CN104350181A - Liquid level control in an electrolytic cell for the generation of fluorine - Google Patents

Abstract

The invention pertains to a method of measuring and/or controlling the electrolytic bath liquid level in an electrolysis cell for the generation of fluorine gas having an anode chamber and a cathode chamber separated from each other by a partition wall for generating fluorine gas by electrolyzing an electrolytic bath (electrolyte) comprising a hydrogen fluoride-containing mixed molten salt of an HF adduct of KF, wherein the method comprises the steps of (a) detecting the pressure in at least one of the anode chamber and the cathode chamber during generation of fluorine gas by pressure sensing means comprising a tube (liquid level sensing tube) reaching (submersing) into the electrolytic bath (electrolyte), and, preferably, (b) supplying through the tube of the pressure sensing means an effective amount of hydrogen fluoride to thereby remove and/or prevent plugging caused by potentially crystallized HF adduct of KF in the tube of the pressure sensing means at any time and/or during measuring and/or controlling the electrolytic bath (electrolyte) liquid level in the anode chamber and/or cathode chamber.

Description

For generation of the Liquid level in the electrolyzer of fluorine

The benefit of priority of the EP number of patent application 11195431.9 that application claims was submitted on December 22nd, 2011, the full content of this patent application is combined in this by reference for all objects.

The present invention relates to one and carry out improving one's methods of Liquid level to the ionogen in electrolyzer (electrolyzer), this electrolyzer is the fusion electrolysis generation simple substance fluoride for the HF adducts by KF; And preferably relate to one carry out Liquid level and prevent and/or remove improving one's methods of the tamper in the pipe for controlling the electrolytical liquid level in electrolyzer (electrolyzer), this electrolyzer is the fusion electrolysis generation simple substance fluoride for the HF adducts by KF simultaneously.

Electrolysis produce simple substance fluoride often intend a kind of for the manufacture of the method for electron device in for supply (conveying).Simple substance fluoride (F ₂) not there is GWP (global warming potential) and ozonosphere is not affected.Simple substance fluoride be suitable for makes fluorizating agent, such as the manufacture of the polymkeric substance be fluorinated from the teeth outwards, for the manufacture of the solvent be fluorinated being particularly useful for Li ionization cell; Be used as the chamber clean agent and etching reagent that manufacture electron device, these electron devices are semi-conductor, barrier-layer cell, microelectromechanical systems (" MEMS "), TFT (thin film transistor of flat-panel monitor or liquid-crystal display) etc. especially.

Manufacturing electron device, the especially etching reagent of semi-conductor, barrier-layer cell, MEMS and TFT about being used as, depositing multiple layer and several consecutive steps etching the part of these layers are necessary.Fluorine may be used for etching by multiple layers of very different contextures, such as, for etching silicon-containing layer or other layers of compound forming volatile reaction product (such as tungsten).Etching especially can under light is auxiliary, carry out with hot mode or under plasmaassisted.

About for chamber clean, usually (be often that (wherein to CVD chamber multiple layer pass through chemical vapour deposition in treatment chamber, such as plasma enhanced CVD, metallorganic CVD or low pressure chemical vapor deposition and the chamber that is deposited in multiple project)) in during the depositing operation that carries out, undesirable settling is formed and must regularly remove on walls of the chamber with in Inner Constitution part.This is by realizing with hot mode or plasma enhancing mode process settling as chamber clean agent with simple substance fluoride.

Especially etching reagent is used as simple substance fluoride, and when it is used as chamber clean agent, desirably this simple substance fluoride is very pure.The intrusion of water, carbonic acid gas, nitrogen and oxygen is considered to undesirable.

Simple substance fluoride can be produced by diverse ways, but often electrolytically (as mentioned above) produced by hydrogen fluoride (HF), this hydrogen fluoride is as the feed material of electrolysis and the source of simple substance fluoride.Under a kind of electrolytic salt exists, if apply at least 2.9V voltage, so HF discharges fluorine.In fact, voltage often remains in the scope of 8 volts to 11 volts.

Typically, the adducts often with the melting HF of formula KF (1.8-2.3) HF, KF is preferred electrolytic salt.HF is sent in the reactor containing fused electrolyte salt, and by applying voltage and making electric current by this melting salt, electrolytically forms F according to reaction formula (1) by HF ₂:

2HF→H ₂+F ₂(1)

Hydrogen fluoride is particularly useful as chemical fabrication processes (as passed through molecular fluorine (F ₂) electrolysis manufactures) and feed material, be suitable for the chamber clean gas in work such as semicon industry, and be applicable to manufacture other chemical fluoridized, as fluorinated hydrocarbons.

After manufacturing fluorine by electrolysis manufacture (or any other method), it can be stored in pressurized cylinder and to be transported to field of employment.There is higher F ₂in the factory of demand, preferably directly produce F at the scene ₂.

WO 2004/009873 discloses a kind of equipment and method for being produced fluorine by hydrogen fluoride electrolysis.Fluorine is produced by HF electrolysis by producing in case at fluorine.Fluorine can use in manufacture electron device, such as, use in production TFT.

This equipment comprises: multiple independent fluorine produces case; Described independent fluorine produces case and to be operably connected on a fluorine gas distribution system for long-range use and to consume described fluorine gas; Described fluorine generation case and described gas distributing system are separable individually and slave unit are demountable for remote maintenance.According to reference paper WO 2004/009873, the supplies of liquid hydrogen fluoride is contained in a storage tank.A hydrogen fluoride vaporizer makes liquid hydrogen fluoride vaporize from storage tank and it is supplied to these casees to maintain the ionogen of constant density, and this ionogen comprises the adducts of the melting HF of KF as previously mentioned.

In electrolysis with during forming simple substance fluoride, hydrogen fluoride (HF) is consumed.The consumption of hydrogen fluoride (HF) have impact on the amount of ionogen in electrolyzer (adducts of the melting HF of such as KF) and therefore affects electrolytical liquid level.Therefore, for lasting formation fluorine, fresh HF must be sent into every now and then in electrolyzer and keep within the specific limits with the liquid level making can be used as the HF of fluorine source, electrolysis can be carried out to obtain that there is the fluorine that can accept purity within the scope of this.Usually, such as, with regard to the preferred electrolyte salt of the adducts of the melting HF of KF, the scope of HF changes according to chemical formula KF (1.8-2.3) HF usually.Further, electrolytical height (electrolyte level) must keep within the specific limits to guarantee that electrolysis runs under proper condition, thus produces the simple substance fluoride with required quality.Therefore, importantly to monitor the electrolyte level in electrolyzer as an index of HF content in electrolyzer regulate hydrogen fluoride to send into amount in electrolyzer and the timed interval as feed material, such as, to use the electrolytic salt of the adducts of the melting HF of KF (scope of HF changes according to formula KF (1.8-2.3) HF usually) to run this electrolyzer in the scope of required electrolyte level.

If the condition in electrolyzer (comprising the electrolyte level in pond) is not fully controlled and regulates to meet the operational condition in electrolyzer noted earlier, so this may cause make temperature and ionogen composition keep on room and time even in go wrong, and consequence is that impurity is (as CF ₄, OF ₂, O ₂) formation may increase in fact, thus it is low-quality to cause fluorine to have in purity.For many application, need high-purity fluorine or be at least the fluorine that there is minimum impurity, particularly at the scene in technique, these site techniques should be simple as far as possible, there is less artificial interference, continuously produce high-purity fluorine and minimum to the demand of additional purification measures.

Typically, in the state of the art, the electrolyzer producing (height) pure fluorine gas by a kind of hydrofluoric electrolytic bath comprising the melting salt form of HF adducts in KF of electrolysis will be equipped with multiple liquid level sensing device, and they can sense in anode chamber and the liquid level of electrolytic bath (ionogen) in cathode chamber accordingly.

For as required with the operation at scene, in electrolyzer, the automatic control of electrolyte level is indispensable for the security in automatic operation.About the technology controlling electrolyte level fluctuation, such as, published patent EP0728228B1, EP0852267B1, EP0965661B1 and USP5688384 propose so-called starting/stopping (ON/OFF) control.But, when using this technology to carry out electrolysis, produce a problem.That is, when fluctuation to a certain degree appears in liquid level, electrolysis is interrupted, and electrolysis cannot be reset before electrolyte level gets back to original level.

Published patent application EP1367149A1 discloses a kind of fluorine gas generator being produced high-purity fluorine gas by a kind of hydrofluoric electrolytic bath comprised in melting mixing salt form of electrolysis, this generator comprises: an electrolyzer, and this electrolyzer is divided into a positioned inside by a dividing wall has the anode chamber of anode and positioned inside to have the cathode chamber of negative electrode; Multiple pressure maintenance device, they are for by electrolyzer inner sustain under atmospheric pressure; And multiple liquid level sensing device, they can sense accordingly in anode chamber and be in the liquid level of three or more liquid level levels with the electrolytic bath in cathode chamber.According to this structure, the minor fluctuations of liquid level can be detected, and can by anode chamber, inner and cathode chamber inner sustain is under atmospheric pressure by means of pressure maintenance device.Consequently, the liquid level of electrolytic bath is integrally stablized.Therefore, the fluctuation of electrolytic condition during can electrolysis being reduced, and the stable supply of fluorine gas becomes possibility.In addition, because anode chamber is inner and cathode chamber inside is maintained under atmospheric pressure, so can prevent air etc. from flowing to chamber from outside, thus high-purity fluorine gas can be produced by stationary mode.

