CN104947135B - A kind of device for preparing gas of nitrogen trifluoride and application - Google Patents
A kind of device for preparing gas of nitrogen trifluoride and application Download PDFInfo
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- CN104947135B CN104947135B CN201510311558.6A CN201510311558A CN104947135B CN 104947135 B CN104947135 B CN 104947135B CN 201510311558 A CN201510311558 A CN 201510311558A CN 104947135 B CN104947135 B CN 104947135B
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Abstract
The present invention relates to a kind of device for preparing gas of nitrogen trifluoride and application, belong to Nitrogen trifluoride preparation field.Described device China electrolyte synthesis system includes NH3Storage tank, HF storage tanks, NH3Storage tank vaporizer, HF storage tanks vaporizer, NH3Storage tank automatic valve, HF storage tanks automatic valve, NH3Storage tank flowmeter, HF storage tanks flowmeter and reactor；Electrolyte storage system includes stock chest, automatic valve A, B, stock chest liquid level gauge and flowmeter；Electrolysis system includes electrolytic cell and electrolytic cell liquid level gauge；Sweeping nitrogen system includes N2Tank, N2Pressure tank table, N2Tank automatic valve A and B；Automation control system passes through signal remote control.The application includes electrolyte and synthesizes and lay in N F3, and NF3It is electrolysed and adds.Described device can realize that automatic electrolyte continuous electrolysis of adding prepares NF3Gas, lifts the electrolytic efficiency of electrolytic cell, reduces artificial high temperature harmful work.
Description
Technical field
The present invention relates to a kind of device for preparing gas of nitrogen trifluoride and application, specifically, it is related to a kind of suitable for electricity
Solution prepares the automation equipment and its application process of gas of nitrogen trifluoride, belongs to Nitrogen trifluoride preparation field.
Background technology
With the fast development of electronics industry, Nitrogen trifluoride (Nitrogen Trifluoride, abbreviation NF3) gas is in electricity
Sub- industry has very extensive and important application.In the prior art, NF is prepared3The main method of gas is fusion electrolysis method, sun
Extremely nickel or carbon plate, negative electrode are nickel, carbon plate or iron, and electrolyte is NH4FxHF fuse salts, electrolysis temperature is 90 DEG C~140 DEG C,
Anode produces NF3, negative electrode generation H2.In the prior art, the NH4FxHF fuse salts mainly have two kinds of preparation methods：One is to use
NH4FHF and HF example 2 in molar ratio:1~1:1 is mixed with and obtains NH4FxHF electrolyte, x=1~2；Another is to use
HF and NH3In N2Example 3 in molar ratio in environment:1~2:1 hybrid reaction generates NH4FxHF electrolyte；At present.Industrialized production
NF3Electrolytic cell be skirtboard formula electrolytic cell.
In actual production, first, the NH as electrolyte4FxHF fuse salts are manually operation synthesis；Secondth,
In NF3, it is necessary to which adding the electrolyte keeps electrolyte liquid level in electrolytic process；3rd, the NH of synthesis4FxHF fuse salts are all
Containing minor amount of water, the presence of water can cause electrolysis abnormal, the quick-fried sound of such as electrolytic cell and N2O content increase, therefore, is carrying out NF3Electrolysis
Before also need to electrolysis water removal.Three kinds of situations described above require existing electrolytic preparation NF3Exist in the process of gas artificial synthesized
Electrolyte process, it is artificial add electrolyte process and water removal process, and in electrolytic preparation NF3In the electrolysing period of gas, need
Frequently carry out manually adding electrolyte process and water removal process.This can have problems with：(1) synthesize and add electrolyte process
Belong to high temperature harmful work, for a long time artificial operation influence enterprise employee health；(2) adding electrolyte process needs electrolytic cell shutdown side
Without NF during energy operation, water removal process3Gas is produced, electrolytic efficiency reduction.
The content of the invention
The defect existed for prior art, an object of the present invention is to provide a kind of gas of nitrogen trifluoride of preparing
Device, described device is automation equipment, and automatic electrolyte continuous electrolysis of adding can be achieved and prepares NF3Gas, lifts electrolytic cell
Electrolytic efficiency, reduce artificial high temperature harmful work.
The second object of the present invention is to provide a kind of application for the device for preparing gas of nitrogen trifluoride.
To realize the purpose of the present invention, there is provided following technical scheme.
A kind of device for preparing gas of nitrogen trifluoride, described device is mainly by electrolyte synthesis system, electrolyte storage system
System, electrolysis system, sweep nitrogen system and automation control system composition.
Wherein, electrolyte synthesis system mainly includes NH3Storage tank, HF storage tanks, NH3Storage tank vaporizer, HF storage tanks vaporizer,
NH3Storage tank automatic valve, HF storage tanks automatic valve, NH3Storage tank flowmeter, HF storage tanks flowmeter and reactor.
Electrolyte storage system mainly includes stock chest, automatic valve A, automatic valve B, stock chest liquid level gauge and flow
Meter.
Electrolysis system mainly includes electrolytic cell and electrolytic cell liquid level gauge.
