CN103180029A

CN103180029A - Method for the removal of f2 and/or of2 from gas

Info

Publication number: CN103180029A
Application number: CN2011800440519A
Authority: CN
Inventors: 约翰内斯·艾歇尔; 弗朗西斯·费斯; 菲利普·莫雷勒; 奥利维耶罗·黛安娜; 彼得·M·普雷迪坎特; 埃尔詹·因韦伦; 霍尔格·珀尼斯; 托马斯·施瓦策; 沃尔夫冈·卡尔布雷耶; 黑尔格·劳
Original assignee: Solvay SA
Current assignee: Solvay SA
Priority date: 2010-09-15
Filing date: 2011-09-13
Publication date: 2013-06-26
Also published as: WO2012035000A1; KR20130111554A; JP2013539717A

Abstract

A method for the removal of F2 and/or OF2 from gases is described wherein a gas comprising F2 and/or OF2 optionally also containing HF is contacted with a liquid comprising a base and a dissolved thiosulfate salt or alkali metal nitrite, preferably the respective sodium compounds. Preferred bases are alkali metal hydroxides and alkali metal carbonates, especially the respective potassium compounds. The method is very suitable to treat gas from industrial processes in which F2 is applied or formed, e.g. in gases resulting from the manufacture of semiconductors, photovoltaic cells or TFTs. It can be applied, for example, for gases comprising F2 resulting from emergency events, from the start-up phase of F2 production, for waste gases from semiconductor etching apparatus including chamber cleaning waste gases and for gases comprising out-of-spec F2. The method allows the removal of F2 without formation of a significant level of OF2 in the treated gas.

Description

Remove F from gas 2And/or OF 2Method

The application requires the U.S. Provisional Patent Application 61/383204 of submitting on September 15th, 2010 and the U.S. Provisional Patent Application 61/383533 of submitting on September 16th, 2010; The European Patent Application No. 10177188.9 that on September 16th, 2010 submitted to; The European Patent Application No. 10177216.8 that on September 16th, 2010 submitted to; The benefit of priority of the european patent application 11165500.7 that the European Patent Application No. 10177206.9 that on September 16th, 2010 submitted to and on May 10th, 2011 submit to, for all purposes, the content of these patent applications is combined in this by reference, the present invention relates to for removing F from a kind of gas ₂And/or OF ₂A kind of method.It is particularly related to from a kind of gas (originating from the gas of making semiconductor, photocell, thin film transistor (TFT) (TFT), liquid crystal display and MEMS (MEMS)) and removes F ₂And/or OF ₂And relate to and removing F ₂Process in the processing that forms gas in reach the OF of low content ₂In these manufacture processes, F ₂Can be used as etching gas, use as chamber clean gas, usually for example with nitrogen and/or argon mixture in from 1% to 50% concentration by volume, perhaps its precursor of from then on using in class process forms, the organic etchant that for example replaces from fluorine, or from inorganic fluoride, SF for example ₆Or NF ₃

In the manufacture process of semiconductor, photocell, thin film transistor (TFT) (TFT) liquid crystal display and MEMS (MEMS), carry out a plurality of steps and the article corresponding to etching of successive sedimentation material in the suitable chamber of being everlasting; These processes are plasmaassisted normally.In this deposition step, deposit is not only through forming on these article of being everlasting but also form on these walls of this chamber and other a plurality of inner bodies.These deposits remove by applying a kind of etchant often.Element fluorine is that a kind of very effective reagent not only is used for the etching article but also be used for these chambers of cleaning to remove undesirable deposit according to observations.These class methods and are illustrated in undocumented WO patent application PCT/EP2010/066109 (it relates to the manufacturing of TFT) for example in WO2007/116033 (it has illustrated that use fluorine and some mixture are as etchant and chamber clean agent), WO2009/080615 (it has illustrated the manufacturing of MEMS), WO2009/092453 (it has illustrated the manufacturing of solar cell).The gas of extracting out from chamber generally includes F ₂Molecule.When some etchant, the organic compound that replaces of fluorine (CF for example for example ₄), or inorganic etchant, for example SF ₆Or NF ₃, when standing high temperature or plasma in etching process or chamber clean process, the F base forms.The new combination of these F basic weights of a part is to form F ₂The F that is used for etching or chamber clean ₂Normally at the scene by HF under the existence of conducting salt, the electrolysis under the existence of KF (it and HF form adduct) produces especially.Be known that in the situation that initial period or damage (anode break), F at anode ₂Can be produced, its purity can not satisfy for making the necessary purity condition of semiconductor, TFT, photocell or MEMS (microelectromechanicdevices devices); This type of gas may contain the F of high magnitude ₂For the production of with send F ₂If facility at the scene of manufacturing works as above, if or at a common F ₂Produce outside device context and can predict for comprising F ₂The precautionary measures of emergent management of gas, for example in production unit, the accident that caused by corrosion in the situation that store or sending or sew, or when a dangerous threat, for example earthquake; Referring to the unpub EP patent application 10177216.8 of submitting on September 16th, 2010.In so a kind of event, from this facility (for example according to the undocumented U.S. Provisional Patent Application 61/383204 of submitting on September 15th, 2010 and submitted on September 16th, 2010 61/383533 described in a F of sliding part (skid) concept ₂Generation unit) inner HF, the F of comprising ₂Or both gas can dilute with vent air, has low F thereby produced ₂The air-flow capacious of concentration.

Therefore, in several different methods, comprise F with extensively different concentration and different volumetric flow of gas ₂And F is being made and used to the gas of HF usually ₂Or produce in corresponding precursor process.Due to F ₂Be a kind of very reactive compound, exist for remove F from this type of gas ₂A kind of needs of reliable method.Be used for removing F from gas ₂Method be known.The gas-solid method (for example will contain F ₂Gas and a kind of solid processing agent such as CaCO ₃Contacting) shortcoming that has is that the dissipation of heat is a problem, and has formed a plurality of layers on solid, has hindered further reaction.Wet method is also known.When making water as a kind of inorganic agent, unless be provided a large amount of times of contact, otherwise can form OF ₂In addition, observed blast.When using potassium hydroxide (KOH) aqueous solution, formed equally OF ₂Referring to H.R.Leech in J.W.Mellor (editor), Comprehensive treatise of inorganic and theoretical chemistry ", appendix II, part I, (Longmans, Green ﹠amp; Co, London1956), the 186th to 197 page.OF ₂Be very responding property and compound toxicity, and its existence in the gas of processing is very undesirable.WO99/61132 has disclosed a kind of F ₂Methods to reduce noises wherein has pending gas to contact with a kind of waterborne compositions with a kind of, and this waterborne compositions comprises a kind of reducing agent, for example sodium thiosulfate, ammonia or KI.

The object of the present invention is to provide for removing F from a kind of gas ₂And/or OF ₂A kind of method, the method is at F ₂And/or OF ₂Concentration and to have aspect pending volume in per time unit be very flexibly.Another object of the present invention is to be provided for to remove F from a kind of gas ₂And/or OF ₂And a kind of method of HF (if existing in pending gas is arranged), the method is at F ₂And/or OF ₂Concentration and to have aspect pending volume in per time unit be very flexibly.These purposes and other purposes are achieved by the present invention.

The invention provides for obtaining and have the F that reduces content ₂And/or OF ₂And a kind of method of a kind of gas of (if existing in pending gas is arranged) HF, the method comprises at least one step, this step is from a kind of F of comprising ₂And/or OF ₂And randomly remove F in the gas of HF ₂And/or OF ₂And HF (if present), wherein this gas is contacted with a kind of fluid composition, this fluid composition comprises water, be selected from the reducing agent of the dissolving of lower group, this group is comprised of the following: alkali metal thiosulfate and alkali metal nitrites salts, and the alkali that is selected from least a dissolving of lower group, this group is comprised of the following: alkali metal hydroxide and alkali carbonate.

According to an embodiment, only comprise or comprise in fact OF ₂Gas can be processed.Term " in fact " refers to OF in the total content of the pollutant that remains to be removed ₂Content be to be equal to or greater than by volume 90%, be F to 100% difference by volume ₂, HF or both.This type of gas can be the gas that leaves gas treatment equipment, does not wherein exist reducing agent to contain F as processing under additive with alkali lye ₂Gas.Therefore, in this embodiment, this processing can be a kind of post processing.

According to another embodiment, can process and comprise F ₂And OF ₂And the gas of HF randomly.This type of gas can be derived from a treatment step, wherein will comprise F ₂Gas process deficiently with a kind of alkali or with a kind of alkali and a kind of combination as the reducing agent of additive.

According to another embodiment, only comprise F ₂And the gas of optional HF is processed.This type of gas particularly is derived from F ₂The gas of the initial period of making, or this gas can comprise out-of-spec F ₂, or be derived from the gas of the emergency in such device; A preferred device is a device of basis sliding part concept as described below.In view of this embodiment, will explain the present invention.

The F that term " specification is outer " refers to not have desirable purity ₂For example, CF ₄Content can be too high, it can be caused by an anode that breaks down in an electrolytic cell.F ₂This specification external admission usually be decomposed because they are considered to not be to be suitable for the field that semiconductor is made.

In above-mentioned embodiment, processed and contained F ₂And/or OF ₂Gas, this type of gas randomly may also contain HF.But what may not necessarily occur very much in these embodiments is, should processing only contains HF does not contain F ₂And do not contain OF ₂Gas.However, if this occurs, can also process the gas that only contains HF by treatment in accordance with the present invention.Although in this case reducing agent exist optionally, advantage is that the gas that only contains HF also can be processed equally.Contingent is that the composition that pending gas is arranged can be different.For example, there is pending gas can comprise F when beginning ₂And HF, and subsequently, due to for example turning off of fluorine generator, this gas may only comprise HF.

In a preferred embodiment, to only contain F when entering this treating apparatus ₂And randomly the gas of HF is processed.As mentioned above, the waterborne compositions of water or causticity is processed F ₂May cause OF ₂Formation.Method of the present invention has been removed formed OF ₂, OF that so at most can the ignorance amount when carrying out method of the present invention ₂Be comprised in handled gas.Therefore, a preferred embodiment of the present invention provides and has been used for obtaining to have the F that reduces content ₂(if present) HF and (if any) can be ignored the OF of content ₂A kind of a kind of method of gas, the method comprises at least one step, this step is from a kind of F of comprising ₂And randomly remove F in the gas of HF ₂(if present) HF, wherein this gas is contacted with a kind of fluid composition, this fluid composition comprises water, be selected from the reducing agent of the dissolving of lower group, this group is comprised of the following: alkali metal thiosulfate and/or alkali metal nitrites salts, and the alkali that is selected from least a dissolving of lower group, this group is comprised of the following: alkali metal hydroxide and alkali carbonate.This term " negligible content if any, " refers to the OF that forms in processing procedure ₂Be completely removed, if or do not remove OF fully in processing procedure ₂, the OF in the gas that leaves the reactor that carries out this processing ₂Content is to be equal to or less than the every volume of 200ppm, preferably is equal to or less than the every volume of 150ppm.

