxygen content is low pure；It can effectively remove and desalt and titanium sponge suction Attached vapor and air, makes the oxygen content in electrolyte be in extremely low level；It can ensure in electrolyte preparation process, it is whole It is closed, so as to prevent the possibility that electrolyte is polluted by outside air.

The above, only the utility model preferably embodiment, but protection domain of the present utility model is not This is confined to, any one skilled in the art can readily occur in the technical scope that the utility model is disclosed Change or replacement, should all cover within protection domain of the present utility model.

Claims (10)

1. a kind of preparation system of molten salt electrolyte, it is characterised in that the preparation system includes reactor (23), feed conduit (8), the first conduit (9), sampler (11), the first vacuum-pumping tube (12), the second conduit (13) and heating furnace (22)；

The reactor (23) includes lid (15) and housing (17) on first；(15) are covered on described first and housing (17) sealing connects Connect；The madial wall lower end of the housing (17) is fixedly connected abacus (20)；

The lower end of first conduit (9) is through lid (15) on described first and extends under the orifice plate (20), for inciting somebody to action TiCl₄The bottom of the reactor (23) is imported with inert gas；

The feed conduit (8), sampler (11), the first vacuum-pumping tube (12) and the second conduit (13) are both passed through on described first Lid (15) is connected with the reactor (23), the reactor (23) is fed respectively, molten salt electrolyte is sampled, taken out Vacuum and it is filled with inert gas；

The heating furnace (22) is used to heat the reactor (23).

2. preparation system according to claim 1, it is characterised in that the preparation system also includes the first vacuum meter (14) With salt discharge pipeline (16)；

First vacuum meter (14) is connected with covering (15) on described first, for measuring the pressure in the reactor (23) Power；

The lower end of the salt discharge pipeline (16) is through lid (15) on described first and extends under the orifice plate (20), for from institute State export molten salt electrolyte (18) in reactor (23).

3. preparation system according to claim 1 or 2, it is characterised in that the preparation system also include feed supplement storehouse (6) and (4) are covered on second；

(4) are covered on described second to be tightly connected with the feed supplement storehouse (6)；The feed supplement storehouse (6) by the feed conduit (8) with Reactor (23) the connection connection.

4. preparation system according to claim 3, it is characterised in that lead between the feed supplement storehouse (6) and feed conduit (8) Cross push-pull valve (7) to be tightly connected, form 2 relatively independent sealing spaces.

5. preparation system according to claim 4, it is characterised in that be provided with second on described second on lid (4) and take out true Blank pipe (2) and the 3rd conduit (3)；

Second vacuum-pumping tube (2) is used to vacuumize the feed supplement storehouse (6)；3rd conduit (3) is used for indifferent gas Body is filled into the feed supplement storehouse (6).

6. preparation system according to claim 5, it is characterised in that be additionally provided with second on lid (4) on described second true Empty table (1), for measuring the pressure in the feed supplement storehouse (6).

7. preparation system according to claim 3, it is characterised in that be additionally provided with second on lid (4) on described second true Empty table (1), for measuring the pressure in the feed supplement storehouse (6).

8. preparation system according to claim 3, it is characterised in that the lower end of first conduit (9) is connected with jet pipe (21)。

9. the preparation system according to claim 1 or 2 or 4 or 5 or 6 or 7, it is characterised in that first conduit (9) Lower end is connected with jet pipe (21).

10. preparation system according to claim 1 or 2, it is characterised in that the material of the orifice plate (20) is nickel, aperture For 1~10mm.