Sweeping nitrogen system mainly includes N2Tank, N2Pressure tank table, N2Tank automatic valve A and N2Tank automatic valve B；
Annexation between system above and its part is as follows：NH3Storage tank, NH3Storage tank vaporizer, NH3Storage
Tank automatic valve and NH3Storage tank flowmeter passes sequentially through pipeline and is connected with reactor；HF storage tanks, HF storage tanks vaporizer, HF storage tanks
Automatic valve and HF storage tank flowmeters pass sequentially through pipeline and are connected with reactor.Stock chest is connected with reactor by pipeline, pipe
Road is provided with automatic valve A, and stock chest is connected with electrolytic cell by pipeline, and pipeline is provided with automatic valve B, automatic valve B and
Pipeline between electrolytic cell is provided with flowmeter, and stock chest liquid level gauge is connected with stock chest by pipeline.Electrolytic cell and electrolytic cell
Liquid level gauge is connected by pipeline.N2Tank and N2After pressure tank table is connected by pipeline, it is divided on two branch roads, a branch road and passes through
Pipeline and N2Tank automatic valve A and reactor are sequentially connected, and another branch road passes through pipeline and N2Tank automatic valve B and stock chest
It is sequentially connected.
Wherein, NH3Storage tank is used to store reaction raw materials NH3, NH3Storage tank vaporizer is used for raw material NH3Be converted to gaseous state,
NH3Storage tank automatic valve is used to control gaseous state NH3Enter reactor, NH into reactor or stopping3Storage tank flowmeter is used to adjust
Measure NH3Flow, HF storage tanks be used for store reaction raw materials HF, HF storage tank vaporizer be used for raw material HF is converted into gaseous state, HF
Storage tank automatic valve is used to control gaseous state HF to enter reactor or stop entering reactor, and HF storage tanks flowmeter, which is used to adjust, to be measured
HF flow, reactor is used as NH3The reaction vessel of gas and HF gas, NH3Gas and HF gas generate NH in a kettle.4FxHF electricity
Solve liquid.
Stock chest is used to store NH4FxHF electrolyte, automatic valve A is used to control the electrolyte from reactor to enter
Stock chest or stopping enter stock chest, automatic valve B be used to controlling the electrolyte from stock chest enter electrolytic cell or stop into
Enter electrolytic cell, flowmeter is used for the flow for measuring the electrolyte, and stock chest liquid level gauge is used to detect to be electrolysed described in stock chest
The level condition of liquid.
Electrolytic cell, for electrolytic preparation NF3Gas, electrolytic cell liquid level gauge is used for the liquid for detecting electrolyte described in electrolytic cell
Position situation.
N2Tank is used to store N2Gas, N2Pressure tank table is used to adjust N2Atmospheric pressure, by N2Air pressure, which enters reactor, makes institute therein
State electrolyte and enter stock chest, or by N2Air pressure, which enters stock chest, makes the electrolyte therein enter electrolytic cell, N2Tank automatic valve
A is used to control N2Gas is from N2Tank enters reactor or stops entering reactor, N2Tank automatic valve B is used to control N2Gas is from N2Tank enters
Enter stock chest or stop entering stock chest.
Automation control system is by signal respectively to NH3Storage tank automatic valve, HF storage tanks automatic valve, N2Tank automatic valve
Door A, N2Tank automatic valve B, automatic valve A, automatic valve B, NH3Storage tank flowmeter, HF storage tanks flowmeter, flowmeter, stock chest
Liquid level gauge, electrolytic cell liquid level gauge and N2The carry out remote control of pressure tank table.
A kind of application of the device of the present invention for preparing gas of nitrogen trifluoride, the applying step is as follows：
(1) electrolyte synthesis and deposit
Signal control NH is sent by automation control system3Storage tank automatic valve and HF storage tanks automatic valve are opened, reaction
Raw material NH3With HF respectively from NH3Storage tank and HF storage tanks enter reactor, NH3Storage tank flowmeter and HF storage tank flowmeters are adjusted respectively
NH3With HF flow, make HF and NH3Mol ratio be 2:1~3:1；Work as NH3Storage tank flowmeter and HF storage tank flowmeters are examined respectively
Measure NH3When reaching the capacity of reactor with HF integrated fluxs, automation control system is signaled to, is received after signal, from
Dynamic networked control systems send signal control NH3Storage tank automatic valve and HF storage tanks automatic valve are closed, NH3Stop entering anti-with HF
Answer kettle；NH in a kettle.3Gas and HF solid/liquid/gas reactions generation electrolyte；
After reaction terminates, automation control system sends signal control N2Tank automatic valve A and automatic valve A is opened, control
N processed2Pressure tank table adjusts N2Pressure, by by N2Press-in reactor makes the electrolyte in reactor enter stock chest, works as stock chest
When liquid level gauge shows that numerical value reaches the storage cap of stock chest, signal is sent to automation control system, is received after signal, automatically
Networked control systems send signal control N2Tank automatic valve A and automatic valve A is closed, N2Stopping enters reactor, and electrolyte stops
Into stock chest.
(2)NF3It is electrolysed and adds
Automation control system sends signal control N2Tank automatic valve B and automatic valve B is opened, and controls N2Pressure tank table
Adjust N2Pressure, by N2Press-in stock chest makes the electrolyte in stock chest enter in electrolytic cell, when electrolytic cell liquid level gauge shows numerical value
When reaching the liquid level upper limit of electrolytic cell, signal is sent to automation control system, is received after signal, automation control system is sent
Signal controls N2Tank automatic valve B and automatic valve B is closed, and cell reaction produces NF to electrolyte in a cell3Gas.