Can use the known device that is useful on liquid-solid/liquid/gas reactions of expert will have pending gas to contact with fluid composition.For example, can make this gas pass this fluid composition in a reactor.Preferably provide the formal distribution means in liquid of gas with rill, for example from tolerance F ₂Material for example from steel or the metal frit of monel metal, and/or provide blend tool, for example turn a shaft-driven blender by one.

Same possible is counter current contacting in a tower with gas and liquid, especially comprise the tower for improvement of the device of the mass exchange between gas and liquid, for example one comprise inner member, particularly filler (for example Raschig ring or Pall ring) or other be used for providing the tower of the device of high contact area between gas phase and liquid phase.For example, the pillar that has bubble cap tray or a Tolman tower tray very well is fit to.In these pillars, the high-quality transfer has occured between gas and liquid.

Jet scrubber is also fit closely.For example, a jet scrubber with the Packed tower access pipeline of tool (in line) is to be suitable for very much processing having high F ₂The gas of content but lower gas flow is to be suitable for very much processing having low F but at the access pipeline, two, ground jet scrubbers are installed ₂The gas of content but high gas flow, as be derived from the gas of emergency.It can be as usually known useful in the technology of gas liquid reaction certainly that other of device arrange.

Certainly, might use two or more alkali metal thiosulfate compounds as reducing agent, for example sodium thiosulfate and potassium thiosulfate, or two or more alkali metal hydroxides, for example NaOH and potassium hydroxide, two or more alkali carbonates, or the combination of one or more alkali metal hydroxides and one or more alkali carbonates.Alternately, or additionally, for using alkali metal thiosulfate, alkali metal nitrites salts can be used as reducing agent.

Advantageous applications wherein alkali metal refers to the compound of potassium.

Term " fluid composition " preferably refers to a kind of waterborne compositions that does not preferably contain organic solvent.

Term " F ₂" refer to element fluorine, particularly contain to be derived from from one and electrolytically produce F ₂The F of gas of initial period of device ₂, or be derived from the out-of-spec F of such device ₂, and from for the production of F ₂A factory in the F of emergency ₂, the F that particularly dilutes ₂

This fluid composition comprises thiosulfate and hydroxide and/or the carbonate of dissolving.This does not get rid of and has in addition solid sulfur thiosulfate, solid hydroxide and/or solid carbonate.

This fluid composition can comprise for F ₂Has reactive other compound, for example ammonia or KI.Preferably, alkali metal thiosulfate and/or alkali metal nitrites salts (more preferably alkali metal thiosulfate) and the alkali that is selected from least a dissolving of lower group are and F ₂And any formed OF ₂Only compound (in composition or water and undesirable impurity from processed gas) of reaction, this group is comprised of the following: alkali metal hydroxide and alkali carbonate.Preferably, this fluid composition does not contain ammonia and KI.

In alkali metal thiosulfate, sodium thiosulfate and potassium thiosulfate are preferred.Sodium thiosulfate is particularly preferred.

In alkali metal nitrites salts, natrium nitrosum and potassium nitrite are preferred.Potassium nitrite is particularly preferred.

In alkali metal hydroxide, potassium hydroxide and NaOH are preferred.Potassium hydroxide is particularly preferred.

In alkali carbonate, sodium carbonate and potash are preferred.In alkali carbonate, potash is particularly preferred.

Can also use alkali metal hydrogencarbonate, particularly sodium acid carbonate.

The shortcoming that alkali metal carbonic acid (hydrogen) salt has is, may form carbon dioxide, and carbon dioxide can cause foaming.If the thiosulfuric acid salt content be low (due to fluorine and OF ₂Reaction in its consumption), another shortcoming of carbonate is that they have removed F ₂And decomposed formed OF ₂Validity, they are not the same with hydroxide effective.Therefore, potassium hydroxide and NaOH are preferred.

Alkali metal thiosulfate is preferred inorganic agent, and sodium thiosulfate particularly.

Comprise the fluid composition of sodium thiosulfate and KOH and comprise sodium thiosulfate and the fluid composition of potash is to be particularly preferred for removing F ₂And any in fact OF that forms as the accessory substance in gas ₂.Most preferably, used fluid composition, at least a alkali that this fluid composition consists of in fact water, sodium thiosulfate and is selected from lower group, this group is comprised of the following: potassium hydroxide and potash.Term " consists of in fact " activating agent that refers in fluid composition, namely refers to water, thiosulfate and hydroxide content; Said composition may further include undesirable impurity, for example at water, thiosulfate, hydroxide or from F ₂With comprise in the product that exists in the fluid composition of the reaction of these reagent and water.Found, at water, alkali metal hydroxide and alkali metal thiosulfate and F ₂Course of reaction in, formed alkali metal sulfates and alkali metal fluoride; Therefore, a kind of have water, alkali metal thiosulfate and alkali metal hydroxide " to form in fact " fluid composition can to comprise alkali metal sulfates and the alkali metal fluoride of significant quantity.

The concentration of alkali metal thiosulfate preferably is equal to or higher than 0.1% by weight, more preferably, be equal to or higher than by weight 0.3%, with respect to the gross weight of said composition.The concentration that particularly preferably is thiosulfate is by weight and is equal to or higher than 1%.

The concentration of alkali metal thiosulfate is to be equal to or less than saturated concentration.This fluid composition can even contain undissolved alkali metal thiosulfate.Preferably, the concentration of alkali metal thiosulfate is by weight and is equal to or less than 10%, more preferably, is equal to or less than by weight 5%, with respect to the gross weight of this fluid composition.Fluid composition preferably includes from being equal to or greater than by weight 0.3% to the thiosulfate that is equal to or less than by weight 5%, more preferably by weight from being equal to or greater than 0.5% to being equal to or less than 5%, most preferably, from being equal to or greater than by weight 1% to the thiosulfate that is equal to or less than by weight 5%.If have a kind of alkali metal nitrites salts rather than a kind of alkali metal thiosulfate, its value is corresponding to for pointed those of thiosulfate.

Generally, the concentration of alkali metal hydroxide preferably is equal to or higher than 10% by weight, more preferably, is equal to or higher than by weight 15%, with respect to the gross weight of said composition.

The concentration of alkali metal hydroxide (if present) is to be equal to or less than saturated concentration.This fluid composition can even contain undissolved alkali metal hydroxide.Preferably, the concentration of alkali metal hydroxide is by weight and is equal to or less than 45%, more preferably, is equal to or less than by weight 35%, with respect to the gross weight of this fluid composition.

The concentration of alkali carbonate (if present) preferably is equal to or higher than 10% by weight, more preferably, be equal to or higher than by weight 15%, with respect to the gross weight of said composition.More preferably, with respect to the gross weight of said composition, the concentration of the alkali of dissolving is by weight and is equal to or greater than 15% and be equal to or less than saturated concentration.

The concentration of alkali carbonate is to be equal to or less than saturated concentration.This fluid composition can even contain undissolved alkali carbonate.Preferably, the concentration of alkali carbonate is by weight and is equal to or less than 45%, more preferably, is equal to or less than by weight 35%, with respect to the gross weight of this fluid composition.

If alkali metal hydroxide and alkali carbonate both are present in this fluid composition, the preferable range of their total content is by weight from 10% to by weight 45%, with respect to the gross weight of said composition.

In a preferred embodiment, the concentration of alkali metal thiosulfate is by weight from 1% to 5%, and the concentration of alkali metal hydroxide is by weight from 10% to 45%.In another preferred embodiment, the concentration of sodium thiosulfate is by weight from 1% to 5%, and the concentration of potassium hydroxide is by weight from 10% to 45%.

In a further preferred embodiment, the concentration of alkali metal thiosulfate is by weight from 1% to 5%, and the concentration of alkali metal hydroxide is by weight from 15% to 45%.In another preferred embodiment, the concentration of sodium thiosulfate is by weight from 1% to 5%, and the concentration of potassium hydroxide is by weight from 15% to 45%.

In a further preferred embodiment, the concentration of alkali metal nitrites salts is by weight from 1% to 5%, and the concentration of alkali metal hydroxide is by weight from 10% to 45%.In another preferred embodiment, the concentration of natrium nitrosum is by weight from 1% to 5%, and the concentration of potassium hydroxide is by weight from 10% to 45%.

In a further preferred embodiment, the concentration of alkali metal nitrites salts is by weight from 1% to 5%, and the concentration of alkali metal hydroxide is by weight from 15% to 45%.In another preferred embodiment, the concentration of natrium nitrosum is by weight from 1% to 5%, and the concentration of potassium hydroxide is by weight from 15% to 45%.

According to an embodiment, use a kind of fluid composition, wherein do not replenish this alkali metal thiosulfate, alkali metal hydroxide and alkali carbonate in course of reaction.In this case, the concentration that more than provides refers to the corresponding concentration when contacting between beginning gas and liquid.Because thiosulfate and hydroxide consume in reaction gradually, corresponding concentration will drop to below initial value.

According to another embodiment, alkali metal thiosulfate, alkali metal hydroxide and/or alkali carbonate constantly or are every now and then added in this fluid composition to keep corresponding concentration a predefined level.In this case, thus it is to be equal to or higher than the above corresponding Cmin that provides that reagent corresponding to preferred addition makes its concentration in fluid composition.Another replacement scheme is to add alkali metal thiosulfate from a container that comprises the little separation of automation feature, is used for additive is fed to the wash liquid that contains alkali metal hydroxide or alkali carbonate, only works as detector and sends F ₂During alarm signal, in case of emergency or, be in secure side, even in the situation that during a HF alarm.This container can for example be connected to the suction side of this pump, and it makes this wash liquid circulation.Preferably, this pump is in case of emergency running only, and in this case, this alkali metal thiosulfate is incorporated in circulation cleaning liquid automatically.

If a kind of alkali metal nitrites salts rather than alkali metal thiosulfate or also be used as additive except alkali metal thiosulfate, these substitutes are applicatory equally.

