CN1266031C - Fluorine gas generator - Google Patents
Fluorine gas generator Download PDFInfo
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- CN1266031C CN1266031C CNB2003101196923A CN200310119692A CN1266031C CN 1266031 C CN1266031 C CN 1266031C CN B2003101196923 A CNB2003101196923 A CN B2003101196923A CN 200310119692 A CN200310119692 A CN 200310119692A CN 1266031 C CN1266031 C CN 1266031C
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- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000007789 gas Substances 0.000 claims abstract description 239
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 43
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 36
- 230000007246 mechanism Effects 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 abstract description 8
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 229910000792 Monel Inorganic materials 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ISQINHMJILFLAQ-UHFFFAOYSA-N argon hydrofluoride Chemical compound F.[Ar] ISQINHMJILFLAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
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- 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)
- Analytical Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
A fluorine gas generator for generating fluorine gas by electrolysis of an electrolytic bath comprising a hydrogen fluoride-containing mixed molten salt in which generator the electrolytic bath will not corrode the upstream line even upon interruption of HF feeding or in case of emergency is provided. The generator has a hydrogen fluoride gas feed line for feeding hydrogen fluoride gas into the electrolytic bath, a first automatic valve disposed on the hydrogen fluoride gas feed line and capable of being closed on the occasion of interruption of hydrogen fluoride gas feeding, and an inert gas substitution means for eliminating the hydrogen fluoride gas remaining in the line on the side downstream from the first automatic valve on the hydrogen fluoride gas feed line and substituting an inert gas therefor when hydrogen fluoride gas feeding is interrupted.
Description
Technical field
The present invention relates to apparatus for generating fluorine gas, particularly about the apparatus for generating fluorine gas of the few high purity fluorine gas of the impurity that takes place to use in the manufacturing process such as semi-conductor.
Technical background
All the time, fluorine gas is an indispensable crucial gas in the field of semiconductor manufacture for example.And, though the situation of direct use is also arranged, particularly be with the fluorine gas the synthetic gas of nitrogen trifluoride in basis (below, be called NF
3Gas) etc., its demand as semi-conductive purge gas or dry etching gas is increased rapidly.Again, fluoridize the neon body (below, be called NeF gas), argon fluoride gas (below, be called ArF gas), KrF gas (below, be called KrF gas) etc. be that gas is used in the excimer laser vibration that the semiconductor integrated circuit pattern uses when forming, its raw material adopts the mixed gas of rare gas and fluorine gas more.
The fluorine gas or the NF that use during semi-conductor etc. are made
3It is the few high-pure gas of impurity that gas requires.And be to use at the gas that the on-the-spot gas cylinder from the can fluorine gas of semi-conductor manufacturing takes out necessary amount.Therefore, the site of storage of gas bomb, guarantee gas safety and keep the management of purity etc. extremely important.And, because NF
3Supply falls short of demand for the rapid increase of demand that gas is nearest so some, also must guarantee a certain amount of stock.If consider these problems, compare with using high-pressure fluorine, not as production, on-the-spot used apparatus for generating fluorine gas as required are set in the field of employment.
Usually, fluorine gas utilization electrolyzer as shown in Figure 4 takes place.Fig. 4 is the mode chart of apparatus for generating fluorine gas.The material of electrolyzer body 201 is used Ni, Monel metal, carbon steel etc. usually.And,,, the base plate 212 that is made of tetrafluoroethylene etc. is set for the hydrogen that prevents to produce and fluorine gas mix in the bottom of electrolyzer body 201.In electrolyzer body 201, the mixed melting salt that is full of Potassium monofluoride-hydrogen fluoride system (below be called KF-HF system) is as electrolytic solution 202.And, be beneficial to the skirtboard 209 that forms by Monel metal etc., be separated into anolyte compartment 210 and cathode compartment 211.Carbon in being accommodated in this anolyte compartment 210 or nickel (below be called Ni) anode 203 and be accommodated between the Ni negative electrode 204 in the cathode compartment 211 and apply voltage produces fluorine gas by electrolysis.In addition, the fluorine gas of generation from mouthful 208 discharges take place, is discharged from hydrogen relief outlet 207 at the hydrogen that cathode side produces.When the liquid level of the electrolytic solution owing to the generation of fluorine gas descends, directly to electrolytic solution, provide HF from HF supplying opening 213, and HF supplying opening 213 is to be connected from the outside of electrolyzer to extend on hydrogen fluoride the electrolytic solution of cathode compartment (below be called HF) the gas supply pipe road.The supply of HF is (for example with reference to the Patent Document 1) with the transmitter interlock of the liquid level of the supervision electrolytic solution that do not show of figure.