In addition, published patent application EP1457587A1 discloses a kind of fluorine gas generator being produced fluorine gas by a kind of electrolytic bath comprising fluorinated hydrogen mixed melting salt of electrolysis, this generator comprises the anode chamber and a cathode chamber that are separated by a dividing wall each other and is provided with electrolytic bath fluid level control device, for controlling the height of the electrolytic bath liquid level in the interval anode chamber that produces at fluorine gas and cathode chamber at least one chamber.Multiple pressure control devices that this electrolytic bath Liquid level comprises multiple pressure-sensing device and operates explicitly with these pressure-sensing devices.In a kind of change type, electrolytic bath fluid level control device (in particular for determining the liquid level of 5 position levels) for controlling the liquid level in anode chamber comprises a pressure-sensing device and a pressure control device, and this pressure control device and this pressure-sensing device operate explicitly and the pressure controlled in anode chamber controls the liquid level difference in anode chamber and cathode chamber with the electric current be suitable for by anode supply.

The object of the present invention is to provide a kind of method being used for measuring and/or controlling electrolyte level, the method allows to measure the liquid level regardless of position level, but measures any desired liquid level.

According to the first embodiment, the invention provides and a kind ofly measure and/or control in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, this electrolyzer has at least one anode chamber of being separated by dividing wall each other and at least one cathode chamber and electrolytic bath (ionogen) for the fluorinated hydrogen mixed melting salt of the HF adducts that comprised KF by electrolysis produces fluorine gas, wherein the method comprises the following steps: (a) stretches into the pressure-sensing device of the pipe (liquid level sensing pipe) in (immersion) this electrolytic bath (ionogen) to detect the pressure in anode chamber and cathode chamber at least one chamber during fluorine gas produces by comprising.Preferably, the liquid thereby in this pipe helps a kind of rare gas element of having replaced liquid in this pipe and replaces, and to measure in this rare gas element and this anode chamber and cathode chamber the pressure difference between at least one the gas space.

Immerseable pipe is that the one in framework of the present invention preferably measures sensing apparatus.

In a replacement scheme, preferably measure the electrolyte level of anode chamber.In a further alternative, the electrolyte level in cathode chamber is preferably measured.Needless to say, structured material reply ionogen used and H ₂there is resistance, if analyze negative electrode liquid level (such as PTFE material is applicable); And to ionogen and F ₂there is resistance, if analyze anode liquid level (such as stupalith can be used).

A kind of optimal way measuring electrolyte level is pressed in this pipe by a kind of rare gas element, makes some rare gas elementes leave this pipe.The pressure of replacing needed for the ionogen in this pipe is the one instruction of electrolyte level height: liquid level is lower, and the pressure of replacing in this pipe needed for liquid is lower, and correspondingly, lower with the pressure difference of the gas space in anodal compartment and cathodic compartment.Depend on corresponding pipe, pond etc., can calibrate between measured pressure difference and electrolyte level.If necessary or if desired, indicated by level gauging, ionogen can be supplied manually or automatically.Pressure difference or absolute pressure can be measured.

Electrolyte level can be measured in cathode chamber or in anode chamber.Often, electrolyte level is measured and will be carried out in anode chamber.N ₂a kind of preferred rare gas element, especially for the measurement in cathode chamber, F ₂also may be used in anode chamber; This is preferred, because F ₂gas can not produce pollution thus in anode chamber.If measure liquid level in cathode chamber, N ₂or H ₂it is preferred rare gas element.Other rare gas elementes can be used equally.

Also likely apply HF as the rare gas element for the level gauging in these two compartments, but the possibility of result is not as using F ₂or N ₂equally accurate.

Must be pointed out, method of the present invention and can have one or more anode and wherein cell container is used as to apply in the equipment of negative electrode in the electrolyzer with one or more anode and one or more negative electrode (having corresponding chamber).Term " chamber " is intended to comprise term " compartment ".Method as indicated above allows to measure any desired electrolyte level; It is not limited to measure liquid level level.However, still there is a shortcoming hereinafter described in this method of the present invention.

Observe, when using multiple pressure-sensing device measure and control electrolytical liquid level, composition due to the electrolytic salt of the adducts of the melting HF of KF changes in time and may go wrong, wherein the scope of HF changes according to formula KF (1.8-2.3) HF usually, as previously mentioned.When the composition of the adducts of the melting HF of KF changes, such as when dropping to lower than value 2 according to the HF content in the salt of formula KF (1.8-2.3) HF, fusing point becomes relatively high and may cause the adducts salt-pepper noise of immerseable pressure measuring tube inside (salt of crystallization is also referred to as " freezing " salt); Can the splash ionogen of crystallization also can throw into question in pipe subsequently.Consequently, when pipe inside diameter reduces and particularly when blocking occurs pipe, the pressure survey of electrolytic bath and Liquid level impaired because of this crystallization.

Therefore, another object of the present invention is that providing a kind of is measured by pressure-sensing and control device and/or control improving one's methods for generation of the electrolyte level in the electrolyzer of fluorine, and in this electrolyzer, electrolytic salt is the adducts of the melting HF of KF.This is improved one's methods and also should allow stable and produce safely in the electrolysis of (height) pure fluorine gas and undertaken reliably by pressure-sensing and/or control device and particularly continuous print level gauging and/or control to run electrolyzer, such as, this is because level gauging and/or the inner undesirable HF-KF adducts salt-pepper noise of control tube can be minimized and can prevent blockage.

This object of the present invention is realized by second embodiment of the invention, this embodiment comprises amendment and is measured by pressure-sensing and/or control device and/or control in this method for generation of the electrolyte level in the electrolyzer of fluorine, and in this electrolyzer, electrolytic salt is the adducts of the melting HF of KF.According to the second embodiment of the invention measured by pressure-sensing and/or control device and/or control electrolyte level improve one's methods should as Fig. 1 paint, and Fig. 2 depicts first embodiment of the inventive method.

As in Fig. 1 second embodiment of the present invention of summarizing, that is, comprising this method according to improvement of the present invention, be a highly preferred embodiment, and referenced in schematic further describes hereinafter.

Brief Description Of Drawings

Fig. 1 shows this second embodiment, that is, to be measured by pressure-sensing and/or control device according to the present invention and/or control improving one's methods of electrolyte level in electrolyzer.

Fig. 2 describes this first embodiment, that is, by means of applying rare gas element (such as nitrogen) for measure differences in pressure, being measured and/or control the method for the electrolyte level in electrolyzer by pressure-sensing and/or control device.The valve marked by " X " is no longer required.

Detailed description of the invention

According to the first embodiment of the present invention (see Fig. 2), in the electrolyte level of carrying out every now and then is measured, by nitrogen or a kind of applicable rare gas (such as helium or argon gas) or as described above accordingly by F ₂or H ₂or or even the pipe that stretches in ionogen by means of one under certain superpressure of HF be applied to electrolyzer.Depend on electrolytical height in electrolyzer, detecting pressure difference is as an index of electrolyte level.Under such a configuration, if drop to lower than value 2 according to the HF content in the salt of formula KF (1.8-2.3) HF, so the freezing HF adducts and may cause for tonometric pipe weekly until block every day of KF.This salt that freezes cannot be removed simply by brushing pipe with nitrogen.Therefore, the ionogen solidified, such as KF freezes HF adducts, must be removed by scraping every now and then, and this operation quite bothers.

Object of improving one's methods (see Fig. 1) of the present invention to be measured by pressure-sensing and/or control device by a kind of and/or controlled to realize at the modification method for generation of the electrolyte level in the electrolyzer of fluorine, in this electrolyzer, electrolytic salt is the adducts of the melting HF of KF, be except nitrogen or any other rare gas element be applicable to according to the feature of modification method of the present invention, under certain superpressure, also hydrogen fluoride (HF) is applied to electrolyzer by means of the same pipe stretched in ionogen, this pipe is for measuring and/or controlling electrolyte level.

In the context of the present invention, wording " rare gas element " be intended to refer to do not disturb ionogen and electrolytic spawn-such as do not occur with them chemical reaction-a kind of gas (if desired, may be a kind of gaseous mixture).

Specifically, the object of the invention is by a kind of measure and/or control to realize in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, this electrolyzer has at least one anode chamber of being separated by dividing wall each other and at least one cathode chamber and is that the electrolytic bath (ionogen) of the fluorinated hydrogen mixed melting salt of the HF adducts for being comprised KF by electrolysis produces fluorine gas, wherein the method comprises the following steps: (a) during fluorine gas produces by comprise stretch into pipe in electrolytic bath (ionogen) (liquid level senses pipe) pressure-sensing device to detect the pressure in anode chamber and cathode chamber at least one chamber, and by the pipe of the hydrogen fluoride supply of significant quantity through this pressure-sensing device during (b) electrolytic bath (ionogen) liquid level at any time and/or in measurement and/or control anode chamber and/or cathode chamber, remove and/or prevent the blocking caused by the HF adducts of the KF of possible crystallization in the pipe of this pressure-sensing device thus.

As mentioned above, the electrolyzer of other types applies one or more anode and uses the container of electrolyzer as negative electrode.Often, 20 or more, nearly 30 and even more anode are accommodated in an electrolyzer.Space around each anode and the liquid of encirclement are such as separated by " skirt encloses (skirt) ", to prevent formed F ₂dissipate arrive cathodic compartment in the electrolyte or in a gaseous form, this is because in cathodic compartment F ₂with H ₂combine again and form HF, cause a kind of chemical reaction of danger strongly.The gas space in this anodal compartment is by F ₂formed, extract out and collect F ₂for being further purified, storing or carrying.Such equipment describe be especially applicable to is in international patent application WO 2012/066054 (application number PCT/EP 2011/070286 submitted on November 16th, 2011), and the full content of this application is combined in this by reference.

Wording " one ", such as, in the statement of such as " step ", is not intended to this statement is restricted to an one step.Term " comprise " comprise implication " by ... composition ".

Wording " pipe " represents a hollow pipeline with the certain internal diameter allowing gaseous state and/or fluent meterial to flow through, and synonymously can use with wording " pipeline " or " pipeline " in the art.

In a preferred embodiment, the present invention relates to a kind of as hereinbefore defined for generation of the electrolyzer of fluorine gas in measure and/or control the method for electrolytic bath liquid level, in this electrolyzer, molten salt electrolyte is the adducts of the melting HF of KF, preferably have the scope of the HF according to formula KF (1.8-2.3) HF, the adducts of the melting HF of KF.