Electrolysis production NF3During gas, it is by electrolyte consumes the electrolyte method of adding carried out：1) electrolyte is worked as
When liquid level gauge shows that numerical value reaches the liquid level lower limit of electrolytic cell, signal is sent to automation control system, is received after signal, automatically
Networked control systems send signal control N2Tank automatic valve B and automatic valve B is opened, and controls N2Pressure tank table adjusts N2Pressure, will
N2The addition speed that stock chest controls electrolyte is pressed into, electrolyte electrolytic cell is pressed into from stock chest, flowmeter, which is shown, adds speed
Rate；2) when electrolytic cell liquid level gauge shows that numerical value reaches the liquid level upper limit of electrolytic cell, signal is sent to automation control system, is received
To after signal, automation control system sends signal control N2Tank movable valve B and automatic valve B is closed, and stops adding to electrolytic cell
Enter the electrolyte；3) when stock chest liquid level gauge does not show that numerical value reaches the liquid level lower limit of stock chest, repeat step 1) and 2)
Add electrolyte；When stock chest liquid level gauge shows that numerical value reaches the storage lower limit of stock chest, sent to automation control system
Signal, is received after signal, and automation control system sends signal control NH3Storage tank automatic valve and HF storage tank automatic valves are beaten
Open, the synthesis of repeat step (1) electrolyte and deposit process.
The raw material NH3Middle NH3Weight/mass percentage composition >=99.8%, weight/mass percentage composition≤0.008% of water, preferably
≤ 0.005%；HF weight/mass percentage composition >=99.9% in raw material HF, weight/mass percentage composition≤0.008% of water, preferably≤
0.005%.
The electrolyte is NH4FxHF fuse salts, HF and NH4F molar ratios x is 1~2；
Electrolyte adds speed for 10kg/1000Ah~100kg/1000Ah, and preferably 14kg/1000Ah~
50kg/1000Ah, add speed it is too small that liquid level can be caused to go up is not enough, be finally stopped NF3Electrolysis；Add that speed is too fast to be led
Cause problems with：1) electrolytic slag of bottom of electrolytic tank can be whipped into electrolytic cell, cause Faradaic current to decline；2) part H is had2
Anode region is brought into from the cathodic region of electrolytic cell, causes electrolytic cell to there is the potential danger of quick-fried sound.
Faradaic current is 50mAcm-2~150mAcm-2, decomposition voltage be 5.5V~8V, electrolysis temperature be 80 DEG C~
140℃。
The existing fusion electrolysis method of electrolytic cell prepares NF3Skirtboard formula electrolytic cell used in gas, anode is nickel or carbon plate, the moon
Extremely nickel, carbon plate or iron, the electrolytic cell can be using carbon steel, stainless steel, nickel, nickel alloy, fluorine resin or the processing of Fluorine-lined material
Form, range can be between 500A~10000A.
Beneficial effect
1. the invention provides a kind of device for preparing gas of nitrogen trifluoride, described device using automation control system and
Automated system equipment can realize the automation of electrolyte synthetic job and add operation automation, so that it is poisonous to reduce artificial high temperature
Operation；
2. the invention provides a kind of application for the device for preparing gas of nitrogen trifluoride, by controlling raw material HF and NH3In
Water content, be prepared into non-aqueous eletrolyte, can use tranquil machine operation and water removal operation, and electrolysis operation in directly add to electricity
Groove is solved, continuous electrolysis is realized, the electrolytic efficiency of electrolytic cell is lifted.
Brief description of the drawings
Fig. 1 is a kind of apparatus structure schematic diagram for preparing gas of nitrogen trifluoride in embodiment.
Wherein：1—NH3Storage tank, 2-HF storage tanks, 3-NH3Storage tank vaporizer, 4-HF storage tank vaporizers, 5-NH3Storage tank
Automatic valve, 6-HF storage tank automatic valves, 7-NH3Storage tank flowmeter, 8-HF storage tank flowmeters, 9-N2Tank, 10-N2Tank pressure
Power table, 11-automation control system, 12-N2Tank automatic valve A, 13-N2Tank automatic valve B, 14-automatic valve A, 15-
Reactor, 16-stock chest, 17-stock chest liquid level gauge, 18-automatic valve B, 19-flowmeter, 20-electrolytic cell, 21-electricity
Solve groove liquid level gauge
Embodiment
1 the present invention is described in detail below in conjunction with the accompanying drawings.
A kind of device for preparing gas of nitrogen trifluoride used is as follows in comparative example 2,3 and embodiment 1~3：
Described device it is main by electrolyte synthesis system, electrolyte storage system, electrolysis system, sweep nitrogen system and automation
Control system 11 is constituted.
Wherein, electrolyte synthesis system mainly includes NH3Storage tank 1, HF storage tanks 2, NH3Storage tank vaporizer 3, the vaporization of HF storage tanks
Device 4, NH3Storage tank automatic valve 5, HF storage tanks automatic valve 6, NH3Storage tank flowmeter 7, HF storage tanks flowmeter 8 and reactor 15.
Electrolyte storage system mainly includes stock chest 16, automatic valve A 14, automatic valve B 18, stock chest liquid level gauge
17 and flowmeter 19.
Electrolysis system mainly includes electrolytic cell 20 and electrolytic cell liquid level gauge 21.
Sweeping nitrogen system mainly includes N2Tank 9, N2Pressure tank table 10, N2Tank automatic valve A 12 and N2Tank automatic valve B 13.