[Patent Document 1]
Te Biaoping 9-505853 communique
But, on such apparatus for generating fluorine gas, when the HF supply stops, make the downstream side of the valve in the HF supply line become negative pressure owing to cutting off the valve that is configured on the HF supply line, electrolytic solution flows in the HF supply line by HF supplying opening 213, and pipeline inside is stopped up because of the curing of electrolytic solution.The pipeline that is stopped up by electrolytic solution must all be changed, need expend time in and money in the recovery of device.
Again, HF itself also is the strong gas of corrodibility, in order to protect the various device that is installed on the pipeline, must shorten the duration of contact with HF as far as possible.
Summary of the invention
The present invention, in view of the above problems, purpose is to provide, even when apparatus for generating fluorine gas promptly stops or the supply of HF when stopping, electrolytic solution can not flow into upstream yet and solidify and make obstruction pipeline in, and in pipeline the apparatus for generating fluorine gas of residual HF not.
Be the solution of the present invention 1 described apparatus for generating fluorine gas that solves above-mentioned problem, be to be used for electrolysis by containing the electrolytic solution that hydrofluoric mixed melting salt constitutes and produce the apparatus for generating fluorine gas of fluorine gas, it is characterized in that having: the hydrogen fluoride gas supply line that hydrogen fluoride gas is provided in aforementioned electrolyte; Be configured on the aforementioned hydrogen fluoride gas supply line and the 1st self-acting valve of when the supply of aforementioned hydrogen fluoride gas stops, closing; When the supply of aforementioned hydrogen fluoride gas stops, discharging aforementioned the 1st self-acting valve of the ratio hydrogen fluoride gas in the pipeline in downstream side and be replaced into the inert gas replacement mechanism of rare gas element more remain in aforementioned hydrogen fluoride gas supply line.
If adopt this formation, when apparatus for generating fluorine gas stops the supply of HF because with ratio the 1st self-acting valve of HF supply line more in the pipeline in downstream side remaining HF be replaced into rare gas element, so, can not become negative pressure in the HF supply line.Therefore, electrolytic solution can not flow the HF supply line, can prevent the obstruction in the pipeline that the curing because of electrolytic solution causes, simultaneously, can protect the machine that is configured on the pipeline of having replaced rare gas element not to be subjected to the corrosion of HF.In addition, as rare gas element, can exemplify out N
2, He, Ne, Ar, Kr, Xe (xenon), Rn (radon), but be not limited to these gas.
If adopt this formation, when apparatus for generating fluorine gas stops the supply of HF because automatically with ratio the 1st self-acting valve of HF supply line more in the pipeline in downstream side remaining HF be replaced into rare gas element, so, can not become negative pressure in the HF supply line.Therefore, electrolytic solution can not flow into the HF supply line, can prevent the obstruction in the pipeline that the curing because of electrolytic solution causes conscientiously, simultaneously, can protect the machine that is configured on the pipeline of having replaced rare gas element not to be subjected to the corrosion of HF.
If adopt this formation, because have the rare gas element hold-up vessel in the device, so even the rare gas element that provides from the outside is unstable or when stopping, also can pressure stable provide a certain amount of rare gas element to the HF supply line.
Scheme 4 described apparatus for generating fluorine gas, be to be used for electrolysis by containing the electrolytic solution that hydrofluoric mixed melting salt constitutes and produce the apparatus for generating fluorine gas of fluorine gas, it is characterized in that having: the hydrogen fluoride gas supply line that hydrogen fluoride gas is provided in aforementioned electrolyte; Be configured on the aforementioned hydrogen fluoride gas supply line and the 1st self-acting valve of when the supply of aforementioned hydrogen fluoride gas stops, closing; When aforementioned hydrogen fluoride gas is unusual, discharge aforementioned the 1st self-acting valve of the ratio hydrogen fluoride gas in the pipeline in downstream side and be replaced into the inert gas replacement mechanism of rare gas element more remain in aforementioned hydrogen fluoride gas supply line.