Use removes according to hydrogen fluoride of the present invention (HF) and/or prevents any obstruction caused by the HF adducts of the KF of possibility crystallization in the pipe of pressure-sensing device, a kind of simple and favourable measure, this is because specifically hydrogen fluoride (HF) is all be used as generation of the feed material in the electrolysis of fluorine gas in any case.Therefore, it can be drawn from the identical storage receptacle for the supply HF when being manufactured fluorine by electrolysis.By the hydrogen fluoride (HF) of significant quantity being supplied the pipe through this pressure-sensing device, the HF adducts any that may freeze, KF that can effectively dissolve in this pipe itself and/or pipe near zone maybe can increase HF by local and effectively prevent freezing of the HF adducts of KF.Under this background of the present invention, wording " effectively " or " effectively " have following implication: be increased to the value being equal to or greater than 2, particularly in pipe itself and/or pipe near zone according to the HF content in the salt of formula KF (1.8-2.3) HF.Thus, according to the present invention, can at any time and/or measure and/or remove simply and/or prevent during controlling electrolytic bath (ionogen) liquid level in anode chamber and/or cathode chamber thisly to freeze salt.

Hydrogen fluoride (HF) can be supplied to this liquid level to sense pipe by liquid HF form or gaseous state HF form." hydrogen fluoride " (HF) is interpreted as referring in particular to for anhydrous hydrogen fluoride.When being included in a storage receptacle, hydrogen fluoride is liquid normally.Therefore, when supplying liquid HF, HF can directly draw by required amount and transfer in this liquid level sensing pipe from storage receptacle, such as, shift by pumping or simply by applying pressure to this container and being pressed into by HF in liquid level sensing pipe.When supplying gaseous state HF, this storage receptacle is equipped with a vaporizer in addition, and liquid HF evaporates subsequently and transfers in liquid level sensing pipe from storage receptacle.

In addition, the chamber of any one type of electrolyzer can be applied to according to method of the present invention (step (a) of the method and (b)), such as, it can be applied to anode chamber (fluorine generation side) and cathode chamber (hydrogen generation side) comparably.Preferably anode chamber (fluorine generation side), and can optionally be replaced by fluorine gas for the nitrogen of level gauging or rare gas in this case.If the present invention is applied to cathode chamber (hydrogen generation side) (in the step (a) of method according to the present invention and (b)), so in this case can optionally by hydrogen exchange for the nitrogen of level gauging or rare gas.

Before describing the present invention in more detail, first the present invention should set forth the content of the electrolyzer for generation of fluorine, and in this electrolyzer, electrolytic salt is the adducts of the melting HF of KF.Fluorine gas produces in the electrolyzer comprising an anode chamber and a cathode chamber.Electrolyzer main body is normally by Ni, Monel metal (Monel), carbon steel etc. or to H ₂, F ₂, KF and the HF other materials with resistance makes.In the bottom of electrolyzer main body, a base plate be made up of nickel or tetrafluoroethylene etc. is settled to enter in an anodal compartment and F to prevent the hydrogen produced in conductive bottom ₂mix and enter in the reaction of formation HF.A kind of electrolytic bath is filled with, that is, a kind of Potassium monofluoride-hydrogen fluoride system in melting salt form (in this article so-called " KF-HF adducts " etc.) by electrolyzer main body.Pond or bath are enclosed by means of a skirt be made up of Monel metal etc. and are divided at least one anode chamber or anodal compartment and at least one cathode chamber or compartment.Each pond preferably containing several anodes, typically 20 to 30, they can such as by nickel, carbon, agglomerated material, be coated with adamantine anode or comparable material is made, but be usually made up of carbon.When applying voltage between a nickel cathode contained in a carbon contained in anode chamber or nickel anode and cathode chamber, there is electrolysis and produce fluorine gas.The fluorine gas produced is discharged by a product pipeline, and is discharged by a hydrogen discharge pipe line at the hydrogen that cathode side is formed.

The minor fluctuations of liquid level can be detected, and can by means of pressure maintenance device by anode chamber inner and cathode chamber inner sustain under atmospheric pressure or preferably a little higher than normal atmosphere.Pressure maintenance device in fluorine gas generator generally includes the multiple self-acting valves operating (opening/closing) with the multiple pressure warning units be connected to accordingly in anode chamber and cathode chamber explicitly, and the multiple self-acting valves operated explicitly with the liquid level sensing device be placed in accordingly in anode chamber and cathode chamber.This structure make with one easily and reliably mode control electrolyzer internal pressure and become possibility.These self-acting valves and the operation be associated of liquid level sensing device and the hydrogen fluoride HF of significant quantity is supplied the liquid level that the pipe through this pressure-sensing device makes automatic control electric solution bathe and become possibility.Therefore, likely in a kind of reliable mode at any time and/or measure measuring and/or carry out continuous and maintenance-free electrolyte level during controlling electrolytic bath (ionogen) liquid level in anode chamber and/or cathode chamber easily.According to the present invention, detect the electrolytic bath liquid level in electrolyzer during electrolytic bath (ionogen) liquid level likely at any time and/or in measurement and/or control anode chamber and/or cathode chamber, and therefore detect even very little liquid level change.

According to these embodiments of the present invention, the method comprises by pressure-sensing device to detect electrolyzer internal pressure, such as, the method comprises the following steps: (a) stretches into the pressure-sensing device of the pipe (liquid level sensing pipe) in (immersion) electrolytic bath (ionogen) to detect the pressure in anode chamber and cathode chamber at least one chamber during fluorine gas produces by comprising.

Can lower than under the pressure of ambient pressure, around under pressure and measure under the pressure of projecting pressure, this is because principle measures pressure difference.

Therefore, according to one embodiment of the invention, lead to rare gas (such as, as the rare gas of helium (He gas), neon (Ne gas), argon gas (Ar gas) or Krypton (Kr gas)) or the another kind of rare gas element (such as nitrogen (N of the one or more cathode chamber ₂gas)) or hydrogen (H ₂) or lead to the fluorine gas (F of the one or more anode chamber ₂gas), send in cathode chamber and/or anode chamber, to provide certain superpressure in the chamber of correspondence by multiple self-acting valve.Also may apply not with ionogen or the gas reaction produced or other gases not disturbing them.In a preferred embodiment of the invention, under a little higher than atmospheric pressure, carry out electrolysis, and subsequently may by described rare gas or the chamber preferably nitrogen is applied to enduringly in corresponding chamber, such as cathode chamber or anode chamber.Alternately or additionally, the F produced during electrolysis ₂and H ₂pressure can be provided.Must be pointed out, described rare gas element may produce undesirable impurity, especially at produced F ₂in.

This structure can make following situation become possibility: such as, the electrolyte level fluctuation controlling the electrolytic bath rising because differential pressure causes more accurately or decline and cause, and prevent the strainer etc. be positioned in downstream line and pipeline from blocking due to the splash of electrolytic bath.

This control makes to guarantee to operate in a kind of safe and stable mode and detect even very little liquid level change to become possibility.

Hereinafter, should according to for measuring and/or controlling describing the present invention in more detail for generation of the preferred embodiment of the electrolytic bath liquid level in the electrolyzer of simple substance fluoride and change type.

To comprise by pressure-sensing device to detect electrolyzer internal pressure and then to be comprised the following steps to the inventive method calculating the liquid level in electrolyzer by observed differential pressure: (a) during fluorine gas produces by comprising the pressure-sensing device of the pipe (liquid level senses pipe) stretched in electrolytic bath (ionogen) to detect the pressure in anode chamber and cathode chamber at least one chamber.(the compartment (" F producing fluorine can be such as represented in the anode chamber of electrolyzer ₂side ")) middle detecting pressure; But the pressure preferably measured in cathodic compartment.Therefore, a preferred embodiment provides a kind of and measures and/or control in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine, and the pipe (liquid level sensing pipe) wherein stretched in (immersion) electrolytic bath (ionogen) is for the cathode chamber (" H at electrolyzer ₂side ") in carry out pressure detection.

The present invention also measures and/or controls in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas for a kind of, and wherein this electrolytic bath (ionogen) liquid level is by by means of rare gas or nitrogen or its any mixture, preferably by means of nitrogen (N ₂) gas measures differential pressure (Δ P) and measure, described gas is stretched into pipe in (immersions) electrolytic bath (ionogen) (liquid level sensing pipe) be pressed in electrolyzer by by means of this.In order to measure differential pressure (Δ P), do not having under pressure compensated condition, by means of the pipe stretched in electrolytic bath (ionogen) (liquid level sensing pipe) by the one press-in electrolyzer in rare gas mentioned above or nitrogen or its any mixture; Under these conditions, be closed (see Fig. 2) for carrying out this valve pressure compensated between the gas zone above the liquid electrolyte in pipe and electrolyzer or preferably even do not exist.Thus, progressively mineralization pressure P in pipe ₁, and depend on the pressure P of the gas zone above the liquid electrolyte in electrolytical actual liquid level and electrolyzer ₂, determine differential pressure (delta-P, Δ P).By rule of thumb, technician can carry out electrolytical liquid level computing pool from Δ P subsequently.Often, automatically calculating is performed by program control system (" PCS ") or digital control system (" DCS ").After the measurement, compensate pressure in electrolyzer and this pond get back to measurement before previous conditional.But by pressure compensation, ionogen may to be thus lifted in pipe and to there is fused electrolyte salt at pipe intercrystalline and may cause not wishing the risk of the blockage occurred subsequently.Likely with a certain amount of N without interruption ₂pressed gas is so that by a small amount of N ₂blast enduringly in ionogen, it is unimpeded to attempt holding tube thus, but even if has the N of minute quantity ₂, also cannot prevent a small amount of ionogen splash around pipe and still can cause crystallization and finally cause blockage.