Contacting between gas and liquid preferably be equal to or higher than 1 bar (absolute value), more preferably be equal to or greater than and carry out under the pressure of 1.1 bar (absolute value).Preferably, the pressure in the contact process of liquid and gas is to be equal to or less than 3 bar (absolute value), more preferably to be equal to or less than 2 bar (absolute value).A preferred pressure limit is from 1 to 3 bar (absolute value), and more preferably 1.1 to 2 bar (absolute value) are particularly from 1.1 bar (absolute value) to 1.5 bar (absolute value).

Temperature in the contact process of gas and liquid preferably remains in the scope of 10 ℃ to 80 ℃, more preferably in the scope of 20 ℃ to 40 ℃.Should be noted that F ₂With the reaction of water, alkali and thiosulfate be heat release, and effectively cooling providing is favourable.If temperature has surpassed predefined level, if for example the temperature of wash liquid is greater than 80 ℃, cooling may be essential, and maybe this processing can be ended.

F in pending gas is arranged ₂Concentration can be extensively different.This is one of advantage of method of the present invention.

Method of the present invention is particularly suitable for removing F from gas ₂Composition, these gases comprise and are equal to or greater than by volume 0.5% F ₂And by volume even less than 0.5%, even F for example ₂Content be ppm scope (if for example it is equal to or greater than 100ppm), still can use the method.Method of the present invention is suitable for removing F from comprising being equal to or less than by volume 100% gas equally ₂Composition.

Therefore, the method can be applied to removing the F that is in any concentration ₂, and this flexibility is that a large advantage particularly is used for etching or chamber clean purpose for the making in site fluorine.

For pending gas being arranged about F ₂There are two main sources in concentration and volume flow.

Main source is the F that contains from initial period and specification external admission ₂Gas.Gas from this source has high F usually ₂Concentration, and this volumetric flow of gas is lower.If pending atmospheric origin is arranged in being used for F ₂The initial period of the electrolysis cells of producing or from specification external admission, F ₂Can be very high, for example by volume from 70% to 98%.Preferably, in this embodiment, the concentration of alkali metal thiosulfate is by weight from 1% to 5%, and the concentration of alkali metal hydroxide is by weight from 15% to 45%, and the F in pending gas is arranged ₂Concentration be by volume from 70% to 98%.Still in preferred embodiment, the concentration of sodium thiosulfate is by weight from 1% to 5% at one, and the concentration of potassium hydroxide is by weight from 15% to 45%, and the F in pending gas is arranged ₂Concentration be by volume from 70% to 98%.Volumetric flow of gas in this embodiment is 1.5m per hour preferably ³To 15m ³

Other main sources are the gas that comes from emergency.In the gas from this source, F ₂Content is normally lower, and volumetric flow of gas is higher.If pending gas source is arranged from emergency, it can dilute by vent air usually, and F ₂Content can be in from 0.5% to 5% scope by volume.

Preferably, in the embodiment for the treatment of the gas that is derived from emergency, the concentration of alkali metal thiosulfate is by weight from 1% to 5%, and the concentration of alkali metal hydroxide is by weight from 15% to 45%, and the F in pending gas is arranged ₂Concentration be by volume from 70% to 98%.Still in preferred embodiment, the concentration of sodium thiosulfate is by weight from 1% to 5% at one, and the concentration of potassium hydroxide is by weight from 15% to 45%, and the F in pending gas is arranged ₂Concentration be by volume from 0.5% to 10%.Volumetric flow of gas in this embodiment is preferably per hour from 100m ³To 15.000m ³

If pending gas source F outside specification is arranged ₂Air inlet, F ₂Content can be in any scope of from 0.5% to about 100% by volume, this depends on the degree of purifying or dilution, the concentration of alkali metal thiosulfate preferably by weight from 1% to 5%, the concentration of alkali metal hydroxide preferably by weight from 15% to 45%.At one still in preferred embodiment, F ₂Content be that this depends on the degree of purifying or dilution in any scope of from 0.5% to 100% by volume, the concentration of sodium thiosulfate is by weight from 1% to 5%, and the concentration of potassium hydroxide is by weight from 15% to 45%.

If pending gas source is arranged from the F of electrolysis ₂The initial period of making, F ₂Content preferably by volume 70% to about 100% scope by volume, preferably by volume 98%, the concentration of alkali metal thiosulfate preferably by weight 1% to 5%, the concentration of alkali metal hydroxide preferably by weight from 15% to 45%.Still in preferred embodiment, pending gas source is arranged from out-of-spec air inlet, F at one ₂Content be by volume from 70% in about 100% scope by volume, preferably by volume 98%, the concentration of sodium thiosulfate is by weight from 1% to 5%, and the concentration of potassium hydroxide is by weight from 15% to 45%.

The gas that is derived from the dilution of an emergency may occur.In a kind of like this emergency, F ₂May leak, perhaps have potential F ₂The danger of leaking, for example when earthquake threatens, or in the situation that the component failure of this equipment, for example pipeline or a valve invalidation of damage.In the situation that emergency, equipment can for example use and ventilate to F ₂Dilution is to reduce the F that is leaked ₂Potential hazard.In this case, high volume (common 5.000m ³/ h to 15.000m ³/ h) the F of dilution ₂Must effectively and reliably be processed.Method of the present invention is particularly well adapted for a kind of like this processing.Ladies and gentlemen inventor of the present invention further finds, Na ₂S ₂O ₃Even the solution in KOH be still for oxidation after air contacts several weeks highly stablely, this has replenished another advantage.This has ensured, any prefabricated aqueous solution of alkali metal thiosulfate keeps activity until emergency occurs.

Ladies and gentlemen inventor of the present invention finds, the nitrite in the aqueous solution of potassium hydroxide (for example potassium nitrite) with oxidation very lentamente after water contacts a couple of days.However, thus the solution of nitrite in alkaline solution under physical condition be sufficiently stable be what can accept very much as the safe handling agent.

Affect F ₂The OF that removes and form ₂The principal element of removal degree is the time of staying (it is inversely proportional with volumetric flow of gas), and the concentration of thiosulfate.Therefore, can be set to lower or higher level the time of staying by increasing or reduce volumetric flow of gas.Gas and the time of staying that contacts of the liquid treatment composition that comprises a certain thiosulfuric acid salinity are the F in the gas that is set as after processing ₂And OF ₂Removed satisfactorily.The time of staying can be for example in the scope of 1 second to 10 minutes.The preferred time of staying is from being equal to or greater than 1 second to being equal to or less than 5 minutes.

Method of the present invention can be applied to comprise F ₂The gas in any source.It can for example be applied to provide F ₂Any factory in and be applied to produce F ₂Any method, for example by the solution of electrolysis KF in HF, or be used for F ₂Set the method that does not contain the metal fluoride that is in higher valent state, for example, be used for working as MnF ₄Be heated to form F ₂And MnF ₃The time a kind of gas.The method is particularly suitable for factory, has wherein produced at the scene F ₂Remain the article that are selected from lower group for the manufacture of a kind of, this group is comprised of the following: semiconductor, photocell, TFT and MEMS, or clean one for the manufacture of the chamber of described article, because method of the present invention is at contained F ₂The concentration aspect, be very flexibly aspect the volume that pending gas is arranged, and be very effectively and reliably.

Usually, need to process different types of F that comprises ₂Gas.First kind gas is to appear at regularly the F with prediction ₂Those in the predefined gas of concentration; For example, from the F of electrolysis ₂The initial period of making or from the gas of specification external admission.Equations of The Second Kind gas occurs in uncertain mode, for example from the F that comprises dilution of emergency ₂Gas.

Therefore, comprise F ₂The gas preferred source from etching or the chamber clean of method that be used for to make semiconductor, MEMS or photronic manufacturing; More preferably, it is derived from F ₂The specification external admission of gas, or it is derived from electrolysis manufacturing F ₂Initial period, or it is derived from an emergency.

In order to process first kind gas (for example from F ₂The initial period of producing, specification external admission), in a preferred embodiment, with 2 or even 3 for the treatment of comprising F ₂The device of gas be installed in series.This type of gas has the F of high concentration usually ₂But occur with lower volumetric flow of gas.Therefore, a device for the treatment of first kind gas comprises at least one reactor that is suitable for processing the gas with relatively lower gas flow.Depend on from HF/KF and produce F ₂The number of electrolytic cell, reactor volume can be to make to process to be in from 1.5m ³/ h to 15m ³Volumetric flow of gas in/h scope is to remove F ₂And remove or avoid OF ₂Be formed into a gratifying level.The combination of jet scrubber or a jet scrubber and a Packed scrubbing tower of tool (the access pipeline is installed) is very suitable as reactor.If desired, when being installed in series 2 or more treating apparatus, the first treating apparatus can operate lacking under a kind of reducing agent with alkali metal hydroxide, is for example lacking under thiosulfate, ammonia or alkaline metal iodide such as KI with KOH.The gas that leaves treating apparatus can comprise the OF of certain content ₂And can comprise even residual F ₂Then gas is processed in one second device, this second device comprises KOH or K ₂CO ₃, preferred KOH, and thiosulfate, for example Na ₂S ₂O ₃If desired, can connect (purifying that high level is provided) or be installed in parallel some devices; This has allowed the processing that continues if a device must stop (for example for maintenance).Certainly, can also use known other devices that can be applicable to gas liquid reaction.

The fact that can be suitable for for the treatment of the device (usually being derived from emergency) of Equations of The Second Kind gas is that this type of gas has low F usually ₂(the 5.000m for example of content but very high volumetric flow of gas/per time unit ³/ h and larger for example 10.000m ³/ h to 15.000m ³/ h and larger), and therefore, the lower time of staying.In order to process these gas, preferably, this treating apparatus must be designed to reasonably processing so a large amount of gas in the time, and use a kind of fluid composition of abundant high volume, this fluid composition when beginning or permanent comprise a kind of thiosulfate of relative high-load, preferably be equal to or greater than by weight 1.5%, more preferably 2% thiosulfate by weight.Fluid composition in this sentinel plant can comprise KOH (or another kind of alkali, for example NaOH), preferably in from 10% to 35% scope by weight, and preferably by weight 25% to 35%.What can prove is, be in from by weight 1% to 2% Na by weight this can comprising ₂S ₂O ₃Fluid composition be to be suitable for very much " overdimensioned " sentinel plant.Although in the technique device that uses, by K2SO ₄Formation and the obstruction risk that causes of precipitation be low-down, this is owing to comparing larger pipe size with a laboratory installation and considering other devices; For example, compare with a laboratory scrubber post of having filled irregular filler, a jet scrubber is insensitive for obstruction, and however, lower a little KOH concentration has reduced the risk of filling.But if desired, the content of KOH or another kind of alkali can be higher, for example by weight up to 45% or larger.