If adopt this formation, under apparatus for generating fluorine gas is pressed unusual situation such as urgent stop button because with ratio the 1st self-acting valve of HF supply line more in the pipeline in downstream side remaining HF be replaced into rare gas element, so, can not become negative pressure in the HF supply line.Therefore, electrolytic solution can not flow into the HF supply line, can prevent the obstruction in the pipeline that the curing because of electrolytic solution causes, simultaneously, can obtain to protect the machine that is configured on the pipeline of having replaced rare gas element not to be subjected to the corrosive effect of HF.
If adopt this formation, because have the rare gas element hold-up vessel in the device, so, also can provide a certain amount of rare gas element when unusual to the HF supply line even when the rare gas element that provides from the outside is cut off.
The simple declaration of drawing
Fig. 1 is the mode summary figure of the major portion of apparatus for generating fluorine gas of the present invention.
Fig. 2 is the enlarged view around the HF supply line among Fig. 1.
Fig. 3 is the variation of the rare gas element supply line among Fig. 2.
Fig. 4 is the mode chart of the apparatus for generating fluorine gas of tradition use.
Nomenclature
1 electrolyzer
2 electrolytic solution
3 anolyte compartments
4 cathode compartments
5 the 1st level detection mechanisms
6 the 2nd level detection mechanisms
7,8 self-acting valves
12 hot-water heating systems
14,15HF removes tower
16 partitions
22, mouth takes place in 23 gases
The 24HF supply line
The 25HF introducing port
31～34,84 pressure warning units
51 anodes
52 negative electrodes
65,66 manual valves
73 the 2nd self-acting valves
74,82 self-acting valves
81 the 1st self-acting valves
83,85 under meters
91 rare gas element supply lines
92 rare gas element storage tanks
The optimised form that carries out an invention
The following embodiment that apparatus for generating fluorine gas of the present invention is described with reference to Fig. 1, Fig. 2.
Fig. 1 is the synoptic diagram of major portion of the apparatus for generating fluorine gas of present embodiment.In Fig. 1, the 1st, electrolyzer, the 2nd, KF-HF are the electrolytic solution, the 3rd that mixed melting salt constitutes, anolyte compartment, the 4th, cathode compartment.The 5th, the 1st level detection mechanism of detection anolyte compartment liquid level.The 6th, the 2nd level detection mechanism of detection cathode compartment liquid level.The 22nd, the generation mouth of 3 fluorine gas that produce from the anolyte compartment, the 23rd, the generation mouth of the hydrogen that produces from cathode compartment 4, the 24th, the HF supply line of HF is provided to electrolyzer 1.The 81st, be configured in the 1st self-acting valve (the 1st self-acting valve) on the HF supply line, the 82nd, be configured in the self-acting valve on the HF supply line, the 83rd, monitor under meter by the flow of the HF in the HF supply line 24.At this so-called self-acting valve is such valves that are used to outside certainly signaling switch such as magnetic valve.The 84th, the pressure warning unit of the pressure of metering HF.The 91st, the rare gas element supply line of rare gas element is provided to HF supply line 24, the 92nd, the rare gas element hold-up vessel of rare gas element is provided to the rare gas element supply line, the 73rd, be configured in the 2nd self-acting valve (the 2nd self-acting valve) on the rare gas element supply line 91, the 74th, be configured in the self-acting valve on the rare gas element supply line 91.The 14th, the HF that removes HF the hydrogen of discharging from cathode compartment 4 and the mixed gas of HF removes tower, and the 15th, the F of 3 discharges from the anolyte compartment
2Remove tower with the HF that removes HF in the mixed gas of HF and discharge fluorine gas.
And, has the HF that stops to supply with supply the stopping proofing unit (feeler mechanism) that detects HF as unshowned equipment.Again, inert gas replacement mechanism is supplied with by rare gas element supply line 91, rare gas element hold-up vessel the 92, the 2nd self-acting valve 73, self-acting valve 82, self-acting valve 74 and HF and stops proofing unit and constitute.Having the pipeline of rare gas element hold-up vessel 92 and common rare gas element supply line 91 can be provided with respectively, also rare gas element hold-up vessel 92 can be set on same pipeline.Be preferably in pressure warning unit and reducing valve are set on the pipeline.