Annexation between system above and its part is as follows：NH3Storage tank 1, NH3Storage tank vaporizer 3, NH3
Storage tank automatic valve 5 and NH3Storage tank flowmeter 7 passes sequentially through pipeline and is connected with reactor 15；HF storage tanks 2, HF storage tank vaporizers
4th, HF storage tanks automatic valve 6 and HF storage tanks flowmeter 8 pass sequentially through pipeline and are connected with reactor 15.Stock chest 16 and reactor 15
Connected by pipeline, pipeline is provided with automatic valve A 14, stock chest 16 is connected with electrolytic cell 20 by pipeline, and pipeline is provided with
Automatic valve B 18, pipeline between automatic valve B 18 and electrolytic cell 20 is provided with flowmeter 19, stock chest liquid level gauge 17 with
Stock chest 16 is connected by pipeline.Electrolytic cell 20 and electrolytic cell liquid level gauge 21 are connected by pipeline.N2Tank 9 and N2Pressure tank table 10
After being connected by pipeline, it is divided on two branch roads, a branch road and passes through pipeline and N2Tank automatic valve A 12 and reactor 15 according to
Secondary connection, another branch road passes through pipeline and N2Tank automatic valve B 13 and stock chest 16 are sequentially connected.
The gas that anode is produced when being electrolysed using chromatographic.
Comparative example 1
Use the electrolytic preparation NF of skirtboard formula carbon steel electrolytic cell 20 that the specification of electrolytic cell 20 is 1000A for range3Gas, it is described
The electrolyte liquid level of electrolytic cell 20 is up to 550mm, and minimum liquid level is 450mm, and anode and negative electrode are nickel plate, HF and NH3Press
2.7:1 mol ratio is in 1200L, and highest liquid level is 700mm, and minimum liquid level is is modulated into 100mm nickel stock chest 16
NH4F1.7HF fuse salts, weight/mass percentage composition >=0.01% of raw material HF reclaimed waters, raw material NH3The weight/mass percentage composition of reclaimed water >=
0.08%.Using manually adding electrolyte after the electrolytic cell 20, start electrolysis, electrolysis temperature is 120 DEG C.
The electrolysis of electrolytic cell 20 flow is as follows：1) the electrolysis water removal 50h under the conditions of voltage is 5.5V, measurement anode is produced
Gas, NF3Volumn concentration be 25%, H2Volumn concentration be 3.5%, due to working as H2Volumn concentration
For≤2% when could safe collection anode produce NF3Gas, therefore continuation electrolysis removes water to 100h, the gas that measurement anode is produced
Body, NF3Volumn concentration be 45%, H2Volumn concentration be 0.4%, can now enter collection phase；2) electricity is lifted
It is depressed into 7V to continue to be electrolysed, Faradaic current is 82mAcm-2, collect NF3Gas, until electrolyte liquid level is less than the electrolytic cell 20
Minimum liquid level；3) stop electrolysis, manually add electrolyte, comprise the following steps that：Remove the Anodic of electrolytic cell 20 and negative electrode and receipts
The connecting tube of collector, installs the connecting tube of anode and negative electrode and blow-down pipe, and nitrogen is swept in unlatching, and the time is 4h, is mended from electrolyte entrance
Plus electrolyte, the whole activity duration is 6h；4) added after electrolyte, voltage be 5.5V under the conditions of carry out electrolysis water removal until
Measure H in the gas that anode is produced2Volumn concentration be≤2%, the time is 24h；5) repeat step 2)~4), until electricity
Solution is carried out 90 days, Faradaic current reduction by 30%, and the anode working life-span expires, and the operation of electrolytic cell 20 expires.
During the electrolytic cell 20 is electrolysed, electrolysis water removal and manually adds the time used in electrolyte and account for total cycle of operation
15%, i.e. NF3Effective production time accounts for the 85% of total cycle of operation.
Comparative example 2
One kind prepares NF in this comparative example3The reactor 15 of the device of gas is using 1500L nickel reactor 15；Stock chest
16 and electrolytic cell 20 with comparative example 1.
The applying step of described device is as follows：
(1) electrolyte synthesis and deposit
Signal control NH is sent by automation control system 113Storage tank automatic valve 5 and HF storage tanks automatic valve 6 are opened,
Reaction raw materials NH3With HF respectively from NH3Storage tank 1 and HF storage tanks 2 enter reactor 15, NH3Storage tank flowmeter 7 and HF storage tank flows
Meter 8 adjusts NH respectively3With HF flow to 220L/min and 545L/min；Work as NH38 points of storage tank flowmeter 7 and HF storage tanks flowmeter
NH is not detected33.62 × 10 are reached with HF integrated fluxs5L and 8.96 × 105During L, automation control system is signaled to
11, receive after signal, automation control system 11 sends signal control NH3Storage tank automatic valve 5 and HF storage tanks automatic valve 6 are closed
Close, NH3Stop entering reactor 15 with HF；The NH in reactor 153Gas and HF solid/liquid/gas reactions generation NH4F1.7HF electrolyte；
After reaction terminates, automation control system 11 sends signal control N2Tank automatic valve A12 and automatic valve A
14 open, and control N2Pressure tank table 10 adjusts N2Pressure, by by N2Press-in reactor 15 enters the electrolyte in reactor 15
Stock chest 16, when it is 700mm that stock chest liquid level gauge 17, which shows numerical value, sends signal to automation control system 11, receives letter
After number, automation control system 11 sends signal control N2Tank automatic valve A 12 and automatic valve A 14 are closed, N2Stop entering
Reactor 15, electrolyte stops entering stock chest 16.
Weight/mass percentage composition >=0.01% of the raw material HF reclaimed waters, raw material NH3The weight/mass percentage composition of reclaimed water >=
0.08%.