This sentinel plant can be considered to have for processing the F that contains of lower gas volume flow and the high time of staying ₂Gas be overdimensioned, but be however favourable and even necessary (if having the risk of emergency).Can deliver to and pass urgent scrubber (or be designed to other devices of the emergency gas treatment) with only directly wearing from the gas that contains fluorine of urgent situation.If desired, this sentinel plant can be connected to upgrade any thiosulfate of using with a storage tank of thiosulfate.For example, comprise that a storage tank (preferably being equipped with the automation feature) that is in the thiosulfate that is equal to or greater than by weight 1.5% concentration can be connected with the entrance (suction side) of a pump, this pump makes this fluid composition circulation.In emergency, this pump actuated and fresh thiosulfate solution is joined in sentinel plant.Term " automation feature " refers to for measuring thiosulfate at the equipment of the concentration of storage tank and referring to if the thiosulfate of the too low beginning of the concentration of measuring outside this storage tank supplementary quota.

This device or these devices for the treatment of first kind gas and Equations of The Second Kind gas can be installed in parallel.

In a very reliable and preferred embodiment, will contain F for the treatment of the first kind ₂This device of gas (from the outer gas of initial period and specification) or these devices and (contain F from what an emergency was processed for the treatment of Equations of The Second Kind gas ₂Gas) a device be installed in series.Usually, will be for the treatment of two scrubbers of first kind gas (for example 2 jet scrubber or a gas jet washer and the scrubbing tower with inner part or filler) (at this, due to the high efficiency of the first scrubber, the second scrubber is normally unnecessary) and one be used for " overdimensioned " scrubber that emergency processes and be installed in series.First kind gas is passed three all scrubbers, and will directly pass from the gas of emergency the scrubber of processing for emergency.In such equipment, be used for removing F ₂And OF ₂Level of security be very high.

For the treatment of containing F ₂The method of the present invention of gas (gas that wherein leaves reactor contains the OF of trace at the most ₂) can be applied to processing the F that comprises from any source ₂This type of gas, comprise the waste gas from chamber clean, or from the F that contains of etching semiconductor, MEMS, photocell or TFT ₂Gas.It preferably merges in a process, has produced F in this process ₂And it directly is delivered to the scene.For etching as previously discussed article or for the required F of chamber clean ₂Therefore do not arrive the field of employment by highway or rail transport.F ₂A kind of like this integrated approach of making and using is a second aspect of the present invention.

Therefore a second aspect of the present invention relates to a kind of for be selected from the method for article of lower group the manufacturing of at least one chamber, this group is comprised of the following: semiconductor, photocell, TFT and MEMS, the method comprises at least one step that is selected from lower group, and this group is comprised of the following: with a kind of F of containing ₂These article of gas etch step and with a kind of F that contains that is suitable for etching or chamber clean ₂Gas clean step, wherein a F of this chamber ₂That a solution in HF is made at the scene by electrolysis KF (as electrolyte), and wherein will be from F ₂The initial period or the F that make ₂The specification external admission contain F ₂Release or be derived from the F that contains of emergency ₂Gas stand a treatment step to obtain to have the F of reduction ₂And/or OF ₂A kind of gas of (forming in processing procedure) content wherein will contain OF ₂Gas contact with a kind of fluid composition, this fluid composition comprises alkali metal thiosulfate and/or the nitrite of dissolving and the alkali that is selected from least a dissolving of lower group, and this group is comprised of the following: alkali metal hydroxide and alkali carbonate.Have in pending gas if HF is present in, it also is removed.

Therefore, first embodiment of a second aspect of the present invention relates to the manufacturing of the article that are selected from lower group, and this group is comprised of the following: semiconductor, photocell, TFT and MEMS, and this manufacturing comprises a step, wherein these article are placed in a chamber, add a kind of F of containing ₂Etching gas, these article of etching randomly by applying a kind of plasma support, will contain F ₂Gas atmosphere remove from this chamber, wherein the gas of removing is contacted with a kind of fluid composition, the alkali that this fluid composition comprises the alkali metal thiosulfate of dissolving and is selected from least a dissolving of lower group has the F of reduction with acquisition ₂A kind of gas of content, this group is comprised of the following: alkali metal hydroxide and alkali carbonate.Advantage (except other things) is as previously discussed, to leave the OF of this device ₂Level be low-down, and if the words that HF exists also are removed.

Second embodiment of a second aspect of the present invention relates to the manufacturing of the article that are selected from lower group, and this group is comprised of the following: semiconductor, photocell, TFT and MEMS, or be used for chamber clean, wherein F ₂To comprise that by electrolysis the HF of the KF of dissolving produces, the F that wherein produces ₂Be intended to as the etching gas of article or for chamber clean, and the F that wherein produces ₂Not to be fit to use, because it is derived from the initial period of electrolytic cell or it is out-of-spec, therefore and the method according to this invention is processed with a kind of fluid composition, and the alkali that said composition comprises the alkali metal thiosulfate of dissolving and is selected from least a dissolving of lower group has the F of reduction with acquisition ₂A kind of gas of content, this group is comprised of the following: alkali metal hydroxide and alkali carbonate; Equally in this embodiment, advantage is except other things, as previously discussed, and OF ₂The level that forms is low-down, and HF (if it should be comprised in this gas) also is removed.The 3rd embodiment of a second aspect of the present invention relates to the manufacturing of the article that are selected from lower group, this group is comprised of the following: semiconductor, photocell, TFT and MEMS, wherein, in being selected from least one step of lower group, this group is comprised of the following

Make F ₂, by electrolysis HF/KF solution, comprise its cleaning and be delivered to and use point to locate,

These article are placed in a chamber, wherein add a kind of F of containing ₂Etching gas,

These article of etching are randomly supported by applying a kind of plasma,

Remove from this chamber and contain F ₂Gas atmosphere,

Wherein a kind of crash time occurs and will contain F ₂Gas dilute with air and the gas of dilution contacted with a kind of fluid composition, the alkali that said composition comprises the alkali metal thiosulfate of dissolving and is selected from least a dissolving of lower group has the F of reduction with acquisition ₂A kind of gas of content, this group is comprised of the following: alkali metal hydroxide and alkali carbonate.

The explanation that provides more than of the present invention relates to some specific embodiments, as processing the F that comprises from initial period ₂Gas, contain F ₂The specification external admission of gas and the F that contains from emergency that usually is diluted ₂Gas.These specific embodiments are preferred.

However, method of the present invention also is suitable for processing the F that contains in other sources in self etching and chamber clean framework ₂Gas.For example, if some the organic or inorganic compound that is replaced by fluorine atom be used as one in treatment chamber etching gas or as chamber clean gas, particularly in the method that plasma is supported, the gas that leaves this chamber may contain F ₂Same these gases can the method according to this invention be processed.

Method of the present invention is particularly suitable for processing and is derived from F ₂The gas of making in site but it can also be for the treatment of the F that comprises that is derived from for the manufacture of the etching in semiconductor, MEMS or photronic method or chamber clean ₂Gas.

In a preferred embodiment of the invention, method of the present invention is carried out with treating apparatus, for example is incorporated into a F according to the sliding part concept ₂A scrubber in manufacturing cell.For the manufacture of F ₂, it purifying, storage (if yes), be delivered to the sliding part concept of using point and amenities be described in detail in the U.S. Provisional Patent Application 61/383204 of submitting on September 15th, 1 and submitted on September 16th, 2010 61/383533 in.

The invention provides a kind of improved factory is suitable for the on-the-spot fluorine that produces and is particularly useful as etchant and chamber clean agent in the manufacturing of semiconductor, photocell, Thin Film Transistor-LCD and MEMS.

This sliding part concept provides a factory to provide fluorine gas to an instrument, this tool applications fluorine gas carries out chemical action in this instrument as reactant, this utensil comprises the module that a plurality of sliding part formulas are installed, comprising at least one module that is selected from the sliding part formula installation of lower group, this group is comprised of the following:

-comprise the module of a sliding part formula installation of at least one HF holding vessel, be expressed as sliding part 1,

-comprise that at least one produces F ₂Sliding part formula of electrolytic cell module of installing, be expressed as sliding part 2,

-comprise for purifying F ₂Sliding part formula of purification devices module of installing, be expressed as sliding part 3,

-comprise the module that fluorine gas is delivered to a sliding part formula installation of the device that uses point, be expressed as sliding part 4,

-comprise the module of a sliding part formula installation of chilled(cooling) water return (CWR), be expressed as sliding part 5,

-comprise the module of a sliding part formula installation of the device of processing waste gas, be expressed as sliding part 6,

-comprise for analyzing F ₂Sliding part formula of device module of installing, be expressed as sliding part 7, and

-comprise the module of a sliding part formula installation of the device that operates these electrolytic cells, be expressed as sliding part 8.

Preferred factory of the present invention provides fluorine gas to a kind of instrument, and this tool applications fluorine gas carries out chemical action in this instrument as reactant, and this utensil comprises the module that a plurality of sliding part formulas are installed, comprising the following:

This factory preferably also comprises sliding part formula module, can separate with them but these modules can be positioned near the of sliding part formula module 1 to 8, namely

-one sliding part formula module 9, it is an electric substation that is mainly used in middle voltage is changed into low-voltage, and/or

-one sliding part formula module 10, it is accommodated in the inner practical facility (control room, laboratory, lobby).

In addition, this device can comprise the instrument for supplying inert gas, for example is used for providing the device of liquid nitrogen and gas nitrogen; Be used for providing the air of compression and the instrument of water; And supplement and amenities.At least, sliding part 1,2,3,4 and 7, preferably all sliding parts, comprise housing for security reasons.

In sliding part 1, each hydrogen fluoride hold-up vessel has from 10 to 5000 liters, common 500 to 4000 liters, the preferred capacity of from 500 to 3000 liters generally.The instantiation of hydrogen fluoride hold-up vessel is the tank by RID/ADR-IMDG approval, UN T22 type or UN T20 type preferably.This type of tank is commercially available.

Each HF hold-up vessel in sliding part 1 can be properly connected on the hydrogen fluoride supply line by a manifold.

Each HF hold-up vessel in sliding part 1 is preferably isolable separately with the hydrogen fluoride supply line.

HF hold-up vessel in sliding part 1 can separate by a remote control, a preferred remote-controlled valve with the hydrogen fluoride supply line generally.More preferably, each hold-up vessel is equipped with a remote control, a preferred remote-controlled valve, allows container is separated with the hydrogen fluoride supply line.