Electrolyzer 1 utilizes metal or alloy such as Ni, Monel metal, pure iron, stainless steel to form.Electrolyzer 1 utilizes the partition 16 that is made of Ni or Monel metal to be separated into anolyte compartment 3 and cathode compartment 4.Configuration anode 51 in anolyte compartment 3.And, negative electrode 52 is set in cathode compartment 4.In addition, anode preferably uses the hypopolarization carbon dioxide process carbon electrode.As negative electrode, preferably use Ni etc. again.On the loam cake 17 of electrolyzer 1, the generation mouth 22 of the sweeping gas gangway that connects as the gas piping that the figure that keeps one of atmospheric pressurizer in anolyte compartment 3 and the cathode compartment 4 is not shown, fluorine gas that anolyte compartment 3 produces, the generation mouth 23 of hydrogen that cathode compartment 4 produces are set.These take place mouthfuls 22,23, have the pipe that is had the bending that the corrosive material of anti-fluorine gas forms by stainless steel, heat-proof corrosion-resistant nickel-base alloy etc., suppress in the spittle intrusion gas piping from anolyte compartment 3 and cathode compartment 4.On loam cake 17, when descending, the liquid level that is arranged on electrolytic solution 2 provides HF introducing port the 25, the 1st level detection mechanism 5 and the 2nd level detection mechanism 6 of HF from HF supply line 24 again.
Fig. 2 is the HF supply line enlarged view on every side among Fig. 1.HF supply line 24 is connected with the HF supply source of apparatus for generating fluorine gas outside, and extends to the connection section of the HF introducing port 25 that disposes with electrolyzer 1 from this connection section.Near electrolyzer 1, on HF supply line 24 from the upstream arranged in order the 1st self-acting valve 81, under meter 83, self-acting valve 82, pressure warning unit 84 downstream.The 1st self-acting valve 81 stops the proofing unit linked switch and cuts off supply to the HF of electrolyzer 1 by supplying with HF.Under meter 83 monitors the flow that offers the HF of electrolyzer 1 by the HF supply line.Self-acting valve 82 utilizes the 1st level detection mechanism and the 2nd level detection mechanism to detect the decline of the liquid level of electrolytic solution, thereby and switch provide HF to electrolytic solution.Again, HF supply line 24 is used to prevent that the heater for regulating temperature of HF liquefaction from covering.
Rare gas element supply line 91 is connected with the rare gas element supply source of apparatus for generating fluorine gas outside, and from this connection section by rare gas element hold-up vessel 92 extend to electrolyzer 1 near, and near this electrolyzer 1, be divided into 2.2 rare gas element supply lines 91 after the shunting, be connected respectively on the HF supply line 24 on the upstream side connection section between the 1st self-acting valve 81 of configuration and the under meter 83 and HF supply line 24 and between self-acting valve 82 and the pressure warning unit 84 and downstream side connection section HF supply line 24 on.The 2nd self-acting valve 73 is configured near the upstream side connection section on the rare gas element supply line 91 after the shunting.Self-acting valve 74 is configured near the downstream side connection section on the rare gas element supply line 91.The normal confession from the rare gas element of rare gas element supply source is accepted in the input of rare gas element hold-up vessel 92, utilizes that the output of rare gas element hold-up vessel 92 is permanent to provide stable rare gas element with certain pressure to rare gas element supply line 91.