(2)NF3It is electrolysed and adds
Automation control system 11 sends signal control N2Tank automatic valve B 13 and automatic valve B 18 are opened, and control N2
Pressure tank table 10 adjusts N2Pressure, by N2Press-in stock chest 16 makes the electrolyte in stock chest 16 enter in electrolytic cell 20, works as electrolysis
When groove liquid level gauge 21 shows numerical value for 550mm, signal is sent to automation control system 11, is received after signal, Automated condtrol
System 11 sends signal control N2Tank automatic valve B 13 and automatic valve B 18 are closed, and electrolyte is electrolysed instead in electrolytic cell 20
NF should be produced3Gas.
Electrolysis production NF3During gas, it is by electrolyte consumes the electrolyte method of adding carried out：1) electrolyte is worked as
When liquid level gauge shows numerical value for 450mm, signal is sent to automation control system 11, is received after signal, automation control system
11 send signal control N2Tank automatic valve B 13 and automatic valve B 18 are opened, and control N2Pressure tank table 10 adjusts N2Pressure, will
N2The addition speed that stock chest 16 controls electrolyte is pressed into, electrolyte electrolytic cell 20 is pressed into from stock chest 16, flowmeter 19 shows
Show and add speed, add speed for 18Kg/1000Ah；2) when it is 550mm that electrolytic cell liquid level gauge 21, which shows numerical value, to automation
Control system 11 sends signal, receives after signal, and automation control system 11 sends signal control N2The Hes of tank automatic valve B 13
Automatic valve B 18 is closed, and stops adding the electrolyte to electrolytic cell 20；3) when stock chest liquid level gauge 17 shows that numerical value is not arrived
During up to 100mm, repeat step 1) and 2) add electrolyte；When it is 100mm that stock chest liquid level gauge 17, which shows numerical value, to automation
Control system 11 sends signal, receives after signal, and automation control system 11 sends signal control NH3The He of storage tank automatic valve 5
HF storage tanks automatic valve 6 is opened, the synthesis of repeat step (1) electrolyte and deposit process.
The electrolysis of electrolytic cell 20 flow is as follows：
Electrolytic cell 20 is within the cycle of operation, and electrolysis temperature is 120 DEG C.The electrolysis of electrolytic cell 20 flow is as follows：1) in electricity
Press the gas produced for electrolysis time under the conditions of 5.5V to 100h, measurement anode, NF3Volumn concentration be 51%, H2Body
Product percentage composition is 0.2%, can now enter collection phase；2) booster tension is to 7V, and Faradaic current is 83mAcm-2Continue electricity
Solution, collects NF3Gas, carries out feed supplement when electrolyte liquid level is less than 20 minimum liquid level of electrolytic cell during operation, is not stop
Continuous feeding under machine state；When electrolytic cell 20 is continuously run to 40 days, the gas that measurement anode is produced, NF3Volume hundred
It is 62%, H to divide content2Volumn concentration be 3%, there is vexed sound in electrolytic cell 20, and electrolysis stops.
Comparative example 3
One kind prepares NF in this comparative example3Reactor 15, stock chest 16 and the same comparative example of electrolytic cell 20 of the device of gas
2。
The applying step of described device is as follows：
(1) electrolyte synthesis and deposit
Weight/mass percentage composition≤0.008% of raw material HF reclaimed waters, raw material NH3Weight/mass percentage composition≤0.008% of reclaimed water,
Remaining is with the step of comparative example 2 (1).
(2)NF3It is electrolysed and adds
Speed is added for 200Kg/1000Ah；Remaining is with the step of comparative example 2 (2).
Electrolytic cell 20 is within the cycle of operation, and electrolysis temperature is 120 DEG C.The electrolysis of electrolytic cell 20 flow is as follows：1) in electricity
Press the gas produced for electrolysis time under the conditions of 5.5V to 5h, measurement anode, NF3Volumn concentration be 57.6%, H2Body
Product percentage composition is 0.15%, can now enter collection phase；2) booster tension is to 7V, and Faradaic current is 84.5mAcm-2After
Continuous electrolysis, collects NF3Gas, carries out feed supplement when electrolyte liquid level is less than 20 minimum liquid level of electrolytic cell during operation, is
The not continuous feeding under stopped status；When electrolytic cell 20 is continuously run to 50 days, Faradaic current drops to 68mAcm-2, survey
Measure the gas that anode is produced, NF3Volumn concentration be 61.3%, H2Volumn concentration be 2%, electrolytic cell 20 occurs
Vexed sound, electrolysis stops.
Embodiment 1
One kind prepares NF in the present embodiment3Reactor 15, stock chest 16 and the same comparative example of electrolytic cell 20 of the device of gas
2。
The applying step of described device is as follows：
(1) electrolyte synthesis and deposit
Work as NH3Storage tank flowmeter 7 and HF storage tanks flowmeter 8 detect NH respectively34.7 × 10 are reached with HF integrated fluxs5L
With 1.16 × 106During L, automation control system 11 is signaled to；Remaining is with the step of comparative example 3 (1).
(2)NF3It is electrolysed and adds
With the step of comparative example 2 (2).