When having remote-controlled valve, hand-operated valve is installed suitably in addition.These remote-controlled valves for example allow to operate this HF hold-up vessel from a telecontrol room.

In a preferred embodiment, these HF hold-up vessels comprise an automatic HF horizon sensor.Particularly, these HF hold-up vessels can be installed on platform scale.In the sort of situation, preferably, process treatment system, a concrete automatic process control system be exercisable with close first remote-controlled valve, with the HF vessel empty and open another the second remote-controlled valve that contains HF hydrogen fluoride hold-up vessel.This embodiment is effective especially for the manual operation of avoiding the HF valve and for the HF supply of guaranteeing to continue.

One preferred aspect, these valves are exercisable with (process in a process device that for example is connected with the HF supply line is interrupted) autoshutdown in the situation that the abnormal operation state.

Another preferred aspect, these valves are exercisable with autoshutdown under the HF leakage situation in sliding part 1.This HF leaks the leakage that may be for example connected by the optional flange of HF hold-up vessel inside and causes, has the possibility of closing these valves by remote control.This has specifically been avoided in this case the necessity near the hydrogen fluoride supply line.

This sliding part comprises that also valve is used to turn off the supply of HF and nitrogen.Preferably, sliding part 1 comprises 3 to 10 HF containers; Particularly preferably, it comprises 4,5,6,7 or 8 containers.For 150 tons of F ₂The productivity ratio in/year, 4 HF containers are fit to.Especially, the tank (if they can be closed by independent valve) that has smaller szie has improved the security of factory.These tanks can be from the material that the material of tolerance HF is made or liner tolerates HF at least.These walls should be enough thick; Preferably, they have the equivalent thickness of 10mm IMDG code (IMDG CODE).

In a specific embodiments, preferred permanent at least one the HF emergency container that comprises of sliding part 1.This HF emergency container is a HF hold-up vessel that preferably is connected to the sky as described herein on the HF supply line preferably.This HF emergency container is normally exercisable to receive the HF that leaks the HF hold-up vessel from.This HF emergency container is suitably remained under a kind of inert gas pressure or remains under vacuum.

They can be transported and/or can be lifted by a fork lift by lorry thereby these tanks preferably can be portable.

Sliding part 1 comprises a ventilating system, and surrounding air preferably for good and all is vented to a scrubber, particularly " emergency response scrubber " and be used for removes HF and F in (ERS) ₂(as described below).

Sliding part 2: describe now the sliding part (sliding part 2) that comprises electrolytic cell or a plurality of electrolytic cells in detail.It contains at least one electrolytic cell.Preferably, it contains at least two electrolytic cells.More preferably, it contains at least 6 electrolytic cells.A sliding part 2 with 8 electrolytic cells is fit closely.This sliding part preferably is constructed so that (if desired) if can increase other electrolytic cell when the needs of fluorine gas increase.These ponds comprise a plurality of chucks, can pass their recirculated cooling waters.If desired, sliding part 2 can be provided with the independent forms such as sub-sliding part 2A, 2B.In this a little sliding part, assembled the electrolytic cell of quantification.Independent sub-sliding part 2A and 2B (and any other sub-sliding part) are connected together to form an electrolytic cell chamber.Usually, this electrolytic cell chamber will comprise 4,6 or more electrolytic cell, for example 8 electrolytic cells or even more.Provide the advantage of several electrolytic cells to be in order to safeguard or to repair and of carrying out or closing of even a plurality of ponds can compensate by the output that improves other ponds.In order to assemble the advantage that some sub-sliding parts have be, within size can remain on admissible full-size for road transport usually.With these electrolytic cells be connected to for generation of F ₂And H ₂Collector on.Sliding part 8 comprises that at least one rectifier is to supply the DC electric current to electrolytic cell anode.Should be noted that, each battery can comprise one or more anodes.Typically, each electrolytic cell comprise 20 to 30 anodes and even more, up to 70 and more.A cable is connected each anode with this rectifier.Each cathode of electrolytic tank is connected on this rectifier by a copper or aluminium bus bar.A rectifier can provide electric current to the some of one or more electrolytic cells or all anodes.Preferred each anode is used a rectifier.Advantage is, depend on concrete anode feature, intensity at each independent anode place can be finely tuned, in the abnormal conditions at a concrete anode place (for example, overvoltage, short circuit or the anode that breaks down) can be detected immediately, thus allow to continue to produce F at all gas anode and electrolytic cell ₂The time automatically turn off out of order anode.

Sliding part 2 comprises that a chilled(cooling) water return (CWR) supplies with cooling water the chuck in these ponds.

Sliding part 2 also comprises a flow tank, preferably, is used for F with one ₂Flow tank and one be used for H ₂Flow tank be connected with each pond.These flow tanks are used for the F that reduces to produce in the pond ₂And H ₂Gas velocity, be pulled away to avoid the electrolyte dust.Preferably, these flow tanks comprise that a vibrator and a heater melt the electrolyte dust of these separation so that remove.

Collect the F that produces ₂Collector be connected with sliding part 3 by a pipe, for generation of H ₂Collector be by in a pipe and sliding part 5B (this will in following detailed description) for H ₂A scrubber be connected.In a preferred embodiment, sliding part 2 comprises that also a ventilating system is to process F ₂With HF and/or H ₂Accident release.

The surrounding air of sliding part 2 is ventilated with a scrubber, particularly for security reasons ERS scrubber (following this scrubber of having described).

Sliding part 3: it comprises the F that produces for purifying ₂Device.It comprises a cooler, wherein with F ₂Pre-cooled.Sliding part 3 also comprises a HF washer, wherein pre-cooled F ₂Contact with the HF under remaining on unusual low temperature.This HF washer comprises a cooling jacket, and a kind of cooling agent passes this chuck.This cooling agent can be the known a kind of liquid coolant of those of ordinary skill in the art or a kind of mixture that more preferably is in the gentle nitrogen of liquid nitrogen of the evaporation under definite mixing temperature.Sliding part 3 further comprises a surge tank, a compressor, and for example a HF condenser and at least one HF absorbing column of diaphragm type compressor and operation at low temperatures, preferably contain NaF as the absorbent that is used for HF.Preferably, at least two absorbing columns are included in sliding part 3.If desired, be in absorption mode thereby these adsorption columns are unnecessary one group, another group can be regenerated.These adsorption columns comprise a heater.If desired, the absorbing column of another group may reside in sliding part 3 or in the position that is used for reinstalling adsorbent.By a plurality of pipes, this HF condenser is connected on electrolysis sliding part 2.Preferably, at least one group of post is arranged in a go-cart that wheel arranged to keep them from this sliding part removable (can remove).

This HF condenser can be cooled to a temperature, and wherein the HF condensation is to form a kind of liquid or even a kind of solid.If preferably it is condensed to form liquid HF.Most suitable is that cooling this trap arrives the temperature of-60 ℃ to-80 ℃, preferably is cooled to approximately-70 ℃.As cooling medium, exercisable known cooling liquid is suitable under desirable low temperature.Preferably use a kind of N ₂Gas, this gas are by with liquid N ₂With gas N ₂Mix to obtain with suitable amount.This type of cooling is very reliable.Therefore, sliding part 3 comprises that a plurality of pipelines are to send and to extract cooling medium.

The surrounding air of sliding part 3 is ventilated with a scrubber, particularly for security reasons ERS scrubber (following description).

Sliding part 4: this sliding part is as storing fluorine gas and sending fluorine gas to using a place.Sliding part 4 comprises that a plurality of filters are used for removing any remaining entrained solid.Preferably, sliding part 4 also comprises a filter to remove solid.For example, the F that produces in electrolytic cell ₂May comprise the entrained solid electrolyte from electrolytic cell, usually, the adduct of KF and HF.This filter is preferably from the material structure of tolerance HF and fluorine; Stainless steel, copper, monel metal metal and especially nickel be particularly suitable.The filter of making from the particle of the sintering of these metals is very suitable, and these particles comprise that nano level aperture is to provide semiconductor grade F ₂, for example have the aperture that is equal to or less than 5nm, and more preferably, have the aperture that is equal to or less than 3nm.

If desired, sliding part 4 comprises that a prefilter has the F in the aperture that is equal to or less than 1 μ m with removal ₂Coarse grain.

Sliding part 4 preferably includes for the device of storing fluorine gas.It can for example comprise a surge tank and be used for fluorine gas.

Except surge tank, but a permanent or provisional fluorine gas storage unit that preferably replaces surge tank, sliding part 4 also to comprise being in a plurality of hollow body forms is used for storing F ₂This storage unit is attachable with other sliding parts.

" permanent fluorine gas storage unit " is interpreted as specifically referring to being incorporated into a fluorine gas storage unit in fluorine factory.For example, this fluorine gas storage unit can be a transmissible or preferred fixing unit, and the operation that this unit runs through fluorine factory is present in sliding part 4.Preferably, this permanent fluorine gas storage unit be designed to comprise with respect to the gross weight that is stored in the fluorine gas in this factory more than 90wt%, more preferably more than 95wt%, most preferably greater than the fluorine gas of 100wt%

Sliding part 4 further can be sent to fluorine gas and use point from sliding part 2.The possible parts of sliding part 4 are including, but not limited to supply line, compressor, mixer and surge tank.It can also comprise monocell FT-IR and be used for the fluorine analysis.

" attachable " is interpreted as specifically referring to that this permanent fluorine gas storage unit is equipped as on parts that can be connected to sliding part 4.Preferably, this permanent fluorine gas storage unit fitted to be and can be connected on a fluorine gas supply line.One preferred aspect, run through the operation of this fluorine gas factory, this fluorine gas storage unit be connected on parts of sliding part 4, specifically on fluorine gas supply line.One further preferred aspect, the fluorine gas storage unit is directly to be connected with parts of sliding part 4.

The suitable equipment that connects for the fluorine gas storage unit on parts that will be connected to sliding part 4 comprises a manifold, thereby this manifold is connected on each hollow body of fluorine gas storage unit and preferably has a valve-off on each pipeline and allows separately separately each hollow body by a pipeline, and described manifold is further to be connected on parts of sliding part 4.

Sliding part 4 preferably includes from 4 to 25 hollow bodies, from 5 to 8 hollow bodies more preferably.These hollow bodies preferably have identical in fact shape and size.Cylindrical shape hollow body (pipe) is preferred.Each hollow body that fluorine gas is stored preferably has a shut off valve.

A plurality of hollow bodies of fluorine gas storage unit can be fixed together suitably by a suitable framework.Concrete frame geometry comprises triangle, square and rectangular geometry.