In addition, rare gas element supply line 91 not only can adopt above-mentioned formation, also can adopt formation shown in Figure 3.Fig. 3 is the variation of the supply line of Fig. 2.For example shown in Fig. 3 (a) like that, the 2nd self-acting valve 73, self-acting valve 74 also can be set and directly utilize the 1st self-acting valve 81 of HF supply line 24 to connect downstream sides by reverse checkvalve to constitute.At this moment, have only than the 1st self-acting valve 81 rare gas element is provided when more the pressure in downstream side is lower than pressure in the rare gas element supply line 91.Otherwise when pressure is high, utilize reverse checkvalve to prevent refluence to rare gas element supply line 91.Again, also can adopt as Fig. 3 (b), the formation that the 2nd self-acting valve 73 replaces the reverse checkvalve among Fig. 3 (a) and under meter 83 is set in its downstream side is set.At this moment, the supply of HF will be carried out exerting pressure in the HF supply line 24.The 2nd self-acting valve 73 is closed when supplying with HF, and the 2nd self-acting valve 73 is opened with the under meter interlock and with the remaining HF of inert gas replacement when the supply of HF stops.Also can adopt the permanent supply rare gas element in downstream side of the 1st self-acting valve 81 that as Fig. 3 (c), rare gas element supply line 91 is connected HF supply line 24 and utilize mixed effect in pipeline, to import N again,
2The formation of HF in the escape route.At this moment, even the supply of HF stops also can to continue the supply of rare gas element in the same old way, and HF remaining in the pipeline is replaced as rare gas element.
Below, the principle of work of HF when moving usually, the apparatus for generating fluorine gas that present embodiment is described is provided to electrolytic solution.Consume electrolytic solution when obtaining fluorine gas by utilizing electrolysis to carry out reaction in the electrolytic solution.The consumption of electrolytic solution utilizes the 1st level detection mechanism 5 and the 2nd level detection mechanism 6 to monitor that the decline of electrolytic solution detects.When detect electrolytic solution be depleted to specified amount the time carry out the supply action of HF.Particularly, close on the rare gas element supply line 91 on the upstream side connection section that is connected HF supply line 24 the 2nd self-acting valve 73 of configuration, the self-acting valve 74 of configuration on the rare gas element supply line 91 on the downstream side connection section that open the 1st self-acting valve 81, the self-acting valve 82 that dispose on the HF supply line, is connected HF supply line 24.Like this, the rare gas element of the certain pressure that provides from rare gas element hold-up vessel 92 offers ratio self-acting valve 82 downstream side more in the HF supply line 24 from the downstream side connection section of HF supply line 24 and rare gas element supply line 91.The rare gas element that offers HF supply line 24 becomes vector gas and the HF in the HF supply line is offered electrolytic solution.The amount that offers the HF of electrolytic solution is measured by under meter 83.
When owing to when HF electrolytic solution rising specified amount is provided, is supplied with stop gear by the 1st level detection mechanism 5 and the 2nd level detection mechanism 6 by HF and detect, that carries out HF stops to supply with action.Particularly, the 1st self-acting valve 81 is closed the supply of cutting off HF, self-acting valve 82 and the 2nd self-acting valve 73 are opened, self-acting valve 74 is closed, like this, more provide rare gas element in the downstream side from ratio the 1st self-acting valve 81 of upstream side connection section in HF supply line 24 of HF supply line 24 and rare gas element supply line 91 from the certain pressure of rare gas element hold-up vessel 92, and than the 1st self-acting valve 81 more the HF in downstream side be replaced as rare gas element.Like this, remaining HF in the HF supply line 24 all can be delivered to the pressure that can keep simultaneously in the electrolyzer 1 in the pipeline.And the rare gas element that is provided to usually in the electrolyzer 1 is discharged from gas generation mouth 23 with the hydrogen of generation.
Below, the electrolytic solution to apparatus for generating fluorine gas during specification exception provides the principle of HF.When apparatus for generating fluorine gas was unusual, the supply that utilizes HF supply stop gear to carry out HF stopped action.Particularly, the 1st self-acting valve 81 is closed the supply of cutting off HF, self-acting valve 82 and the 2nd self-acting valve 73 are opened, self-acting valve 74 is closed, like this, more provide rare gas element from the certain pressure of rare gas element hold-up vessel 92 in the downstream side from the 1st self-acting valve 81 of upstream side connection section in HF supply line 24 of HF supply line 24 and rare gas element supply line 91, the 1st self-acting valve 81 more HF in downstream side is replaced as rare gas element.Like this, remaining HF in the HF supply line 24 all can be delivered in the electrolyzer 1.Even when the supply of the rare gas element of rare gas element hold-up vessel 92 was cut off, the rare gas element that has also stored sufficient quantity was used for remaining HF in the HF supply line 24 is delivered to electrolyzer 1 and the HF in the pipeline is replaced as rare gas element from the rare gas element supply source.