The electrolytic cell 20 is within the cycle of operation, and electrolysis temperature is 120 DEG C.The electrolysis of electrolytic cell 20 flow is as follows：1)
The gas that electrolysis time is produced to 5h, measurement anode under the conditions of voltage is 5.5V, NF3Volumn concentration be 56%, H2's
Volumn concentration is 0.08%, can now enter collection phase；2) booster tension is to 7V, and Faradaic current is 84mAcm-2After
Continuous electrolysis, collects NF3Gas, carries out feed supplement when electrolyte liquid level is less than 20 minimum liquid level of electrolytic cell during operation, is
The not continuous feeding under stopped status；When electrolytic cell 20, continuously operation was to 90 days, and Faradaic current reduces by 30%, anode working life-span
Expire, more than 99.7% time is all in production NF during the operation of electrolytic cell 203, electrolytic cell 20 is without exception, and measurement anode is produced
Gas, NF3Volumn concentration be 59.7%.
Embodiment 2
One kind prepares NF in the present embodiment3Reactor 15, stock chest 16 and the same comparative example of electrolytic cell 20 of the device of gas
2。
The applying step of described device is as follows：
(1) electrolyte synthesis and deposit
NH3Storage tank flowmeter 7 and HF storage tanks flowmeter 8 adjust NH respectively3With HF flow to 220L/min and 585L/
min；Work as NH3Storage tank flowmeter 7 and HF storage tanks flowmeter 8 detect NH respectively34.49 × 10 are reached with HF integrated fluxs5L and
1.19×106During L, automation control system 11 is signaled to；The NH in reactor 153Gas and HF solid/liquid/gas reactions generation NH4F·
1.9HF electrolyte；Remaining is with the step of comparative example 3 (1).
(2)NF3It is electrolysed and adds
With the step of comparative example 2 (2).
The electrolytic cell 20 is within the cycle of operation, and electrolysis temperature is 120 DEG C.The electrolysis of electrolytic cell 20 flow is as follows：1)
The gas that electrolysis time is produced to 5h, measurement anode under the conditions of voltage is 5.5V, NF3Volumn concentration be 58.7%, H2
Volumn concentration be 0.1%, can now enter collection phase；2) booster tension is to 7V, and Faradaic current is 82mAcm-2After
Continuous electrolysis, collects NF3Gas, carries out feed supplement when electrolyte liquid level is less than 20 minimum liquid level of electrolytic cell during operation, is
The not continuous feeding under stopped status；When electrolytic cell 20, continuously operation was to 90 days, and Faradaic current reduces by 33%, anode working life-span
Expire, the operation of electrolytic cell 20 expires, and electrolytic cell 20 is without exception during running, the gas that measurement anode is produced, NF3Volume basis
Content is 60.9%.
Embodiment 3
One kind prepares NF in the present embodiment3The reactor 15 of the device of gas is with comparative example 2；Stock chest 16 is 4000L nickel
Container, highest liquid level is 700mm, minimum 100mm；Electrolytic cell 20 is that range is 6000A skirtboard formula carbon steels electrolytic cell 20, institute
Electrolyte liquid level up to 650mm, the minimum 530mm of electrolytic cell 20 are stated, anode and negative electrode are nickel plate.
The applying step of described device is as follows：
(1) electrolyte synthesis and deposit
Work as NH3Storage tank flowmeter 7 and HF storage tanks flowmeter 8 detect NH respectively34.7 × 10 are reached with HF integrated fluxs5L
With 1.16 × 105During L, automation control system 11 is signaled to；Remaining is with the step of comparative example 3 (1).
(2)NF3It is electrolysed and adds
When it is 650mm that electrolytic cell liquid level gauge 21, which shows numerical value, signal is sent to automation control system 11；
Electrolysis production NF3During gas, it is by electrolyte consumes the electrolyte method of adding carried out：1) electrolyte is worked as
When liquid level gauge shows numerical value for 530mm, signal, 2 are sent to automation control system 11) when electrolytic cell liquid level gauge 21 shows numerical value
During for 650mm, signal is sent to automation control system 11；Remaining is with the step of comparative example 2 (2)
The electrolytic cell 20 is within the cycle of operation, and electrolysis temperature is 120 DEG C.The electrolysis of electrolytic cell 20 flow is as follows：1)
The gas that electrolysis time is produced to 5h, measurement anode under the conditions of voltage is 5.5V, NF3Volumn concentration be 53.6%, H2
Volumn concentration be 0.18%, can now enter collection phase；2) booster tension is to 7V, and Faradaic current is 99.5mA
cm-2Continue to be electrolysed, collect NF3Gas, is mended during operation when electrolyte liquid level is less than 20 minimum liquid level of electrolytic cell
Material, is the continuous feeding not under stopped status；When electrolytic cell 20, continuously operation was to 90 days, and Faradaic current reduces by 40%, anode work
Expired as the life-span, the operation of electrolytic cell 20 expires, and electrolytic cell 20 is without exception during running, the gas that measurement anode is produced, NF3Body
Product percentage composition is 61.7%.