According to the present invention, prediction makes hydrogen fluoride (HF+N together with nitrogen ₂) (this is preferred) or dividually (only HF) by this pipe., can continue to supply N in supply line to prevent the electrolyte backflow when stopping supply HF ₂.HF tends to the incrustation dissolving KF-HF adducts.Now, when applying the method according to the invention, if such as process in accordance with the present invention (b), by the supply of the hydrogen fluoride (HF) of significant quantity through the pipe of this pressure-sensing device, so hydrogen fluoride is likely removed thus and/or is prevented in the pipe of pressure-sensing device by may the blocking that causes of the HF adducts of KF of crystallization.There is N ₂or another advantage of supply hydrogen fluoride (HF) is, when using liquid HF, normal pressures as described above compensates not necessarily.When liquid HF being supplied to pipe, pressure compensation can have been come (see Fig. 1) by the HF itself added.Therefore, safeguard if wish to simplify electrolyzer and reduce it, such as required with in the operation at scene, so can remove the pressure-compensated valve shown in Fig. 2, in these operations, automatically and safely the electrolytic bath liquid level controlled in electrolyzer is indispensable, but manual maintenance should minimize by simplifying electrolyzer and electrolytic process as much as possible.

Although likely by the pipe through this pressure-sensing device without interruption for the hydrogen fluoride of significant quantity being implemented the present invention in step (b), but in a preferred embodiment of the invention, this measurement and/or control in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas to be allow in a kind of hydrofluoric mode being just periodically supplied with effective amount.In this embodiment of the present invention, hydrogen fluoride is (HF+N together with nitrogen preferably ₂) supply; If continue supply N after stopping supply HF ₂, electrolyte backflow so can be prevented in supply line.As an alternative, HF is supplied dividually (that is, only supplying HF) and stretch into pipe in (immersion) electrolytic bath (ionogen) (liquid level sensing pipe) through this.Like this, this measurement and/or control to continue supply N when this embodiment provides as interrupt delivery HF of the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas ₂.

The hydrofluoric cycle (interval) being supplied with effective amount may even for from the cycle of a several thoughtful complete cycle (such as seven days), from some skies (such as seven days) to the cycle of one day (such as 24 hours), cycle from some hours (such as 24 hours) to one hour (such as 60 minutes), or from cycle of some minutes (such as 60 minutes) to one minute (such as 60 seconds), or even from some seconds to the cycle of several seconds.Be in operating electrolyzer, cycle or interval depend on accordingly (b) at any time and/or measure and/or during controlling electrolytic bath (ionogen) liquid level in anode chamber and/or cathode chamber by the hydrogen fluoride supply of significant quantity through the pipe of this pressure-sensing device to remove thus and/or to prevent in the pipe at pressure-sensing device by may the actual demand of blocking that causes of the HF adducts of KF of crystallization.

In this context, if the cycle measures with week, so wording " several " represents that the time length in corresponding cycle is greater than one week, such as surrounding, but is usually no more than three weeks or preferably two weeks; If or the cycle be to measure second, so its represents and is greater than one second, such as at least five seconds, but at least ten seconds or preferably at least 20 seconds usually, and more preferably about 30 (30) seconds.

For example be not restriction, if the cycle measures with week or sky, so one week or more preferably cycle of one day is desirable.If the cycle is hour to measure, so such as 1 hour to 5 hours, preferably 1 hour to 4 hours, more preferably 1 hour by 3 hours and even more preferably the shorter interval of 1 hour to 2 hours be desirable.If the cycle is that so such as the shorter interval of 1 minute to 60 minutes, 1 minute to 50 minutes, 1 minute to 40 minutes, 1 minute to 30 minutes, 1 minute to 20 minutes or 1 minute to 10 minutes is the interval be in fact suitable for minute to measure; Preferably shorter interval can be selected, such as 1 minute to 5 minutes, preferably 1 minute to 4 minutes, more preferably 1 minute by 3 minutes and even more preferably 1 minute to 2 minutes interval and most preferably from about the interval of a minute be very desirable.If the cycle is to measure second, so such as 1 second to 60 seconds, the 1 second even shorter interval to 50 seconds, preferably 20 second to 50 seconds, 1 to 40 seconds, preferably 20 second to 40 seconds, 1 second to 30 seconds, preferably about 30 seconds, 1 second to 20 seconds or 1 second to 10 seconds is in fact suitable for and desirable interval; Can select even shorter interval, the interval of the interval of such as 1 second to 5 seconds, 1 second to 4 seconds, 1 second to 3 seconds, 1 second to 2 seconds and about a second, but these very short intervals are not too preferred.

In more preferred of the present invention, interval is at least one complete cycle, preferably one day, more preferably indicated with any cycle of measuring second above, and even more preferably indicated with any preferred cycle measured second above.

In even more preferred of the present invention, interval be 1 minute to 5 minutes, preferably 1 minute to 4 minutes, more preferably 1 minute by 3 minutes and even more preferably cycle of 1 minute to 2 minutes, and the most preferably from about interval of a minute.

In even more preferred of the present invention, interval be 20 seconds to 50 seconds, more preferably 20 second by 40 seconds and most preferably from about 30 seconds.

According to the present invention, likely in step (b) at any time and/or in measurement and/or control the pipe of the hydrogen fluoride supply of significant quantity through this pressure-sensing device during electrolytic bath (ionogen) liquid level.Therefore, hydrogen fluoride (HF+N together with nitrogen is likely made ₂) or dividually (only HF) through this pipe.In a preferred embodiment of the invention, for tonometric hydrogen fluoride (HF) and nitrogen (N ₂) be separately directed through this pipe, such as, represent under different time or cycle, such as, under the cycle (interval), apply the nitrogen (N of step (a) as elucidated before ₂) and the hydrogen fluoride (HF) of step (b).In this preferred embodiment, the present invention be more particularly directed to a kind ofly measure and/or control in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, the hydrogen fluoride that wherein step (a) detects in anode chamber and cathode chamber at least one pressure and step (b) is supplied with effective amount carries out at different time, and preferably step (a) and (b) carry out with alternate mode.

Alternate mode according to the present invention is very favorable, this is because condition when its allows electrolysis more steadily and provide the possibility in fact realizing continuously (" lastingly ") and the measurement of maintenance-free electrolyte level thus.If select shorter alternate cycle, so it also has beneficial effect to the quality of produced fluorine, this is because, as O ₂, OF ₂and/or CF ₄impurity content due to electrolysis procedure more stable and even and keep lower.For example, O ₂and OF ₂concentration is just to fluctuate up and down by a small margin, and CF ₄content keeps below 20ppmv and may be even lower under the several minutes cycle under a few hours period.

The alternate cycle of step (a) of the present invention and (b) can be same to each other or different to each other.For each step in step (a) and (b), the cycle (interval) indicated above may be suitable for individually.Preferably, in the step (a) and (b) of method according to the present invention, the cycle (interval) indicated above has the roughly the same time length.Therefore, in this preferred embodiment of the present invention relating to alternate mode, two kinds of intervals of step (a) and (b) are all indicated with any cycle of minute to measure above, and it is even furthermore preferable that indicated with any preferred cycle measured second above.

Have step (a) and (b) interval alternate mode, in even more preferred of the present invention, interval be 1 minute to 5 minutes, preferably 1 minute to 4 minutes, more preferably 1 minute by 3 minutes and even more preferably cycle of 1 minute to 2 minutes, and the most preferably from about interval of a minute.Have step (a) and (b) interval alternate mode, in even more preferred of the present invention, interval be 20 seconds to 50 seconds, more preferably 20 second by 40 seconds and most preferably from about 30 seconds.

Therefore, it is not restriction as an example, measuring and/or controlling in the inventive method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this electrolyzer has the anode chamber and cathode chamber that are separated by dividing wall each other and is that the electrolytic bath (ionogen) of the fluorinated hydrogen mixed melting salt of the HF adducts for being comprised KF by electrolysis produces fluorine gas, the pressure-sensing device of a pipe (liquid level sensing pipe) that () is stretched into by comprising in (immersion) electrolytic bath (ionogen) during fluorine gas produces has the time of 20 seconds to 40 seconds to the step detecting the pressure at least one chamber in anode chamber and cathode chamber, the preferably time of about 30 seconds, and (b) by the hydrogen fluoride supply of significant quantity through the pipe of this pressure-sensing device to remove thus and/or to prevent in the pipe of pressure-sensing device by this step of blocking of causing of the HF adducts of KF of crystallization having time of 20 seconds to 40 seconds, the preferably time of about 30 seconds.

If foregoing embodiment of the present invention combines with another preferred embodiment of the present invention that make use of the pressure-sensing device comprising the pipe (liquid level senses and manages) (wherein this pipe is limited by a flow orifice with particular inside diameters) stretched in (immersion) electrolytic bath (ionogen), so foregoing embodiment is particularly suitable.

The internal diameter in a given pond depends on the throughput of HF supply through the pressure in the inlet pressure in this aperture, pond and pond.Orifice diameter under high HF inlet pressure may be less than the orifice diameter under low HF inlet pressure.

As described in detail below, HF supply is lower than 20kg/h and be often that factory between 7kg/h and 9kg/h relates to a preferred embodiment.Therefore, in this preferred embodiment of the present invention, the feature stretching into the pipe (liquid level sensing pipe) in electrolytic bath (ionogen) is the flow orifice in pipe with about 2.5mm (inside) diameter.In this context, term " about " represents that the value of 2.5mm may slightly change, such as to greatest extent ± 0.1mm to ± 0.25mm, preferably change ± 0.1mm to ± 0.2mm.Therefore, the feature of flow orifice diameter may be as follows: 2.5mm ± 0.25mm, 2.5mm ± 0.2mm or 2.5mm ± 0.1mm, etc.Must be pointed out, this aperture may be depended on the amount of the HF of supply per hour and the inlet pressure of HF and change.HF for supply per hour exceedes the situation lower than 20kg/h, and having larger-diameter aperture may be suitable for.Supply HF for the speed as much lower in 6kg/h with ratio, the aperture with small diameter may be favourable.For the aperture of 2.5mm, cross-sectional area is about 5mm ².Cross-sectional area should be associated with the amount of the HF by it per hour.Assuming that the relation between HF feeding coal per hour and cross-sectional area is linearly.If assuming that the amount of HF per hour doubles, cross-sectional area so should be used also to increase to the aperture of twice.Assuming that the aperture of diameter in the scope from 1mm to 1cm can be applied in supply line.However, if necessary, the aperture with smaller or greater diameter can also be used.