As described above, the apparatus for generating fluorine gas of present embodiment, by the effect that provides rare gas element to play the vector gas of HF to the HF supply line, simultaneously when HF stops to supply with or is unusual, will than the 1st self-acting valve of closing more the HF in the HF supply line in downstream side be replaced as rare gas element.
Embodiments of the invention more than have been described, but have the invention is not restricted to above-mentioned form of implementation, can shown in Fig. 3 (a)～Fig. 3 (c), do various design alterations like that in the claim scope.For example, in form of implementation, the 2nd self-acting valve 73 is and promptly stops the formation that feeler mechanism's interlock is opened, but but the formation of also often opening.In addition, if adopt this formation, even when HF stops to supply with, can a switch the 1st self-acting valve 81, rare gas element supply line the 91, the 3rd self-acting valve in the downstream side after not needing to shunt, self-acting valve 74.
In the above-mentioned form of implementation,, also can adopt the formation of not establishing rare gas element hold-up vessel 92 from the supply of the stable rare gas element of outside by accepting though utilize rare gas element hold-up vessel 92 to make the supply of rare gas element stable again.
Form of implementation of the present invention constitutes as described above, when the supply of the HF of apparatus for generating fluorine gas stops, or when unusual, the 1st self-acting valve 81 is closed, self-acting valve 82 is opened, self-acting valve 74 is closed and the 2nd self-acting valve 73 is opened, and ratio the 1st self-acting valve 81 in HF gas supply pipe road 24 more provides rare gas element in the downstream side.Like this, even when the supply that stops HF, can not become negative pressure in the downstream side than the 1st self-acting valve 81, electrolytic solution can not flow in the HF gas supply pipe road 24 more yet.Again, because outside during HF supplies with, HF is replaced as rare gas element, so, can reduce the time that devices such as the under meter 83 that is configured on the pipeline, pressure warning unit 84 contact with HF.
Again, by rare gas element hold-up vessel 92 is set, even when stopping, also can stably provide rare gas element to HF supply line 24 from the supply instability of rare gas element supply source or supply itself.
If employing the present invention, even when the supply to the HF of electrolyzer stops, cutting off by ratio the HF supply line HF supply self-acting valve more in the pipeline in downstream side remaining HF be replaced as rare gas element, can not become negative pressure in the HF supply line.Like this, can prevent that electrolytic solution from flowing into the HF supply line, can obtain to protect to be installed in simultaneously not to be subjected to HF corrosive effect by the machine on the pipeline of inert gas replacement.
Claims (5)
1. apparatus for generating fluorine gas is to be used for electrolysis by containing the electrolytic solution that hydrofluoric mixed melting salt constitutes and produce the apparatus for generating fluorine gas of fluorine gas, it is characterized in that having: the hydrogen fluoride gas supply line that hydrogen fluoride gas is provided in aforementioned electrolyte; Be configured on the aforementioned hydrogen fluoride gas supply line and the 1st self-acting valve of when the supply of aforementioned hydrogen fluoride gas stops, closing; When the supply of aforementioned hydrogen fluoride gas stops, discharging aforementioned the 1st self-acting valve of the ratio hydrogen fluoride gas in the pipeline in downstream side and be replaced into the inert gas replacement mechanism of rare gas element more remain in aforementioned hydrogen fluoride gas supply line.
2. apparatus for generating fluorine gas as claimed in claim 1, it is characterized in that: aforementioned inert gas replacement mechanism has the feeler mechanism that the supply that detects aforementioned hydrogen fluoride gas stops, to than aforementioned the 1st self-acting valve the more aforementioned hydrogen fluoride gas supply line in downstream side the rare gas element supply line of rare gas element is provided, with be configured on the aforementioned rare gas element supply line and with the 2nd self-acting valve of aforementioned feeler mechanism linked switch, when the supply that detects aforementioned hydrogen fluoride gas by aforementioned feeler mechanism stopped, the 2nd self-acting valve was opened and is more provided rare gas element in the pipeline in downstream side to aforementioned the 1st self-acting valve of the ratio of aforementioned hydrogen fluoride gas supply line.