In fluorine gas according to the present invention factory, these fluorine gas storage facilities can contain the fluorine gas of the pressure that is at least 25 pounds/square inchs (about 1.72 gauge pressures) generally.Usually this pressure is to be equal to or greater than 35 pounds/square inchs (about 2.4 gauge pressures), preferably is equal to or greater than 40 pounds/square inchs (about 2.8 gauge pressures).In factory according to the present invention, these fluorine gas storage facilities can comprise or comprise the fluorine gas that is in 400 pounds/square inchs at the most (about 27.6 gauge pressures), preferably is equal to or less than the pressure of 75 pounds/square inchs (about 5.2 gauge pressures) generally.Usually this pressure is to be equal to or less than 65 pounds/square inchs (about 4.5 gauge pressures), preferably is equal to or less than 60 pounds/square inchs (about 4.1 gauge pressures).It will be appreciated that, the hollow body of fluorine gas storage unit can comprise or comprise the fluorine gas that is in above-mentioned pressure generally.Particularly preferably be these hollow bodies and contain the fluorine gas that is in above-mentioned pressure.

In fluorine gas according to the present invention factory, the molecule F that stores in the fluorine storage facility ₂Molecule F every day with fluorine gas equipment ₂The ratio of production capacity is from 0.1 to 1, preferably from 0.1 to 0.25 generally.

Preferably, each hollow body can be closed separately from this factory; This has improved security.Fluorine leaves sliding part 4 and preferably is transported to by double-wall pipe and uses the some place.Fluorine gas transports in inner tube; Outer double wall big envelope comprises nitrogen.These pipings comprise that a pressure sensor analyzes the nitrogen pressure in outer double wall big envelope.Preferably, the wall of these pipes is thicker than the wall that is generally used for transporting gas, that is, preferably, their thicker 1mm, preferably, thicker 4mm; The wall thickness that is equal to or greater than 5mm is particularly preferred; The pipe that is categorized as " catalogue listing 80 " is fit closely.They are for improvement of security.Piping with welding of RADI is fit closely.

It is upper or transportable by a fork lift truck that this or these hold-up vessel can be arranged on wheel.

The surrounding air of sliding part 4 is ventilated with a scrubber, particularly ERS scrubber (for security reasons) as described below.

In fluorine gas according to the present invention factory, using point can be to be connected with an other making factory, and for example chemical device or concrete one use fluorine gas for surface-treated factory.Use the site normally to be connected with a semiconductor fabrication factory, the manufacturing of preferred light electric installation or flat-panel monitor.

In a preferred embodiment of fluorine gas according to the present invention factory, the sliding part 4 that comprises the fluorine gas storage unit is spaces of a sealing.A fluorosensor that is connected that comprises the space that to trigger sealing and scrubber sliding part 6 on the spatial overall of this sealing.Suitably, the space of this sealing is to be connected to an aspiration line on fan by one to be connected on sliding part 6, thereby this fan is exercisable gas to be transported to sliding part 6 from the space of the sealing of sliding part 4.

In another embodiment, factory further comprises a blender, a preferred static mixer according to fluorine gas of the present invention, described blender preferably can be accepted from the fluorine of sliding part 4 and accept inert gas from an inert gas supply line, as preferably argon and/or nitrogen.

In an optional embodiment, a pressure control loop has been regulated, will be fed to generally and use a pressure decreased of the fluorine gas at place to desirable value.

Sliding part 5 provides by water quench or has heated the part of factory.It is preferably placed near the sliding part 2 or sub-sliding part 2A and 2B or any other sub-sliding part 2X of electrolysis, and more preferably, it is to be positioned at these above sliding part.Sliding part 5 comprise at least one be used for when when beginning reaction heating electrolytic cell with molten electrolyte salt and when reaction moves the loop of cooling these electrolytic cells.Cooling water has been filled in this loop, and this water can be running water or distilled water.This loop comprises a surge tank, a pump (preferably unnecessary) and the drying cooling device with fan (having variable speed drives).In operating process, cooling water preferably remains on 75 ℃ to 95 ℃ to avoid electrolytical the solidifying in electrolytic cell.

Other heat exchangers that are used for cooling this device in another loop that sliding part 5 comprises.It contains a kind of cooling fluid, and a mixture of preferred water and ethylene glycol more preferably, comprises by weight the water of 40% ethylene glycol.Same this loop comprises a kind of buffer solution, a pump (preferably unnecessary) and a drying cooling device.This cooling circuit comprise for a plurality of detectors of the temperature of measuring cooling water, be used for heating and cooling water device (for example electrical heating), be used for the heat exchanger of cooling this type of circulating fluid.

Sliding part 6 comprises at least one scrubber, and each is used for F ₂And H ₂Preferably, these scrubber pumps are unnecessary.The sliding part of this factory (particularly sliding part 1,2,3,4 and 7) comprises a ventilating system so that the surrounding air of sliding part shell passes through the permanent ventilation of scrubber in sliding part 6.

Preferably, scrubber sliding part 6 comprises a F ₂Scrubber is used for for security reasons or maintenance operation is destroyed any F ₂Or HF ventilating opening.F from the air of the ventilation of sliding part ₂Be treated for emergency response (ERS) in a scrubber with HF.These scrubbers are jet scrubber and suction is provided preferably.These scrubbers can be arranged on sub-sliding part, sub-sliding part 6A for example, and it comprises that at least one is used for the scrubber of emergency response (ERS), a sliding part 6B, it is used for the H that washing produces ₂, purpose is to remove the HF that wherein carries secretly, and scrubber is derived from HF and/or F in the waste gas of ventilation of surrounding air of sliding part with removal ₂(as explained above).

The F of rule ₂The F of the corresponding at least desired amount that remains to be removed in the regular operation process of scrubber (optional being arranged in sub-sliding part 6B) ₂By contacting and remove F with a kind of solution that alleviates ₂This scrubber preferably includes a kind of jet scrubber and a packed column alleviates solution and F to provide ₂Between high contact area.Preferably, leave the F of rule ₂The gas of scrubber passes the support scrubber of ERS scrubber.

These ERS scrubbers are as the F of rule ₂The support scrubber of scrubber, it is used for removing F from the air of ventilating ₂Or HF and be used for containing HF and/or F ₂The emergent management of the gas of ventilating after leaking.The capacity of ERS scrubber (optional be arranged in sub-sliding part 6A) is preferred at least corresponding to the fluorine that remains to be removed in for the emergency situation and the amount of HF, for example, in the situation that the tracheal rupture that may not occur very much, in the accident about the hold-up tank of a pipe containing fluorine or a kind of HF.What advise is the capacity of ERS scrubber of selecting according to the worst situation; If for example exist and have 2m ³The HF tank of capacity and have 8kg F ₂The F of capacity ₂Storage tube, this ERS should be able to reduce corresponding HF and F ₂Amount and factory's hold-up.Preferably, this ERS scrubber comprises for 2 unit that wash to realize high destruction and to remove efficient; Come to unnecessary pumping material by normal and emergency power supply.It preferably includes a kind of jet scrubber and packed column to realize that pending gas is arranged and to alleviate good contact between solution.Other unit that are used for the emergency processing can comprise a packed column, but preferably, it comprises the jet scrubber of two series connection.Can remove F with known being used for ₂Reagent carry out F ₂Remove.Preferably, a kind of KOH solution or NaOH (choose wantonly and comprise a kind of alkali metal thiosulfate, for example sodium thiosulfate or potassium thiosulfate, or a kind of alkali metal nitrites salts, for example potassium nitrite or natrium nitrosum) be used as alleviating solution and come pumping by this scrubber or these scrubbers and this post (if present), as for F ₂Distintegrant.Can predict a cooler and be used for cooling KOH solution.Certainly, this is that an emergency scrubber is for the treatment of HF and F ₂An advantage of design.

Be used for H ₂The scrubber of the sliding part 6 that the HF of air-flow reduces can be arranged in sub-sliding part 6B.Sub-sliding part 6B preferably includes the jet scrubber of a use HF solution-operated to reduce H ₂In HF content.The concentration of HF can be in the scope between 1% and 10% by weight.This scrubber further comprises a packed column, wherein gives fresh water at the top of post to reduce HF content.Sliding part 6B also comprises a pipeline, and it allows to dilute H by nitrogen (it is used as the cooling medium in sliding part 3) ₂

In sliding part 6 or corresponding sliding part 6A and the reliability of the scrubber in 6B be very important.Therefore, be used for making that to alleviate the basic element of character of solution circulation by these scrubbers can be unnecessary as fan or pump.Every now and then, alleviate to circulation and add fresh moderator in solution, for example KOH solution, and/or thiosulfate or its solution are for example provided by a truck.

Sliding part 6 preferably also comprises in the situation that one or more depressions of holding back of the liquid of accidental leakage.

Sliding part 7 relates to the F that produces for analyzing ₂Device.It is preferably mounted near sliding part 2A and 2B; Most preferably, it is positioned at sliding part 2A and above 2B.Sliding part 7 is for example an analyzer barrier.Ambient air around it preferably ventilates and arrives ERS's.This analyzer comprises and is suitable for determining the F that produces ₂The analytical equipment of content of major impurity.An optional ultraviolet spectrometer (it analyzes ultraviolet spectra) and many inputs, many ponds FT-IR spectrometer (Fourier transform infrared spectroscopy) analyzer are fit closely.Preferably, take from the thick F of electrolytic cell ₂And the F of purifying ₂Both are sent to more than one in the FT-IR of pond.At passage of a given time series analysis.HF, CF ₄, C ₂F ₆, COF ₂, SF ₆And SO ₂F ₂Amount for example can measure by FT-IR, and F ₂Content can analyze by UV.Have been found that ultraviolet spectroscopy can be as a direct survey tool for fluorine, it has demonstrated the violent reduction of fluorine concentration when the anode burning occurs; Same time in FT-IR is observed CF ₄Huge increase.Therefore, this burning is easy to by F in combustion process ₂The sharply reduction of concentration detects, and having formed impurity in this process (is mainly CF ₄, C ₂F ₆And COF ₂).The result of this burning (F that produces ₂More CF when containing than regular operation ₄,, C ₂F ₆, COF ₂, HF) be not only the change of impurity content and also have the sharply reduction of the fluorine content of monitoring by detector (being by UV spectroscopy especially in the present invention).In the measuring process of using UV spectroscopy, can use whole UV spectrum.Preferably, be not with whole spectrum and only with the absorption of this certain wave strong point (specifically 200 and 400nm between, more preferably 250 to 330nm, most preferably between 270 to 290nm, even at the UV spectrum at about 280nm place) be used for measuring because it is almost F ₂The maximum that absorbs of UV.FTIR and UV measure the same F that is used for controlling purifying ₂Purity.Therefore, this is analyzed and is used for by measuring thick F with UV ₂And measure CF with FT-IR ₄Detect the anode burning and be used for proof and the F of control purifying ₂Purity.