In another preferred embodiment of the present invention, the pipe (liquid level sensing pipe) stretched in (immersion) electrolytic bath (ionogen), except playing the function according to the step (a) of the inventive method, also may serve as (mainly) hydrogen fluoride feed supply line of the electrolytic action producing simple substance fluoride simultaneously.Then, according to this embodiment of the present invention, do not need an independently HF feed pipeline and one independently liquid level sensing pipe.This embodiment of the present invention is specially adapted to sense with the liquid level being characterized as the flow orifice in pipe with about 2.5mm (inside) diameter manages and according to Combination of Methods mentioned above of the present invention, the pressure-sensing device of pipe (liquid level sensing is managed) that wherein (a) to stretch into by comprising in (immersions) electrolytic bath (ionogen) during fluorine gas produces operates the time of 20 seconds to 40 seconds to the step detecting the pressure at least one in anode chamber and cathode chamber, the preferably time of about 30 seconds, and (b) by the hydrogen fluoride supply of significant quantity through the pipe of this pressure-sensing device to remove thus and/or to prevent in the pipe of pressure-sensing device by the step of blocking that causes of the HF adducts of KF of crystallization operating time of 20 seconds to 40 seconds, the preferably time of about 30 seconds.By this embodiment, the invention provides and a kind ofly manufacture F by HF contained in a kind of ionogen of electrolysis ₂method, wherein form F ₂and H ₂and by supplying fresh HF to supplement consumed HF, wherein the supply of fresh HF is limited to the HF flow of the maximum 10kg/h HF of ionogen per ton.Preferably, HF flow is limited to the maximum 5kg/h HF of ionogen per ton.Term " HF flow " and term " HF feeding coal per hour " are interchangeable.Term " ton " refers to metric ton in framework of the present invention.

Must be pointed out, manufacture F for electrolysis ₂(H ₂produce with equimolar amount substantially as by product) common equipment there is the consumption that ionogen per ton per hour is about 1kg to 3kg HF.Therefore, must to the equipment with 2 tons of electrolyte capacity the fresh HF of supply 2kg to 6kg per hour with the supplementary HF consumed.Often, the consumption in this equipment with about 2 tons of electrolyte capacity is the HF from 3kg to 6kg per hour.

Therefore, as mentioned above, likely with a kind of reliable fashion at any time and/or measure measuring and/or carry out continuous and maintenance-free electrolyte level during controlling electrolytic bath (ionogen) liquid level in anode chamber and/or cathode chamber easily.Except in Liquid level and removal and/or prevent except this advantage stretched in pipe in electrolytic bath (ionogen) (liquid level sensing pipe) blocking, the present invention also provides additional advantage: O ₂and OF ₂impurity concentration low and to fluctuate up and down by a small margin.And, pass through the present invention, automatic HF feeding system is that HF feed measurement (differential pressure during HF feed) of attainable and approximate (" roughly ") becomes possibility, sense pipe especially by making liquid level and adapt to following quantitatively demand: relative to the capacity of electrolyzer, using the hydrogen fluoride (kg/h) of the hydrogen fluoride-such as aequum as feed material-the be supplied to electrolyzer (electrolyzer) for being produced simple substance fluoride by molten salt electrolyte (electrolytically) within the given time.

Hereinafter, should according to for measuring and/or controlling describing the present invention in more detail for generation of the preferred embodiment of the electrolytic bath liquid level in the electrolyzer of simple substance fluoride and change type, wherein supply the step (b) of HF except performing the function of level gauging and/or control, also as the HF feed supply being used for electrolysis generation fluorine, such as, the liquid level sensing pipe in the ionogen that means that this stretches into (immersion) is also used as single HF feed supply line.

According to this embodiment of the present invention, the HF consumed in electrolysis is that the fresh HF by adding aequum in more useful interim in a kind of mode more stably compensates.For example, wording " stably " be intended to represent to physical and chemical process parameter or ionogen have less may for negative interference, in electrolysis, more stable condition is kept thus during HF feed, such as make temperature and ionogen composition on room and time, keep more even, the production efficiency of fluorine can not be affected simultaneously negatively.Wording " stably " also makes the formation of impurity minimize or even can prevent the formation of impurity.Therefore, of the present inventionly this embodiment provides following overall advantage: although join in electrolyzer by HF, but can relatively easily temperature wherein be remained in the preset range desired by, and ionogen composition on room and time (such as in the whole electrolyzer comprising HF feed or inlet zone) keep evenly.Another advantage is to make the formation of impurity minimize or prevent the formation of impurity, and fluorine obtained thus only needs limited additional purification measure or the purity of fluorine that obtains to be ready for use in the technique of fluorine.

Often, HF supply line is through being configured to provide much higher HF flow to supplement.For example, supply line is constructed such that up to 80kg/h and even more HF to be incorporated in electrolyzer.The amount of per hour supplied HF can adjust simply by the suitable pipeline of use.The pipeline that internal diameter is 8mm is enough to the HF providing 80kg/h.But this just mentions as an example, not any restriction intention.According to the present invention, maximum HF flow is obviously lower.Therefore, in this embodiment, the present invention relates to a kind of for hydrogen fluoride to be supplied to the method for the electrolyzer (electrolyzer) for being produced simple substance fluoride by a kind of molten salt electrolyte (electrolytically) as feed material, the method comprises liquid level sensing pipe supply hydrogen fluoride (HF) via immersing in this ionogen, this pipe also serves as the single HF feed supply line leading to electrolyzer thus, wherein with HF per hour (preferred gaseous state) feeding coal (kg/h), the hydrogen fluoride feed of the aequum of the fluorine throughput for regulation is sent in this electrolyzer through the feed interval of regulation as described above, this HF feeding method be different in essence thus in as in ordinary method so far the 80kg/h in shorter complete HF feed interval that applies and even higher complete (maximum) HF feed ability.

Under the background of this embodiment of the present invention, simple substance fluoride produces as carrying out electrolysis for the feed material of electrolysis and the source of simple substance fluoride by using hydrogen fluoride (HF).A kind of electrolytic salt, typically be the melting HF of the KF preferably with formula KF (1.8-2.3) HF the existence of adducts under, if apply the voltage of at least 2.9V, so HF discharge fluorine.In fact, voltage often remains in the scope of 8 volts to 11 volts.

Advantageously supply HF and be no more than specific upper and lower bound level to make the level of electrolytic salt and HF in corresponding pond.Preferably, electrolyzer also comprises multiple sensor, the temperature in these sensor cells, liquid level, pressure and the pressure difference in one or more pond, anodic current and voltage and gas temperature.These ponds are the water quench of about 80 DEG C to 95 DEG C by temperature.

In this embodiment of the present invention, for the equipment with 2 tons of electrolyte capacity, the hydrogen fluoride feed of the aequum relevant to the fluorine throughput of electrolyzer is in the scope of the HF feeding coal of 2kg/h-5kg/h HF, preferably in the scope of 3kg/h-4kg/h HF.

Typically, in another embodiment, the present invention relates to one for supplying hydrofluoric method, wherein for the equipment with 2 tons of electrolyte capacity, HF feeding coal (kg/h) per hour is lower than 20kg/h, preferably lower than 15kg/h, and more preferably less than 10kg/h.In a change type of this embodiment of the present invention, for every 2 tons of ionogen, HF feeding coal (kg/h) per hour is in the scope of 1kg/h-20kg/h, preferably in the scope of 1kg/h-15kg/h, and more preferably in the scope of 1kg/h-10kg/h.In this measurement and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas a preferred embodiment, the method have been applied to and manufacture F by HF contained in a kind of ionogen of electrolysis ₂, form F in the method ₂and H ₂and by supplying fresh HF to supplement consumed HF, wherein the supply of fresh HF is limited to the HF flow (HF feeding coal) of the maximum 10kg/h HF of ionogen per ton.

More particularly, for every 2 tons of ionogen, the HF feeding coal (kg/h) per hour depending on pressure is in the scope of 2kg/h-10kg/h, preferably in the scope of 4kg/h-10kg/h, and more preferably in the scope of 6kg/h-10kg/h, and even more preferably in the scope of 7kg/h-9kg/h, and most preferably HF feeding coal per hour is about 8kg/h.In this context, wording " about " has following implication: HF feeding coal per hour slightly can change about the value of 8kg/h, such as slightly lower than or a little higher than 8kg/h.Therefore, this value alterable about ± 0.5kg/h, so and therefore HF feeding coal preferably 8kg/h ± 0.5kg/h.

In this embodiment of the present invention, HF (preferably in gaseous form) is admitted in electrolyzer, and HF feeding coal per hour (kg/h) be the diameter of flow orifice in liquid level sensing pipe by regulating this to act as hydrogen fluoride supply line simultaneously, the flow orifice that preferably has about 2.5mm internal diameter by means of one obtains.Term " flow orifice " represents that liquid level sensing pipe act as hydrogen fluoride supply line simultaneously, and itself may have and usually will have the internal diameter larger than the described 2.5mm of this flow orifice in the part from HF storage receptacle in the part of flow orifice present position and after this again in immersion ionogen.For purposes of the present invention, if the internal diameter that the internal diameter before and after flow orifice is greater than this HF supply line of described 2.5mm is reduced to the diameter of 2.5mm in the position of the terminal portions stretched in ionogen of HF supply line, just completely enough.This reduction of the internal diameter of HF supply line can be realized by any applicable constructivity device in its broadest sense, and these devices are the internal diameters at a single point place reducing a pipe interior, to produce the aperture with required diameter.