3. apparatus for generating fluorine gas as claimed in claim 1 or 2 is characterized in that: aforementioned rare gas element supply line has the rare gas element hold-up vessel that stores the rare gas element of supplying with.
4. apparatus for generating fluorine gas is to be used for electrolysis by containing the electrolytic solution that hydrofluoric mixed melting salt constitutes and produce the apparatus for generating fluorine gas of fluorine gas, it is characterized in that having: the hydrogen fluoride gas supply line that hydrogen fluoride gas is provided in aforementioned electrolyte; Be configured on the aforementioned hydrogen fluoride gas supply line and the 1st self-acting valve of when the supply of aforementioned hydrogen fluoride gas stops, closing; When aforementioned apparatus for generating fluorine gas is unusual, discharge aforementioned the 1st self-acting valve of the ratio hydrogen fluoride gas in the pipeline in downstream side and be replaced into the inert gas replacement mechanism of rare gas element more remain in aforementioned hydrogen fluoride gas supply line.
5. apparatus for generating fluorine gas as claimed in claim 4 is characterized in that: aforementioned rare gas element supply line has the rare gas element hold-up vessel that stores the rare gas element of supplying with.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP336406/2002 | 2002-11-20 | ||
| JP2002336406A JP3527735B1 (en) | 2002-11-20 | 2002-11-20 | Fluorine gas generator |
| JP336406/02 | 2002-11-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1502548A CN1502548A (en) | 2004-06-09 |
| CN1266031C true CN1266031C (en) | 2006-07-26 |
Family
ID=32212090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101196923A Expired - Fee Related CN1266031C (en) | 2002-11-20 | 2003-11-20 | Fluorine gas generator |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20040108201A1 (en) |
| EP (1) | EP1422319A3 (en) |
| JP (1) | JP3527735B1 (en) |
| KR (1) | KR100543647B1 (en) |
| CN (1) | CN1266031C (en) |
| TW (1) | TWI242537B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104126031A (en) * | 2011-12-22 | 2014-10-29 | 索尔维公司 | Method of feeding hydrogen fluoride into an electrolytic cell |
| US11518696B2 (en) | 2018-08-29 | 2022-12-06 | Mks Instruments | Ozonated water delivery system and method of use |
Families Citing this family (21)
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| JP3569277B1 (en) * | 2003-05-28 | 2004-09-22 | 東洋炭素株式会社 | Current control method and current control device for gas generator |
| CN101248216B (en) | 2005-08-25 | 2010-06-16 | 东洋炭素株式会社 | Fluorogas generator |
| JP4018726B2 (en) * | 2006-02-07 | 2007-12-05 | 東洋炭素株式会社 | Semiconductor manufacturing plant |
| JP4606396B2 (en) | 2006-09-15 | 2011-01-05 | 東京エレクトロン株式会社 | Process gas supply system and process gas supply method |
| JP5659449B2 (en) * | 2008-03-04 | 2015-01-28 | カシオ計算機株式会社 | Fluorine gas generation method |
| ES2401156T3 (en) * | 2008-06-25 | 2013-04-17 | Basf Se | Procedure to safely avoid a return current during the transport of a liquid |
| JP5659491B2 (en) * | 2009-01-30 | 2015-01-28 | セントラル硝子株式会社 | Semiconductor manufacturing equipment including fluorine gas generator |
| JP5521372B2 (en) | 2009-04-03 | 2014-06-11 | セントラル硝子株式会社 | In-situ gas mixing and dilution system for fluorine gas |
| JP2011084806A (en) * | 2009-06-29 | 2011-04-28 | Central Glass Co Ltd | Fluorine gas generation device |
| JP5581676B2 (en) * | 2009-12-02 | 2014-09-03 | セントラル硝子株式会社 | Fluorine gas generator |
| JP5544895B2 (en) * | 2010-01-21 | 2014-07-09 | セントラル硝子株式会社 | Fluorine gas generator |