The thick F of all electrolytic cells ₂And the F of purifying ₂By continuous sampling and analysis.Present FT-IR can accept up to 9 samples.Therefore, the F of purifying ₂And up to the thick F of 8 electrolytic cells ₂Can analyze with many ponds FTIR of electric current-producing device.Alternately, replace the FT-IR of sliding part 7 and optional UV analyzer, sliding part 4 can comprise a single pond FT-IR.

Sliding part 8 comprises rectifier or rectifier tooth bar, BPCS (basic process control system), ESD (emergency shutdown system), F﹠amp; G (fire and gas system) panel (alignd fire alarm and gas alarm), small size motor starter, light intensity distributions and other electric devices that installs to provide electric power and control factory.Sliding part 8 is arranged near sliding part 2A and 2B; Preferably, it is positioned at above them.Each electrolytic cell as previously discussed, has a plurality of anodes usually, for example 26.Preferably, each anode is supplied by a rectifier.The preferably assembling in the rectifier box (cabinet) in being contained in the shell of air conditioning of these rectifiers.

Preferably providing slight superpressure to avoid gas with protection in this sliding part 8 enters.All cables and negative electrode bus bar should be sealed carefully.

Preferably the rectifier box be on a fixing framework with bolt fixing be used for earthquake protection.

Sliding part 8 comprises a plurality of walls and a top cover.It preferably also comprises a fire detection system, particularly a VESDA (very early-stage smog checkout gear) and a shutdown systems, and this system is for example with HFC-227ea or use (mixture of inert gas (nitrogen, argon and carbon dioxide)) operates.

Sliding part 9 is a prefabricated chamber preferably, and this chamber has concrete wall or is similar to a container of making from metal shield.It contain be useful on be connected to electric current and with it therefrom voltage change into the device of low-voltage.Preferably, it contains " sub-power station " sub-sliding part 9A and 9B.Sliding part 9A contains preferably that MV (middle voltage) pond is that be used for introducing to be used for electric current and voltage is changed into low-voltage current with electric current output and by-pass current and transformer.It is exercisable for local area network; For example, these transformers are to be selected as their to be fit to local voltage, and this voltage can be for example 380V or 400V (50Hz) or 440V (60Hz).Sliding part 9 preferably also comprises a fire detection system, particularly a VESDA (very early-stage smog checkout gear) and a shutdown systems, and this system is for example with HFC-227ea or use

(mixture of inert gas (nitrogen, argon and carbon dioxide)) operates.

Sliding part 9B is the prefabricated concrete chamber with a plurality of walls and a top cover equally preferably.This substation has held low-tension switch gear (LVCS) and a diesel-driven generator.It is to be interconnected on the sliding part that needs low voltage power supply by cable, for example by a cable trough.It preferably also comprises a fire detection system, particularly a VESDA (very early-stage smog checkout gear) and a shutdown systems, and this system is for example with HFC-227ea or use

(mixture of inert gas (nitrogen, argon and carbon dioxide) operates.

Sliding part 9B preferably also comprises one for the battery charging plant of a fork lift truck.

Sliding part 9B must be interconnected on the process sliding part, and particularly sliding part 2.

Sliding part 10 comprises the practical facility for the individual, for example, and a control room, a laboratory and a lobby.Preferably, it is divided into sub-sliding part 10A and sub-sliding part 10B.Sub-sliding part 10A contains control room and laboratory.May be that little laboratory comprises a fume hood with good ventilation, for example up to 500m ³/ h and even larger, that this cupboard is preferably made by acid resisting material and can be used for analyze titration, a safety cabinet is used for reagent and sample, a hand basin and a chemical pool, wherein can collect the chemicals waste product, preferably in a cylinder of being made by acid resisting material.This laboratory preferably has a detector, and this detector is arranged on the fresh air inlet place, and a closing organ, the body import of holding one's breath in situation ShiShimonoseki of gas alarm of this mechanism.Sub-sliding part 10A preferably remains under slight superpressure to prevent that air from entering.Sliding part 10A preferably includes air conditioning.

Preferably on on-line joining process to a remote control panel, this remote control panel can be positioned on another facility the control panel in this control room.This has allowed from the single some fluorine gas of a control room operated from a distance production plant.

Sub-sliding part 10B contains the lobby.It contains the useful equipment for the control room individual.The cabinet that it preferably includes a plurality of drawers, a dressing cubicle, a lavatory, a shower and is used for chemicals dustcoat (gloves, tippet etc.).This factory safety shower comprises a shower system and preferably is positioned near the outside of sub-sliding part 10B, because it must be supplied the water quoted of heat.Sliding part 10 preferably includes and ventilates and heating.

Method of the present invention is to carry out in the framework of sliding part 6.

Another aspect of the present invention relates to a kind of aqueous solution, and this aqueous solution contains or consists of by weight a kind of inorganic agent of 1% to 5% (this inorganic agent is selected from lower group, and this group is comprised of the following: KNO ₂, NaNO ₂, Na ₂S ₂O ₃And K ₂S ₂O ₃), 10% to 45% KOH, 10% to 45% NaOH, or KOH by weight and a kind of mixture of NaOH by weight, the total content of described mixture is by weight 10% to 45% of this solution.

A kind of preferred aqueous solution contains or consists of by weight a kind of inorganic agent of 1% to 5% (this inorganic agent is selected from lower group, and this group is comprised of the following: Na ₂S ₂O ₃And K ₂S ₂O ₃), 10% to 45% KOH, 10% to 45% NaOH, or KOH by weight and a kind of mixture of NaOH by weight, the content of this mixture is by weight 10% to 45% of this solution.

Comprise or consist of 1% to 5% Na by weight ₂S ₂O ₃, the solution that is equal to or greater than 50% water and is equal to or greater than by weight 15% KOH by weight is particularly preferred.

Consist of 1% to 5% Na by weight ₂S ₂O ₃, the solution that is equal to or greater than 50% water and is equal to or greater than by weight 15% KOH by weight is most preferred.

These solution are for F ₂Remove and/or OF ₂It is suitable removing (from the gas that contains them).They can be stored in an independent sliding part.

If the disclosure content in any patent, patent application and publication that is combined in by reference this and the application's the afoul degree of explanation may make a term unclear to it, this explanation should be preferential.

Following instance is intended to explain method of the present invention and is not intended to limit the scope of the invention.

Example 1: use KOH and Na ₂S ₂O ₃Or K ₂CO ₃And Na ₂S ₂O ₃Remove F ₂

The device that uses:

With a kind of F ₂/ N ₂Admixture of gas is stored in a pressure bottle, this mixture consist of 10% F by volume ₂And 90% N by volume ₂This bottle by valve with is connected a gas line and is connected with a scrubbing tower, this scrubbing tower comprises the stainless steel helices of any arrangement.To comprise pure N ₂A pressure bottle be connected on this gas line by a valve; Therefore, comprise 10% F by volume ₂Admixture of gas can be diluted to any desirable F ₂Concentration.A kind of scrubbing liquid is included in a hold-up tank.This hold-up tank is to be connected to the bottom of scrubber and top by a plurality of pipelines, and cleaning solution is recycled to the top of scrubber post by a heat exchanger from hold-up tank, with the admixture of gas counter current contacting that contains fluorine and nitrogen, process with wash liquid, and with after wash liquid contacts, be collected in this hold-up tank.The admixture of gas of the processing that the top is stayed passes a cold-trap to remove any liquid of carrying secretly, then it is passed a FTIR analyzer to determine remaining OF ₂Content.F ₂Content to be confirmed as be very near 0 (being pointed out by mass balance, although it may be coarse).This admixture of gas is passed one contain H ₂O and Na ₂S ₂O ₃Trap to ensure any F still be present in admixture of gas ₂Removal.

The volume that has 4 liters in hold-up tank.

Time of staying of the gas of processing with the alkali of different content, thiosulfate, volume/chronomere/different and F in pending admixture of gas is arranged ₂Variable concentrations test.In some tests, alkali or thiosulfate are not comprised in cleaning solution accordingly.

When with F ₂During contact, the cleaning solution temperature in tower remains in the scope of 20 ℃ to 30 ℃.

There is the pressure of pending admixture of gas to keep constant in scrubbing tower in process of the test, between about 1.1 bar to 1.3 bar (absolute value).

The alkali of using:

KOH in water, concentration is about 30% KOH by weight

K ₂CO ₃, concentration is by weight about 20%

Tested following parameter to F ₂OF in the gas of removal validity and processing ₂The inhibiting impact of content:

Na ₂S ₂O ₃Concentration: 0%, by weight 0.5%, by weight 1%, by weight 2%.

The time of staying (in bracket, corresponding gas flow rate liter/h): 140 seconds (25L/h); 70 seconds (50L/h); 14 seconds (250L/h); 7 seconds (500L/h) (is in different F in pending gas is arranged ₂Concentration).

Liquid load density: (in bracket, m ³/ (hm ²)).Higher fluid load density refers to enter the cleaning solution of more volume at the top of this post in the scrubber post, thereby has caused the wetting of better liquid distribution and better random filler.Tested the liquid load density of two scopes, i.e. 30m ³/ (hm ²) to 50m ³/ (hm ²) and 100m ³/ (hm ²) to 120m ³/ (hm ²).

The F that pending admixture of gas is arranged in the porch of scrubbing tower ₂Concentration: by volume 0.8%; By volume 1%; By volume 1.6%; By volume 10%.

The OF that provides with ppm by volume ₂Concentration, as measured by FTIR in the exit at this scrubber.

Mass balance demonstrates effective F that removed ₂

With each test operation stage of about 1 hour to 6 hours.OF for the scrubber exit ₂The minimum and the maximum that provide with ppmv have shown additive Na ₂S ₂O ₃Effect in water-based KOH scrubber liquor and the time of staying are to OF ₂The impact of destroying.At the exit of scrubber OF ₂Content is lower, and the destruction of this compound is better.The longer time of staying in scrubber is for OF ₂The degree of removing is favourable.

Corresponding parameter and the concentration that obtains are compiled in table 1.Comprised that test 1,3,4,6 and 8 is used for relatively.