Claims (6)
1. a kind of device for preparing gas of nitrogen trifluoride, it is characterised in that：Described device is main by electrolyte synthesis system, electrolysis
Liquid storage system, electrolysis system, sweep nitrogen system and automation control system (11) composition；
Electrolyte synthesis system mainly includes NH3Storage tank (1), HF storage tanks (2), NH3Storage tank vaporizer (3), HF storage tank vaporizers
(4)、NH3Storage tank automatic valve (5), HF storage tanks automatic valve (6), NH3Storage tank flowmeter (7), HF storage tanks flowmeter (8) and anti-
Answer kettle (15)；
Electrolyte storage system mainly includes stock chest (16), automatic valve A (14), automatic valve B (18), stock chest liquid level gauge
And flowmeter (19) (17)；
Electrolysis system mainly includes electrolytic cell (20) and electrolytic cell liquid level gauge (21)；
Sweeping nitrogen system mainly includes N2Tank (9), N2Pressure tank table (10), N2Tank automatic valve A (12) and N2Tank automatic valve B
(13)；
NH3Storage tank (1), NH3Storage tank vaporizer (3), NH3Storage tank automatic valve (5) and NH3Storage tank flowmeter (7) passes sequentially through pipe
Road is connected with reactor (15)；HF storage tanks (2), HF storage tanks vaporizer (4), HF storage tanks automatic valve (6) and HF storage tank flowmeters
(8) pipeline is passed sequentially through to be connected with reactor (15)；Stock chest (16) is connected with reactor (15) by pipeline, and pipeline is provided with
Automatic valve A (14), stock chest (16) is connected with electrolytic cell (20) by pipeline, and pipeline is provided with automatic valve B (18), automatically
Pipeline between valve B (18) and electrolytic cell (20) is provided with flowmeter (19), stock chest liquid level gauge (17) and stock chest (16)
Connected by pipeline；Electrolytic cell (20) and electrolytic cell liquid level gauge (21) are connected by pipeline；N2Tank (9) and N2Pressure tank table (10)
After being connected by pipeline, it is divided on two branch roads, a branch road and passes through pipeline and N2Tank automatic valve A (12) and reactor (15)
It is sequentially connected, another branch road passes through pipeline and N2Tank automatic valve B (13) and stock chest (16) are sequentially connected；
Automation control system (11) is by signal respectively to NH3Storage tank automatic valve (5), HF storage tanks automatic valve (6), N2Tank
Automatic valve A (12), N2Tank automatic valve B (13), automatic valve A (14), automatic valve B (18), NH3Storage tank flowmeter (7),
HF storage tanks flowmeter (8), flowmeter (19), stock chest liquid level gauge (17), electrolytic cell liquid level gauge (21) and N2Pressure tank table (10)
Carry out remote control；
The minimum liquid level of stock chest (16) is 100mm；
Reaction raw materials NH3With HF respectively from NH3Storage tank (1) and HF storage tanks (2) enter reactor (15), the NH in reactor (15)3
Gas and HF solid/liquid/gas reactions generation electrolyte, raw material NH3Middle NH3Weight/mass percentage composition >=99.8%, the weight/mass percentage composition of water≤
HF weight/mass percentage composition >=99.9%, weight/mass percentage composition≤0.008% of water in 0.008%, raw material HF；Electrolyte is in electricity
Solve cell reaction in groove (20) and produce NF3Gas, electrolysis production NF3During gas, by electrolyte consumes carried out electrolyte
Speed is added for 10kg/1000Ah~100kg/1000Ah.
2. a kind of application of the device as claimed in claim 1 for preparing gas of nitrogen trifluoride, it is characterised in that：Applying step is such as
Under：
(1) electrolyte synthesis and deposit
Signal control NH is sent by automation control system (11)3Storage tank automatic valve (5) and HF storage tanks automatic valve (6) are opened,
Reaction raw materials NH3With HF respectively from NH3Storage tank (1) and HF storage tanks (2) enter reactor (15), NH3Storage tank flowmeter (7) and HF
Storage tank flowmeter (8) adjusts NH respectively3With HF flow, make HF and NH3Mol ratio be 2:1~3:1；Work as NH3Storage tank flowmeter
And HF storage tanks flowmeter (8) detects NH respectively (7)3When reaching the capacity of reactor (15) with HF integrated fluxs, signal is sent
Automation control system (11) is given, is received after signal, automation control system (11) sends signal control NH3Storage tank automatic valve
(5) closed with HF storage tanks automatic valve (6), NH3Stop entering reactor (15) with HF；The NH in reactor (15)3Gas and HF gas
Reaction generation electrolyte；
After reaction terminates, automation control system (11) sends signal control N2Tank automatic valve A (12) and automatic valve A (14)
Open, control N2Pressure tank table (10) adjusts N2Pressure, by by N2Press-in reactor (15) makes the electrolyte in reactor (15)
Into stock chest (16), when stock chest liquid level gauge (17) shows that numerical value reaches the storage cap of stock chest (16), to automation
Control system (11) sends signal, receives after signal, and automation control system (11) sends signal control N2Tank automatic valve A
(12) closed with automatic valve A (14), N2Stop entering reactor (15), electrolyte stops entering stock chest (16)；
(2)NF3It is electrolysed and adds
Automation control system (11) sends signal control N2Tank automatic valve B (13) and automatic valve B (18) is opened, and controls N2
Pressure tank table (10) adjusts N2Pressure, by N2Press-in stock chest (16) makes the electrolyte in stock chest (16) enter electrolytic cell (20)
In, when electrolytic cell liquid level gauge (21) shows that numerical value reaches the liquid level upper limit of electrolytic cell (20), give automation control system (11)
Signal is sent, is received after signal, automation control system (11) sends signal control N2Tank automatic valve B (13) and automatic valve
B (18) is closed, and electrolyte cell reaction in electrolytic cell (20) produces NF3Gas；
Electrolysis production NF3During gas, it is by electrolyte consumes the electrolyte method of adding carried out：1) when electrolyte liquid level
When meter shows that numerical value reaches the liquid level lower limit of electrolytic cell (20), signal is sent to automation control system (11), is received after signal,
Automation control system (11) sends signal control N2Tank automatic valve B (13) and automatic valve B (18) is opened, and controls N2Tank pressure
Power table (10) adjusts N2Pressure, by N2The addition speed that stock chest (16) controls electrolyte is pressed into, by electrolyte from stock chest
(16) speed is added in press-in electrolytic cell (20), flowmeter (19) display；2) when electrolytic cell liquid level gauge (21) shows that numerical value reaches electricity
When solving the liquid level upper limit of groove (20), signal is sent to automation control system (11), is received after signal, automation control system
(11) signal control N is sent2Tank automatic valve B (13) and automatic valve B (18) is closed, and is stopped described to electrolytic cell (20) addition
Electrolyte；3) when stock chest liquid level gauge (17) does not show that numerical value reaches the liquid level lower limit of stock chest (16), repeat step 1) and
2) electrolyte is added；When stock chest liquid level gauge (17) shows that numerical value reaches the storage lower limit of stock chest (16), automation control is given
System (11) processed sends signal, receives after signal, and automation control system (11) sends signal control NH3Storage tank automatic valve
(5) opened with HF storage tanks automatic valve (6), the synthesis of repeat step (1) electrolyte and deposit process；
Electrolyte is NH4FxHF fuse salts, HF and NH4F molar ratios x is 1~2；
Faradaic current is 50mAcm-2~150mAcm-2, decomposition voltage is 5.5V~8V, and electrolysis temperature is 80 DEG C~140 DEG C.