| KR20130079363A (en) * | 2010-03-26 | 2013-07-10 | 솔베이(소시에떼아노님) | Method for the supply of fluorine |
| JP5431223B2 (en) | 2010-03-29 | 2014-03-05 | 東洋炭素株式会社 | Gas generator |
| TWI525042B (en) * | 2010-09-16 | 2016-03-11 | 首威公司 | Hydrogen fluoride supply unit |
| US20120092950A1 (en) * | 2010-10-15 | 2012-04-19 | Bertrand Michel Jean-Claude Colomb | Low pressure drop blender |
| WO2013092773A1 (en) * | 2011-12-22 | 2013-06-27 | Solvay Sa | Liquid level control in an electrolytic cell for the generation of fluorine |
| CN105089869B (en) * | 2015-06-04 | 2018-12-14 | 武汉大学 | A kind of double telescopic electrode waters make the internal-combustion engine arrangement of fuel |
| CN106757145A (en) * | 2017-03-07 | 2017-05-31 | 洛阳黎明大成氟化工有限公司 | A kind of electrolytic cell automates feeding device and its application method with hydrogen fluoride |
| CN110965078A (en) * | 2019-12-10 | 2020-04-07 | 中核二七二铀业有限责任公司 | Automatic control device for hydrogen fluoride feeding |
| FR3111133A1 (en) * | 2020-06-04 | 2021-12-10 | Université du Mans | AUTOMATED CHEMICAL TREATMENT PROCESS OF A SOLID SUBSTRATE BY A FLUORATION LINE |
| CN114789915B (en) * | 2022-04-11 | 2023-10-24 | 福建省龙德新能源有限公司 | Continuous automatic production method of phosphorus pentafluoride |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2967466A (en) * | 1956-06-20 | 1961-01-10 | Warren Brothers Road Company | Pavement and method of making the same |
| JPH0353090A (en) * | 1989-07-18 | 1991-03-07 | Asahi Glass Co Ltd | Production of fluorine |
| JP2809811B2 (en) * | 1990-04-27 | 1998-10-15 | 三井化学株式会社 | Method for producing nitrogen trifluoride gas |
| US6350425B2 (en) * | 1994-01-07 | 2002-02-26 | Air Liquide America Corporation | On-site generation of ultra-high-purity buffered-HF and ammonium fluoride |
| GB9418598D0 (en) | 1994-09-14 | 1994-11-02 | British Nuclear Fuels Plc | Fluorine cell |
| US6383300B1 (en) * | 1998-11-27 | 2002-05-07 | Tokyo Electron Ltd. | Heat treatment apparatus and cleaning method of the same |
| KR100485490B1 (en) * | 2000-04-07 | 2005-04-28 | 도요탄소 가부시키가이샤 | Apparatus for generating fluorine gas |
| JP2002164335A (en) * | 2000-11-27 | 2002-06-07 | Canon Sales Co Inc | Method for cleaning semiconductor manufacturing apparatus, and the semiconductor manufacturing apparatus |
| US20040037768A1 (en) * | 2001-11-26 | 2004-02-26 | Robert Jackson | Method and system for on-site generation and distribution of a process gas |
-
2002
- 2002-11-20 JP JP2002336406A patent/JP3527735B1/en not_active Expired - Fee Related
-
2003
- 2003-10-24 TW TW092129624A patent/TWI242537B/en not_active IP Right Cessation
- 2003-11-07 US US10/702,646 patent/US20040108201A1/en not_active Abandoned
- 2003-11-19 KR KR1020030082052A patent/KR100543647B1/en not_active IP Right Cessation
- 2003-11-19 EP EP03026445A patent/EP1422319A3/en not_active Withdrawn
- 2003-11-20 CN CNB2003101196923A patent/CN1266031C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104126031A (en) * | 2011-12-22 | 2014-10-29 | 索尔维公司 | Method of feeding hydrogen fluoride into an electrolytic cell |
| US11518696B2 (en) | 2018-08-29 | 2022-12-06 | Mks Instruments | Ozonated water delivery system and method of use |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1422319A2 (en) | 2004-05-26 |
| KR100543647B1 (en) | 2006-01-20 |
| CN1502548A (en) | 2004-06-09 |
| KR20040044371A (en) | 2004-05-28 |
| JP2004169123A (en) | 2004-06-17 |
| JP3527735B1 (en) | 2004-05-17 |
| EP1422319A3 (en) | 2011-08-10 |
| TWI242537B (en) | 2005-11-01 |
| TW200409833A (en) | 2004-06-16 |
| US20040108201A1 (en) | 2004-06-10 |
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