Can draw to draw a conclusion from result of the test:

Both are removing F water-based potassium hydroxide and potash (if using together with thiosulfate) ₂And decomposition OF ₂The aspect is effective.Owing to not having foam to produce, potassium hydroxide is preferred, and in the situation that thiosulfate is finished therein, is to decompose OF than carbonate ₂The aspect is more effective.

In order (for example to be derived from the gas of emergency, wherein to contain F with inert gas dilution from the gas with high volumetric flow of gas ₂Gas) in remove F ₂, the thiosulfuric acid salinity that is in upper extent is favourable.2% to comprise that a kind of fluid composition of thiosulfate is very effective by weight.

The mass balance of test has confirmed removing F for the condition that limits ₂The good effect of aspect, these conditions are as the filling for the device of testing the constant time period and not having to use.Relatively demonstrating of mass balance estimation and testing experiment result is except destroying OF ₂Outside, also realized at least 90% to 95% F ₂Reduce, particularly for comprising lower F ₂The admixture of gas of content and short residence time (emergency).

The shorter time of staying and higher thiosulfuric acid salinity have been improved OF ₂Decomposition, together with higher fluid load amount, for example 100m ³/ (hm ²) to 120m ³/ (hm ²) and 30m ³/ (hm ²) to 50m ³/ (hm ²) compare.

The K of any precipitation ₂SO ₄Can be by water injection or by providing the cleaning solution mixture to dissolve.

Example 2: use NaOH and Na ₂S ₂O ₃Remove F ₂

In the device of example 1, comprise by weight 30% NaOH and 2% Na by weight ₂S ₂O ₃A kind of fluid composition be used as cleaning solution (cleaning fluid).To comprise 10% F by volume ₂(be N to 100% surplus by volume ₂) a kind of gas as described in the test 2 of example 1 with cleaning solution counter current contacting in scrubbing tower.Detected OF ₂Leave the OF that contains in the gas of scrubbing tower in the test 2 of level corresponding to example 1 ₂Level.

Example 3: use Na ₂CO ₃And Na ₂S ₂O ₃Remove F ₂

In the device of example 1, comprise 18% Na by weight ₂CO ₃And 1% Na by weight ₂S ₂O ₃A kind of fluid composition be used as cleaning solution (cleaning fluid).To comprise 10% F by volume ₂(be N to 100% surplus by volume ₂) or 1.6% F by volume ₂(be N to 100% surplus by volume ₂) or 0.8% F by volume ₂(be N to 100% surplus by volume ₂) a kind of gas as described in the test 9 of example 1 with cleaning solution counter current contacting in scrubber column.Detected OF ₂Leave the OF that contains in the gas of scrubbing tower in the test 9 of level corresponding to example 1 ₂Level.

Example 4 (comparison example): use Na ₂CO ₃(there is not Na ₂S ₂O ₃) removal F ₂

Repeat example 3, but do not add Na in this cleaning solution ₂S ₂O ₃OF in leaving the gas of scrubbing tower ₂Content is corresponding to the OF of example 8 ₂Content.

Example 5: a kind of KOH/Na ₂S ₂O ₃The long-term stable experiment of solution

Test in example 5.1:72 hour

The air that will have the pressurization of 100l/h flow velocity passes a kind of aqueous solution and continues 72 hours, and this aqueous solution is included in 1 liter of container, and this container comprises 1.8% Na by weight ₂S ₂O ₃And about 30% KOH by weight.At Na ₂S ₂O ₃The concentration aspect do not observe variation.

Test in example 5.2:15 days

The air that will have the pressurization of 100l/h flow velocity passes a kind of aqueous solution and continues 10 days, and this aqueous solution is included in 1 liter of container, and this container comprises 4.2% Na by weight ₂S ₂O ₃And about 30% KOH by weight.At Na ₂S ₂O ₃The concentration aspect do not observe variation.

Example 5 proofs do not exist a kind of KOH of comprising and Na ₂S ₂O ₃Solution by contact the risk that can become invalid with air; This observed result has increased security elements to method of the present invention, particularly is incorporated in a device in the sliding part concept, and wherein the vent air from sliding part in case of emergency passes this scrubber.

Example 6: use KOH and KNO ₂Remove F ₂

To comprise by weight 28.6% KOH and 1.02% KNO by weight ₂3095g cleaning solution in the scrubbing tower of example 1 with a kind of F of 10% by volume that comprises ₂(be N to 100% surplus by volume ₂) gas contact 3.5 hours.Gas flow rate is 25l/h.At first, the OF in leaving the gas of scrubbing tower ₂Content is about 20ppm.After the process some time, the OF that detects in the gas of processing ₂Level begin to rise until the value of 60ppm.

After described 3.5h, with N ₂Be mixed in the admixture of gas that enters scrubbing tower, thereby make the admixture of gas that obtains comprise 1% F by weight ₂This is processed continued other 3 hours.OF in leaving the gas of scrubbing tower ₂Level is confirmed as about 5ppm to 10ppm and the extremely about 20ppm of rising at first.This has proved, the solution that even almost is finished still is suitable for processing and contains lower F ₂Concentration and have the gas of the satisfaction of low gas flow is as there being pending gas in emergency.Residual KNO ₂Concentration is confirmed as by weight about 0.2%.

After described 6.5h, with wash solution again with comprise 10F ₂The air of (having gas flow 25l/h) contacts.Pass the OF of scrubbing tower ₂Level increases fast and shows that wash liquid used up.

This example shows KNO ₂It is a kind of suitable reducing agent.With Na ₂S ₂O ₃Difference be, pass the OF of processing ₂Level continue to rise, show KNO ₂Early stage consumption, pass the OF of scrubbing tower ₂Level remain and be in over a long time low-level (if Na ₂S ₂O ₃As reducing agent).Suppose KNO ₂Higher initial concentration or replenish the KNO will improve for long-term disposal ₂Adaptability.

Example 7: the oxidation-stabilized property testing of potassium nitrite/KOH solution

Prepared a kind of aqueous solution, this aqueous solution comprises about 1.5% KNO by weight ₂And 30% KOH by weight.Continue 24 hours, the gas-pressurizeds of about 100 l/hs are passed this solution.3% initial nitrite concentration (being set as 100%) is oxidized.After processing 96 hours, the nitrite of about 5% initial existence is oxidized.

This test proved, even under extreme conditions, this nitrite solution is sufficiently stable with to anti-oxidant in this example.

Example 8: use to comprise by weight 15% KOH and 1% Na by weight ₂S ₂O ₃A kind of solution removal F ₂

About 2800g is comprised by weight 15.8% KOH and 1% Na by weight ₂S ₂O ₃A kind of solution contact 5 hours with a kind of gas in the scrubbing tower of example 1, this gas consist of 10% F by volume ₂And 90% N by volume ₂Gas flow rate is 25 liters/h.OF in leaving the gas of scrubbing tower ₂Maximum level determines it is lower than 20ppm by FTIR.

Only comprise that the high efficiency of a kind of cleaning solution of 15% KOH has by weight proved the high efficiency of the combination of KOH and thiosulfate.

Claims

1. one kind is used for obtaining to have the F that reduces content ₂And/or OF ₂And, if exist in pending gas is arranged, the method for the gas of the HF of reduction content, the method comprises at least one step, this step is from comprising F ₂And/or OF ₂And remove F in the gas of optional HF ₂And/or OF ₂, wherein this gas being contacted with fluid composition, this fluid composition comprises the alkali metal thiosulfate of dissolving and/or alkali metal nitrites salts and at least a alkali that is selected from the dissolving in alkali metal hydroxide and alkali carbonate of dissolving.

2. the method for claim 1, wherein this gas comprises F ₂

3. as claim 1 or method claimed in claim 2, wherein this gas is contacted with fluid composition, this fluid composition comprises the alkali metal thiosulfate of dissolving, and wherein this alkali metal thiosulfate is selected from sodium thiosulfate and potassium thiosulfate.

4. method as described in any one in claims 1 to 3, wherein this alkali is selected from potassium hydroxide and NaOH.

5. method as described in any one in claims 1 to 3, wherein this fluid composition comprises potassium hydroxide and sodium thiosulfate or potash and sodium thiosulfate.

6. method as described in any one in claim 1 to 5, wherein with respect to the gross weight of said composition, the concentration of the thiosulfate of this dissolving is equal to or greater than 0.3% and be equal to or less than by weight 5% by weight.

7. method as described in any one in claim 1 to 6, wherein with respect to the gross weight of said composition, the concentration of the alkali of this dissolving is equal to or greater than 15% and be equal to or less than saturated concentration by weight.

8. the described method of any one according to claim 1 to 7 is wherein with this gas and this fluid composition counter current contacting.

9. method as described in any one in claim 1 to 8 is wherein clung to said composition this gas under the pressure of (absolute value), preferred 1.1 bar to 2 bar (absolute value) and is contacted at 1 bar to 3.

10. method as claimed in any one of claims 1-9 wherein, wherein with this gas and this fluid composition in scope from 10 ℃ to 80 ℃, preferably contact at the temperature of 20 ℃ to 40 ℃ in scope.

11. method as described in any one in claim 1 to 10 wherein comprises F ₂Gas source F outside specification ₂Gas, or be derived from electrolysis manufacturing F ₂Initial period, or it is derived from emergency.

12. method as described in any one in claim 1 to 11 wherein comprises F ₂Gas source F outside specification ₂Gas, or be derived from electrolysis manufacturing F ₂Initial period and contain by volume the F of 70% to 98% amount ₂, or it is derived from emergency and contains by volume the F of 1% to 5% amount ₂

13. method as described in any one in claim 1 to 12, the gas that wherein obtains after contacting with this fluid composition comprises the OF that is in the concentration that is equal to or less than by volume 200ppm ₂

14. method as described in any one in claim 1 to 13, wherein this processing is carried out in treating apparatus, and this treating apparatus is incorporated in sliding part.

15. one kind for the manufacture of the method that is selected from the chamber that article in semiconductor, photocell, TFT and MEMS or cleaning use in making described article, the method comprises at least one step, and this step comprises the method for any one according to claim 1 to 14.

16. an aqueous solution contains or it consists of: 1% to 5% inorganic agent by weight, this inorganic agent is selected from KNO ₂, NaNO ₂, Na ₂S ₂O ₃Or K ₂S ₂O ₃10% to 45% KOH by weight; 10% to 45% NaOH by weight; Or the mixture of KOH and NaOH, the total content of described mixture is by weight 10% to 45% of this solution.

17. solution as claimed in claim 16 comprises or it consists of: 1% to 5% Na by weight ₂S ₂O ₃, the KOH that is equal to or greater than 50% water and is equal to or greater than by weight 15% by weight.