The characteristic optimization ground of hydrofluoric supply is that HF feeding coal (kg) and feed interval (h) are regulated by self-acting valve further.Typically, this self-acting valve operates on a preset condition based, operate when optionally revising HF feed parameter in due course every now and then during the technique manufacturing fluorine, this to depend in electrolyzer the time-varying overall conditions when electrolysis is carried out, such as depend on the temperature when molten salt electrolyte electrolysis, HF content, electrolyte level, electric current or any other correlation parameter, or the quality of the fluorine produced.Specifically, HF feeding coal, at least except other modes, is also regulated by the aforesaid method of measurement according to the present invention and/or control electrolytic bath liquid level.Preferably, the maximum possible flow of HF per hour is the total flow being greater than HF per hour.For example, HF flow is 6kg/h to 10kg/h, and the HF consumed is 2kg/h to 6kg/h.In this case, HF supply flow per hour may be greater than actual consumption amount, and therefore the supply of HF can interrupt regular hour scope.Not supplying in the time of HF, advantageously a kind of rare gas element is incorporated in the feed pipeline of HF.In a preferred embodiment, within the time of not supplying HF, electrolyte level is measured.Electrolyte level can such as be measured by the mode described in following paragraph.

This liquid level sensing pipe and HF supply line immerse in fused electrolyte.Usually, the electrolyte level in the immersion part of supply line is substantially the same with surrounding the electrolytical liquid level immersing pipeline.When stopping supply HF and be pressed into by rare gas element as mentioned above in this immerseable liquid level sensing pipe and HF supply line, there is no ionogen in immerseable pipe, this is because the pressure of rare gas element prevents entering of fused electrolyte.Depend on the liquid level of fused electrolyte, the pressure of this rare gas element must be higher or lower to prevent ionogen from entering in this immerseable pipe.Likely being calibrated to relative to liquid level electrolytical in pond prevents ionogen from entering required pressure.Depend on measured pressure, the supply of HF can be regulated: if electrolytical liquid level is relatively low, so by HF Flow-rate adjustment to a high value, and/or can extend supply time; Further, if liquid level is relatively high, so by HF Flow-rate adjustment to a lower value, and/or supply time can be shortened.

In a preferred embodiment, the ratio of HF flow (kg/h) and HF consumption (kg/h) is between 1.2: 1 and 4: 1.Preferably, this ratio is between 1.5: 1 and 3: 1.Therefore, the interval of supply HF is likely provided and does not supply the interval of HF, but electrolyte level measures by being incorporated into by a kind of rare gas element in liquid level sensing pipe and HF supply line as mentioned above.Preferably there is quite high-frequency HF supply and electrolyte solution position-finding.For example, can predict and per hourly have nearly 30 HF supply cycles and have nearly 30 electrolyte level determination periods accordingly.In this case, depending on the ratio of HF flow and consumption, is to illustrate at 1.2: 1 for time ratio, and HF supply will continue 33 seconds, within 27 seconds afterwards, be used for carrying out level gauging, within 33 seconds afterwards, for supplying HF, within 27 seconds afterwards, be used for carrying out level gauging, etc.This represents between HF flow periods, and the amount of the HF supplied is necessary for about 1.9 times of the amount of supplying without the continuous HF supplying mode interrupted.Time for 1: 1 than, such as, if the HF supply of 30 seconds by interruption 30 seconds to measure electrolyte level etc., so the amount of HF is by 2 times of the amount for supplying with the continuous mode of nothing interruption.Certainly, expert can carry out the time length of predefined HF supply and level gauging according to his wish.Frequency is higher, produces F ₂operation more steady.The amount of the HF consumed during supply time and minute is all provide in the interval supplied.

Certainly, pressure must do not measured in each interval not supplying HF.

Can at the F in pond ₂in compartment or at H ₂piezometry is carried out in compartment.If at F ₂piezometry (this is preferred) is carried out, so N in compartment ₂or F ₂it is preferred rare gas element.If at H ₂piezometry (this is preferred) is carried out, so N in compartment ₂or H ₂it is preferred rare gas element.

Even likely use a kind of automatic system regulating the time length of the amount of HF to be supplied, HF feed and level gauging (depending on the data that level gauging provides).

Under the background of these embodiments of the present invention, HF can supply from the hydrogen fluoride storage receptacle of any type.Hydrogen fluoride storage receptacle can be the single hydrogen fluoride storage receptacle with different size, or it can be comprise a multiple hydrogen fluoride storage unit that is fixing or optionally transportable hydrogen fluoride storage receptacle, these storage receptacles can be connected with electrolyzer by a hydrogen fluoride supply line.Vaporizer for evaporated liquid HF can be provided with hydrogen fluoride storage receptacle or this vaporizer for evaporated liquid HF and can obtain in the factory locality that HF will be provided for the manufacture of fluorine and can be connected on hydrogen fluoride storage receptacle or unit and to be connected to hydrogen fluoride supply line.Other additional units, such as, the security device as HF sensor, HF destruction system also may reside in the position residing for hydrogen fluoride storage receptacle or unit.HF storage receptacle used in the present invention generally includes an automatic HF LS.Specifically, HF storage receptacle can be arranged on platform scale.In this embodiment, preferably, program control system, particularly an automatic process control system exercisablely open another second Remote control valve containing the hydrogen fluoride storage receptacle of HF with the Remote control valve of closing first empty HF container.This embodiment efficiently avoid manual operation multiple HF valve especially and ensure that continuous HF supplies.Preferably, these valves are exercisable automatically to close when abnormal operation state, such as, process interrupt in the process facility being connected to HF supply line.Further, these valves to operate automatically close under the HF leakage situation in hydrogen fluoride feeding unit according to the present invention.It may be such as caused by the leakage of the multiple optional flange connector of HF storage receptacle inside that this HF leaks.This avoids especially in this case close to the necessity of hydrogen fluoride feeding unit.

In addition, these storage receptacles can be isolated with HF supply line by two segregaion valve with a closed insulating space.In that case, at least one the interstitial row air valve be connected with one or more closed insulating space is comprised aptly further according to hydrogen fluoride feeding unit of the present invention.This interstitial row air valve is normally exercisable to remove the hydrogen fluoride optionally existed from this closed insulating space.Removal can such as be undertaken by applying vacuum.To otherwise, this removal can such as be undertaken by purging this closed insulating space with the sweeping gas (such as anhydrous air or preferred nitrogen) of a kind of rare gas element and/or a kind of pressurization.This removal can be carried out continuously, but preferably, removal is carried out discontinuously, particularly when HF storage receptacle is connected on liquid level sensing and HF supply line and/or when disconnecting with it.If appropriate, the gas so reclaimed from closed insulating space is discharged into a HF aptly and destroys unit, such as a washer.

In one embodiment, the invention is characterized in that the simple substance fluoride produced in electrolyzer is intended for use a kind ofly to manufacture in the method for electron device, preferably a kind of for the manufacture of the method for electron device in be used as etching reagent or be used as chamber clean agent.

Preferably, these electron devices are selected from lower group, and this group is made up of the following: semi-conductor, barrier-layer cell, MEMS and TFT.In one embodiment of the invention, fluorine is used as the chamber clean agent and etching reagent that manufacture electron device, and these electron devices are semi-conductor, barrier-layer cell, microelectromechanical systems (" MEMS "), TFT (thin film transistor of flat-panel monitor or liquid-crystal display) etc. especially.Be used as to manufacture electron device, the especially etching reagent of semi-conductor, barrier-layer cell, MEMS and TFT about fluorine, deposit multiple layer and the some consecutive steps etching the part of these layers are necessary.Fluorine may be used for etching by the layer of very different contextures, such as, for etching silicon-containing layer or other layers of compound forming volatile reaction product (such as tungsten).Etching can be carried out by hot mode or under plasmaassisted.About for chamber clean, usually (be often that (multiple layer passes through chemical vapour deposition to CVD chamber in treatment chamber, such as plasma enhanced CVD, metallorganic CVD or low pressure chemical vapor deposition and the chamber that is deposited in multiple project)) in during the depositing operation that carries out, undesirable settling is formed and must regularly remove on walls of the chamber with in Inner Constitution part.This is by realizing with hot mode or plasma enhancing mode process settling as chamber clean agent with simple substance fluoride.

Especially etching reagent is used as simple substance fluoride, and when it is used as chamber clean agent, desirably simple substance fluoride is very pure.The intrusion of water, carbonic acid gas, nitrogen and oxygen is considered to undesirable.As illustrated in greater detail above, simple substance fluoride produced according to the present invention meets these quality requirements.

In yet another preferred embodiment, the invention is characterized in what fluorine produced in production plant " scene " or " outside the venue (over the fence) ", be preferably used for manufacturing in the method for electron device.

If desired, fluorine can manufacture at the scene.This is a preferred embodiment of the present invention.Fluorine can be produced in one or more satellite plant, such as, produce in case at such as described in WO 2004/009873 fluorine and produce.If desired, each case can distribute to one or more treatment chamber of carrying out etching wherein; Or multiple fluorine generation case is connected on a fluorine gas distribution system, this fluorine gas distribution system is connected on these chambers.The inventive method for cryogenic purincation can be incorporated in this case.The all right basis of the inventive method is as PCT application WO 2012/034978 (application number PCT/EP2011/065773, on September 12nd, 2011 submit to) described in sled concept (skid concept) be incorporated in a factory, the full content of this application is combined in this by reference.

After manufacture and purifying, fluorine is transported to place to use.This preferably carries out under the pressure of projecting pressure.