3. a kind of application of device for preparing gas of nitrogen trifluoride according to claim 2, it is characterised in that：Raw material NH3In
Weight/mass percentage composition≤0.005% of water；Weight/mass percentage composition≤0.005% of raw material HF reclaimed waters.
4. a kind of application of device for preparing gas of nitrogen trifluoride according to Claims 2 or 3, it is characterised in that：Electrolysis
Liquid adds speed for 14kg/1000Ah~50kg/1000Ah.
5. the application of the device for preparing gas of nitrogen trifluoride according to Claims 2 or 3, it is characterised in that：Electrolytic cell
(20) NF is prepared for fusion electrolysis method3Skirtboard formula electrolytic cell (20) used in gas, anode be nickel or carbon plate, negative electrode be nickel,
Carbon plate or iron, electrolytic cell (20) are processed using carbon steel, stainless steel, nickel, nickel alloy, fluorine resin or Fluorine-lined material, range
Between 500A~10000A.
6. the application of the device according to claim 4 for preparing gas of nitrogen trifluoride, it is characterised in that：Electrolytic cell (20) is
Fusion electrolysis method prepares NF3Skirtboard formula electrolytic cell (20) used in gas, anode be nickel or carbon plate, negative electrode be nickel, carbon plate or
Iron, electrolytic cell (20) is processed using carbon steel, stainless steel, nickel, nickel alloy, fluorine resin or Fluorine-lined material, and range is in 500A
Between~10000A.
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| CN108557785A (en) * | 2018-05-09 | 2018-09-21 | 刘成霞 | A kind of Nitrogen trifluoride purification devices using antimony molybdenum doping material |
| CN112626548A (en) * | 2020-12-22 | 2021-04-09 | 中船重工（邯郸）派瑞特种气体有限公司 | Charging system and method for nitrogen trifluoride electrolytic cell |
| CN112853387A (en) * | 2020-12-29 | 2021-05-28 | 中船重工（邯郸）派瑞特种气体有限公司 | Heat exchange device suitable for preparing nitrogen trifluoride gas by electrolysis method and electrolysis method |
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| JP3162594B2 (en) * | 1995-02-21 | 2001-05-08 | 三井化学株式会社 | Electrolytic solution and method for producing nitrogen trifluoride gas using the same |
| CN1180128C (en) * | 2003-04-30 | 2004-12-15 | 中国船舶重工集团公司第七一八研究所 | Technological method and equipment for preparing nitrogen trifluoride gas |
| CN1328159C (en) * | 2005-07-27 | 2007-07-25 | 中国船舶重工集团公司第七一八研究所 | Equipment and technological process for preparing nitrogen trifluoride by using ammonia and hydrogen fluoride as raw material |
| CN101798689A (en) * | 2010-03-18 | 2010-08-11 | 黎明化工研究院 | Process and device for preparing nitrogen trifluoride by continuous electrolytic process |
| CN202265610U (en) * | 2011-10-10 | 2012-06-06 | 黎明化工研究院 | Anticorrosion electrolytic cell for nitrogen trifluoride |
| US20140110267A1 (en) * | 2012-10-19 | 2014-04-24 | Air Products And Chemicals, Inc. | Anodes for the Electrolytic Production of Nitrogen Trifluoride and Fluorine |
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Effective date of registration: 20190618 Address after: 057550 No. 1 Weiwu Road, Chemical Industry Agglomeration Area, Feixiang County, Handan City, Hebei Province Patentee after: CSIC (Handan) Perry Special Gas Co. Ltd Address before: 056027 17 Exhibition Road, Handan, Hebei Patentee before: No.718 Inst., China Shipping Heavy Industry Group Co. |
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Address after: 057550 No. five Weir Road, chemical industry gathering area, Feixiang District, Handan, Hebei, 1 Patentee after: China shipbuilding (Handan) Perry Special Gas Co.,Ltd. Address before: No.1 Weiwu Road, chemical industry gathering area, Feixiang County, Handan City, Hebei Province Patentee before: PERIC SPECIAL GASES Co.,Ltd. |