In a preferred embodiment, by means of compressor, fluorine is pressurizeed, and do not apply gas under pressure (only simple substance fluoride).

Storing step (if prediction has) preferably represents that simple substance fluoride is stored in applicable storage tank (such as stainless steel cylinder).

Fluorine is preferably on-the-spot by carrying out electrolysis in the equipment that fluid is communicated with and produce being in one or more treatment chamber in its place to use.This represents that the simple substance fluoride that produces is not filled into subsequently by a storage tank disconnecting with line of pipes or in multiple pressurized bottle.If desired, fluorine is stored in and only remains connected in multiple storage tank on line of pipes or multiple bottle.Fluorine generator is often arranged in same factory with using its instrument, that is, be less than 500m with the distance of fabrication tool; This generator often will be positioned near tools, such as, be 100m or shorter with the distance of instrument.They even may be positioned at the adjacent place of the treatment chamber as place to use, and such as distance can be 10m or shorter.

Supplying step preferably represents by fluorine by pipeline, especially by keeping the permanent pipeline connected to be delivered to place to use from producing apparatus, to invade in fluorine and prevent fluorine from leaking out to prevent air.

In yet another aspect, the invention still further relates to the electrolyzer that a kind of adducts for the melting HF by electrolysis KF produces simple substance fluoride, wherein this ionogen is equipped with a liquid level sensing pipe, this liquid level sensing pipe also serves as the hydrogen fluoride supply line that can be connected on hydrogen fluoride feeding unit, and this liquid level sensing pipe that wherein also acts as hydrogen fluoride supply line has the flow orifice of diameter (this represents internal diameter) preferably in the scope from 1mm to 1cm and especially preferably about 2.5mm (inside) diameter.Term " flow orifice " and character and the mode in order to obtain described internal diameter describe existing above.Described description given above and explanation are applicable to this aspect of the present invention comparably, and this aspect relates to the electrolyzer that a kind of adducts for the melting HF by electrolysis KF produces simple substance fluoride.

In a preferred embodiment of the present invention about the electrolyzer for being produced simple substance fluoride by electrolysis, fluorine produces in case, preferably produce in the case of " scene " or " outside the venue " generation fluorine for the production plant at electron device, these electron devices are preferably selected from lower group, and this group is made up of the following: semi-conductor, photoproduction volt battery, MEMS and TFT.HF is supplied to one to describe for the manufacture of existing under the background of the method in the electrolyzer of simple substance fluoride by the concept at " scene " or " outside the venue " of production plant and character and implementation above.Described description given above and explanation are applicable to this aspect of the present invention comparably, and this aspect relates to the electrolyzer that a kind of adducts for the melting HF by electrolysis KF produces simple substance fluoride.

In order to provide the example in the fit closely pond of the present invention for being produced simple substance fluoride (producing fluorine by the adducts of the melting HF of electrolysis KF) by electrolysis, provide every day (24h) 50kg to 100kg fluorine (F to an electrolyzer ₂) throughput, preferred every day (24h) 80kg to 100kg fluorine (F ₂) throughput, and more preferably every day (24h) about 80kg to 90kg fluorine (F ₂) throughput.Other ponds are also applicable to, and such as every day produces less F ₂or more F ₂pond.A preferable range of day output be every day from 40kg to 200kg F ₂.

Method according to the first embodiment of the present invention allows measure any desired electrolyte level and be not limited to position level; Second embodiment allows the lasting long time cycle to measure in addition.

Following instance be intended to describe in detail the present invention and and unrestricted the present invention.

Example 1: for the manufacture of in the electrolyzer of simple substance fluoride, carry out Level Detection to remove and/or to prevent the blocking of level gauging pipe under supply HF

Routinely, a kind of electrolytic salt consisting of about KF2HF is filled in an electrolyzer, is heated to about 80 DEG C-120 DEG C and melting wherein.Apply the voltage between 8V to 10V, and make electric current by the composition of dissolving electrolyte salt in hydrogen fluoride; Inclusion in pond is maintained at about in the scope of 80 DEG C to 100 DEG C.Simple substance fluoride and simple substance hydrogen are formed in the pole compartments of correspondence.Make produced simple substance fluoride by a kind of Monel metal metallic glass material to remove solid and by means of the absolute pressure of a compressor pressurizes to about 10 bar, and be then cooled to the trap of-80 DEG C by one; In this trap, the HF condensation be trapped.Make the gaseous state F leaving this trap ₂by a NaF bed to remove any residual HF.

During electrolysis, in some cycle, a certain amount of HF is incorporated in electrolyzer by liquid level sensing pipe to remove and to prevent the further blocking of this pipe during detection electrolytic bath liquid level.After about 1 minute, interrupt HF supply, and then in 1 minute, there is no the differential pressure being measured electrolyzer under pressure compensated condition by liquid level sensing pipe nitrogen press-in being arranged in fluorine generation chamber (anode) of electrolyzer.Under these conditions, be closed for carrying out pressure compensated valve between the gas zone above the liquid electrolyte in pipe and electrolyzer.Progressively mineralization pressure P in pipe ₁, and depend on the pressure P of the gas zone above the liquid electrolyte in electrolytical actual liquid level and electrolyzer ₂, determine differential pressure (Δ P).Then, electrolytical liquid level in computing pool is carried out by Δ P.After the measurement, compensate pressure in electrolyzer and this pond get back to measurement before previous conditional.

Above-mentioned Level Detection can be repeated every now and then in due course when electrolysis is carried out.The different cycles can be applied for above-mentioned Level Detection.

Example 2: for the manufacture of in the electrolyzer of simple substance fluoride, carry out Level Detection to remove and/or to prevent the blocking of level gauging pipe under supply HF

Electrolysis is arranged according to example 1.In addition, according to example 1, during electrolysis, carry out Level Detection, wherein use the liquid level sensing pipe with flow orifice, wherein the internal diameter of this flow orifice is 2.5mm and HF feeding coal per hour is about 8kg/h.HF feeding coal (kg) and feed interval (h) regulate the feed to provide 3kg/h to 4kg/h HF in view of the throughput (2kg) of electrolyzer by self-acting valve.

Example 3: the Level Detection replaced and by gaseous state HF send into for the manufacture of in the electrolyzer of simple substance fluoride

A kind of electrolytic salt consisting of about KF2HF is filled in an electrolyzer, is heated to about 80 DEG C-120 DEG C and melting wherein.Be incorporated in electrolyzer by gaseous state HF by a HF supply line, wherein the internal diameter of flow orifice is 2.5mm and HF feeding coal per hour is about 8kg/h.HF feeding coal (kg) and feed interval (h) regulate the feed to provide 3kg/h to 4kg/h HF in view of the throughput (2kg) of electrolyzer by self-acting valve, and this depends on the Level Detection replaced hereafter be described in further detail.Apply the voltage between 8V to 10V, and make electric current by the composition of dissolving electrolyte salt in hydrogen fluoride; Inclusion in pond is maintained at about in the scope of 80 DEG C to 100 DEG C.Simple substance fluoride and simple substance hydrogen are formed in the pole compartments of correspondence.Make produced simple substance fluoride by a Monel metal metallic glass material to remove solid and by means of the absolute pressure of a compressor pressurizes to about 10 bar, and be then cooled to the trap of-80 DEG C by one; In this trap, the HF condensation be trapped.Make to leave this trap gaseous state F ₂by a NaF bed to remove any residual HF.

Stopping the interim of supply HF, by by N ₂air pressure enters in HF supply line to measure electrolyte level.Depend on measured electrolyte level, make the supply of HF reduce, increase or keep constant.In this example, preferably there is quite high-frequency HF supply and electrolyte solution position-finding.This frequency is determined by the ratio of HF flow (kg/h) with HF consumption (kg/h), and this ratio is the ratio of 1.8: 1 in this example.Therefore, the HF carrying out nearly 30 cycles per hour supplies and reaches the electrolyte solution position-finding in 30 cycles accordingly.In this example, when HF flow and consumption time, ratio was 1.2: 1 time, HF supply will continue 33 seconds, within 27 seconds afterwards, be used for carrying out level gauging, within 33 seconds afterwards, for supplying HF, within 27 seconds afterwards, be used for carrying out level gauging, etc.

In a change type of this example, for the ratio of 2: 1, the HF supply of 30 seconds will be interrupted 30 seconds to measure electrolyte level, etc.

Example 4: the Level Detection replaced and by gaseous state HF send into for the manufacture of in the electrolyzer of simple substance fluoride

A kind of electrolytic salt consisting of about KF2HF is filled in an electrolyzer, is heated to about 80 DEG C-120 DEG C and melting wherein.Be incorporated in electrolyzer by gaseous state HF by a HF supply line, wherein the internal diameter of flow orifice is 2.5mm and HF feeding coal per hour is about 8kg/h.HF feeding coal (kg) and feed interval (h) regulate the feed to provide 3kg/h to 4kg/h HF in view of the throughput (2kg) of electrolyzer by self-acting valve, and this depends on the Level Detection replaced hereafter be described in further detail.Apply the voltage between 8V to 10V, and make electric current by the composition of dissolving electrolyte salt in hydrogen fluoride; Inclusion in pond is maintained at about in the scope of 80 DEG C to 100 DEG C.Simple substance fluoride and simple substance hydrogen are formed in the pole compartments of correspondence.Produced original simple substance fluoride is made to be maintained at about the jet scrubber of the liquid HF operation at-75 DEG C to-80 DEG C by a use to remove solid and a part of HF be trapped.Through partially purified F ₂then the trap of-80 DEG C is cooled to by one to the absolute pressure of about 10 bar by means of a compressor pressurizes; In this trap, the HF condensation be trapped.Make to leave this trap gaseous state F ₂by a NaF bed to remove any residual HF.

Stopping the interim of supply HF, by by N ₂air pressure enters in HF supply line to measure electrolyte level.Depend on measured electrolyte level, make the supply of HF reduce, increase or keep constant.In this example, preferably there is quite high-frequency HF supply and electrolyte solution position-finding.This frequency is determined by the ratio of HF flow (kg/h) with HF consumption (kg/h), and this ratio is the ratio of 1.8: 1 in this example.Therefore, the HF carrying out nearly 30 cycles per hour supplies and reaches the electrolyte solution position-finding in 30 cycles accordingly.In this example, when HF flow and consumption time, ratio was 1.2: 1 time, HF supply will continue 33 seconds, within 27 seconds afterwards, be used for carrying out level gauging, within 33 seconds afterwards, for supplying HF, within 27 seconds afterwards, be used for carrying out level gauging, etc.

Be combined in disclosure content in this patent, patent application and publication and the afoul degree of this specification sheets by reference if any to making a term must be unclear, so this specification sheets should be preferential.

Claims (25)

1. one kind for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, this electrolyzer has at least one anode chamber and at least one cathode chamber of being separated by dividing wall each other, electrolytic bath (ionogen) for the fluorinated hydrogen mixed melting salt being comprised the HF adducts of KF by electrolysis produces fluorine gas, wherein the method comprises the following steps: (a) stretches into the pressure-sensing device of the pipe (liquid level sensing pipe) in (immersion) this electrolytic bath (ionogen) to detect the pressure at least one in this anode chamber and this cathode chamber during fluorine gas produces by comprising.

2. as claimed in claim 1 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, this electrolyzer has at least one anode chamber and at least one cathode chamber of being separated by dividing wall each other, electrolytic bath (ionogen) for the fluorinated hydrogen mixed melting salt being comprised the HF adducts of KF by electrolysis produces fluorine gas, wherein the method comprises the following steps: (a) stretches into the pressure-sensing device of the pipe (liquid level sensing pipe) in (immersion) this electrolytic bath (ionogen) to detect the pressure at least one in this anode chamber and this cathode chamber during fluorine gas produces by comprising, and (b) at any time and/or during electrolytic bath (ionogen) liquid level measured and/or control in this anode chamber and/or this cathode chamber by the hydrogen fluoride supply of significant quantity this pipe through this pressure-sensing device, to remove and/or to prevent the blocking caused by the HF adducts of the KF of possible crystallization in this pipe of this pressure-sensing device thus.

3. method as claimed in claim 1 or 2, the liquid wherein in this pipe of inert gas replacement, the method comprises the following steps: measure the pressure difference between the gas space of at least one in this rare gas element and this anode chamber and this cathode chamber.

4. as described in claims 1 to 3 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this molten salt electrolyte is the HF adducts of the melting of KF, preferably have according to the HF scope of formula KF (1.8-2.3) HF, the HF adducts of the melting of KF.

5. according to any one of Claims 1-4 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this stretches into pipe in (immersion) this electrolytic bath (ionogen) (liquid level sensing pipe) for this cathode chamber (" H at this electrolyzer ₂side ") in carry out pressure detection.

6. according to any one of Claims 1-4 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this stretches into pipe in (immersion) this electrolytic bath (ionogen) (liquid level sensing pipe) for this anode chamber (" F at this electrolyzer ₂side ") in carry out pressure detection.

7. according to any one of claim 1 to 5 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this electrolytic bath (ionogen) liquid level is by by means of rare gas or nitrogen or its any mixture, preferably by means of nitrogen (N ₂) gas measures differential pressure (Δ P) and measure, this gas is stretched into pipe in (immersions) this electrolytic bath (ionogen) (liquid level sensing is managed) be pressed in this electrolyzer by by means of this.

8. according to any one of claim 1 to 7 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein the method operates in a kind of the hydrofluoric mode being periodically supplied with effective amount, to make this hydrogen fluoride (HF+N together with nitrogen ₂) supply or make this hydrogen fluoride dividually (only HF) supply stretch into pipe in (immersions) this electrolytic bath (ionogen) (liquid level sensing is managed) through this.

9. as claimed in claim 8 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein the method operates in a kind of the hydrofluoric mode being periodically supplied with effective amount, to make this hydrogen fluoride (HF+N together with nitrogen ₂) supply stretches into pipe in (immersions) this electrolytic bath (ionogen) (liquid level sensing is managed) through this.

10. as claimed in claim 9 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein when the confession interrupting HF continues to supply N at once ₂.

11. according to any one of claim 8,9 or 10 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein the hydrogen fluoride of this significant quantity is with from some skies (such as seven days) to the cycle of one day (such as 24 hours), the cycle from some hours (such as 24 hours) to one hour (such as 60 minutes) or the cycle from some minutes (such as 60 minutes) to one minute (such as 60 seconds) or even periodically supply from some seconds to the cycle of several seconds.

12. is as claimed in claim 11 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein the liquid hydrogen fluoride of significant quantity be with 1 minute to 5 minutes, preferably 1 minute to 4 minutes, more preferably 1 minute by 3 minutes and even more preferably 1 minute to 2 minutes cycle and most preferably with the interval of about minute supply.

13. is as claimed in claim 11 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, and wherein the liquid hydrogen fluoride of significant quantity is with second by 40 seconds and the most preferably from about cycle supply of 30 seconds to 50 seconds, more preferably 20 in 20 seconds.

14. according to any one of claim 1 to 13 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, the hydrogen fluoride that wherein step (a) detects in this anode chamber and this cathode chamber at least one pressure and step (b) is supplied with effective amount carries out at different time, and preferably step (a) and (b) carry out with alternate mode.

15. as described in claim 13 and/or 14 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein (a) stretches into the pressure-sensing device of the pipe (liquid level sensing pipe) in (immersion) this electrolytic bath (ionogen) to detect the time that the step of the pressure at least one in this anode chamber and this cathode chamber is 20 seconds to 40 seconds during fluorine gas produces by comprising, the preferably time of about 30 seconds, and (b) by the hydrogen fluoride supply of significant quantity through this pipe of this pressure-sensing device to remove thus and/or to prevent in this pipe of this pressure-sensing device by may the step of blocking that causes of the HF adducts of KF of crystallization be time of 20 seconds to 40 seconds, the preferably time of about 30 seconds.

16. according to any one of claim 1 to 15 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this feature stretching into pipe in (immersion) this electrolytic bath (ionogen) (liquid level sensing pipe) is flow orifice, is preferably characterized as the flow orifice with about 2.5mm (inside) diameter in the tube.

17. according to any one of claim 1 to 16 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein this pipe (liquid level sensing pipe) stretched in (immersion) this electrolytic bath (ionogen), except playing according to except the function of step (a), also serves as (mainly) hydrogen fluoride feed supply line of the electrolytic action producing simple substance fluoride simultaneously.

18. according to any one of claim 13 to 17 due to measure and/or control in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein the method comprises liquid level sensing pipe and the combination with the flow orifice of about 2.5mm (inside) diameter in the tube, and the pressure-sensing device (a) stretching into the pipe (liquid level sensing pipe) in (immersion) this electrolytic bath (ionogen) during fluorine gas produces by comprising carries out the time of 20 seconds to 40 seconds to the step detecting the pressure at least one in this anode chamber and this cathode chamber, the preferably time of about 30 seconds, and (b) by time that the hydrogen fluoride supply of significant quantity is carried out 20 seconds to 40 seconds to remove and/or to prevent the step of the blocking caused by the HF adducts of the KF of possible crystallization in this pipe of this pressure-sensing device thus through this pipe of this pressure-sensing device, the preferably time of about 30 seconds.

19. according to any one of claim 1 to 18 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein the method have been applied to and manufacture F by HF contained in electrolyte ₂, which has been formed F ₂and H ₂and by supplying fresh HF to supplement consumed HF, wherein the supply of fresh HF is limited to the HF flow (HF feeding coal) of the maximum 10kg/h HF of ionogen per ton.

20. according to any one of claim 1 to 19 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein in this electrolysis, for the equipment with 2 tons of electrolyte capacity, the aequum of the hydrogen fluoride feed relevant to the fluorine throughput of this electrolyzer within the scope of the HF feeding coal of 2kg/h-5kg/h HF, preferably in the scope of 3kg/h-4kg/h HF.

21. according to any one of claim 1 to 20 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein in this electrolysis, HF feeding coal (kg) and feed interval (h) are regulated by self-acting valve.

22. according to any one of claim 1 to 21 for measuring and/or controlling in the method for generation of the electrolytic bath liquid level in the electrolyzer of fluorine gas, wherein in this electrolysis, fluorine produces in production plant " scene " or " outside the venue ", is preferably used to manufacture in the method for electron device.

23. 1 kinds of HF adductss for the melting by electrolysis KF produce the electrolyzer of simple substance fluoride, wherein this electrolyzer is equipped with liquid level to sense pipe, this liquid level sensing pipe is used for during fluorine gas produces, detected the pressure at least one in anode chamber and cathode chamber by pressure-sensing device, and this pipe also serves as the hydrogen fluoride supply line that can be connected on hydrogen fluoride feeding unit, and wherein this liquid level sensing pipe and hydrogen fluoride supply line have (inside) diameter is flow orifice from about 1mm to 1cm, preferably there is the flow orifice that (inside) diameter is about 2.5mm.

24. as claimed in claim 21 for producing the electrolyzer of simple substance fluoride by electrolysis, wherein fluorine produces in case, preferably produce in the case for producing fluorine at " scene " or " outside the venue " of production plant, these production plants are preferably used for producing electron device, these electron devices are preferably selected from lower group, and this group is made up of the following: semi-conductor, photovoltaic cell, MEMS and TFT.

25. as described in claim 23 or 24 for producing the electrolyzer of simple substance fluoride by electrolysis, it provides every day (24h) 50kg to 100kg fluorine (F ₂) throughput, preferred every day (24h) 80kg to 100kg fluorine (F ₂) throughput, and more preferably every day (24h) about 80kg to 90kg fluorine (F ₂) throughput.