WO2012034978A1 - Plant for fluorine production - Google Patents
Plant for fluorine production Download PDFInfo
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- WO2012034978A1 WO2012034978A1 PCT/EP2011/065773 EP2011065773W WO2012034978A1 WO 2012034978 A1 WO2012034978 A1 WO 2012034978A1 EP 2011065773 W EP2011065773 W EP 2011065773W WO 2012034978 A1 WO2012034978 A1 WO 2012034978A1
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- Prior art keywords
- skid
- plant
- anyone
- plant according
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/20—Fluorine
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Definitions
- MEMS metal-organic chemical vapor deposition
- etching etching of the respective items
- suitable chambers these processes are often plasma-assisted.
- deposits are often not only formed on the item, but also on the walls and other interior parts of the chamber.
- elemental fluorine is a very effective agent both for etching and for cleaning the chambers to remove undesired deposits. Processes of this kind are for example described in WO 2007/116033 (which describes the use of fluorine and certain mixtures as etchant and chamber cleaning agent),
- the present invention provides an improved plant suitable to produce fluorine on-site especially for the use as etchant and chamber cleaning agent in the manufacture of semiconductors, photovoltaic cells, thin film transistor liquid crystal displays and micro-electromechanical systems.
- the plant of the present invention provides fluorine gas to a tool which applies fluorine gas as reactant to perform chemistry in this tool which apparatus comprises skid mounted modules including at least one skid mounted module selected from the group consisting of
- skid mounted module comprising at least one storage tank for FIF, denoted as skid 1,
- skid mounted module comprising at least one electrolytic cell to produce F 2 , denoted as skid 2,
- skid mounted module comprising purification means for purifying F 2 , denoted as skid 3,
- skid mounted module comprising means to deliver fluorine gas to the point of use, denoted as skid 4,
- skid 5 a skid mounted module comprising cooling water circuits, denoted as skid 5
- skid mounted module comprising means to treat waste gas, denoted as skid 6,
- skid mounted module comprising means for the analysis of F 2 , denoted as skid 7, and
- skid mounted module comprising means to operate the electrolysis cells, denoted as skid 8.
- Figure 1 shows an embodiment of the plant according to the invention with a useful arrangement of the skids.
- the preferred plant of the present invention provides fluorine gas to a tool which applies fluorine gas as reactant to perform chemistry in this tool which apparatus comprises skid mounted modules including
- skid mounted module comprising at least one storage tank for HF, denoted as skid 1,
- skid mounted module comprising at least one electrolytic cell to produce F 2 , denoted as skid 2,
- skid mounted module comprising purification means for purifying F 2 , denoted as skid 3,
- skid mounted module comprising means to deliver fluorine gas to the point of use, denoted as skid 4,
- skid 5 a skid mounted module comprising cooling water circuits, denoted as skid 5
- skid mounted module comprising means to treat waste gas, denoted as skid 6, - a skid mounted module comprising means for the analysis of F 2 , denoted as skid 7, and
- skid mounted module comprising means to operate the electrolysis cells, denoted as skid 8.
- the plant preferably also comprises skid modules which may be located close to the skid modules 1 to 8 but may be separated from them, namely
- skid module 9 which is an electrical sub-station mainly to transform
- skid module 10 which houses utilities (control room, laboratory, rest room).
- the apparatus may comprise means to supply inert gas, e.g. means to supply liquid and gaseous nitrogen ; means to supply compressed air and water ; and ancillaries and amenities.
- inert gas e.g. means to supply liquid and gaseous nitrogen ; means to supply compressed air and water ; and ancillaries and amenities.
- skids 1, 2, 3, 4 and 7, preferably all skids comprise housings for safety reasons.
- fluorine gas denotes in particular molecular fluorine (F 2 ) and mixtures thereof, in particular with inert gases.
- Inert gases are preferably selected for example from argon, nitrogen, oxygen and N 2 0.
- a preferred fluorine gas consists or consists essentially from F 2 .
- Figure 1 shows a plant P according to the present invention.
- the size is 39m by 23m.
- Reference sign 1 in figure 1 indicates skid 1 comprising HF storage and evaporation.
- Reference sign 2 indicates skid 2 indicated by a dotted line, comprising the electrolytic cells ; it is located in the basement of the plant underneath modules 5 and 7.
- Reference sign 3 of the figure refers skid 3 comprising purification means to purify the produced F 2 .
- Reference sign 4 of figure 1 indicates skid 4 comprising the storage means for fluorine gas. Skid 4 may also comprise, according to one embodiment, a single cell FT-IR for final analysis of the purified F 2 ready for use or final storage.
- Reference sign 5 of figure 1 indicates skid 5 housing the cooling water means. It is located above skid 2.
- Reference sign 6A in figure 1 refers to skid 6A which contains the emergency response scrubber ERS, and reference sign 6B indicates skid 6B with F 2 scrubbers and H 2 scrubbers.
- Reference sign 7 in figure 1 indicates skid 7 which includes optional means for analysis of F 2 (it may, for example, contain an FT-IR and/or a UV spectrometer).
- Reference sign 8 in figure 1 refers to the rectifier cabinets in skid 8.
- Reference signs 9 A and 9B refer to the medium voltage electricity sub-skid 9A and the low voltage electricity sub-skid 9B.
- Reference sign 10A indicates the skid 10A comprising a laboratory and a control room, reference sign 10B refers to skid 10B with amenities like rest room and gowning.
- Reference signs 11a and 1 lb indicate escalators and platforms for walking to arrive at skids in the upper story, especially skids 5 and 7.
- Reference sign 12 shows a fork lift in action.
- Reference sign 13 indicates a storage place for KOH solution and other chemicals needed, and reference sign 14 refers to an emergency shower.
- the plant can be fenced in as indicated by the black lines in figure 1.
- a fenced-in plant has advantages because workers not foreseen to operate the F 2 producing plant are kept from entering it, thus reducing the risk for such workers.
- the fluorine gas plant may be built on-site of the fluorine gas consuming semiconductor manufacturing plant, and delivery of fluorine gas occurs over the fence.
- skids can be pre-assembled and tested in a factory ; thus, they are a kind of "off-shelf ' product, and need only be mounted on-site. This saves time. It is also much easier to dismount specific skids for maintenance, repair or substitution by skids comprising parts with the same function but improved performance, or with lower or higher output.
- skid 2 comprises at least one electrolytic cell ; preferably, all electrolytic cells are already filled with the electrolyte and then delivered to the site for being assembled in skid 2.
- the filling can be performed under respective safety considerations and must not be performed on a local site where such safety precautions may not be available.
- the capacity of the plant can be expanded by adding modules.
- the skids have sea container size thus allowing for the easy transport of modules.
- a great advantage is a reliable production for 24 h and 7 days a week of high purity F 2 .
- the cells are blocked and connected to the structure to avoid movements, e.g. as a seismic protection.
- the plant comprises means which detect earthquakes and send a signal to the control room which causes the plant to shut down automatically or personnel to shut it down manually.
- the plant includes at least one seismometer, e.g. a strong motion seismometer (accelerometer) which can detect vibration acceleration of the plant and, if a certain level is reached, e.g. 0.5 G, send a respective signal which triggers an alarm and/or an automatic shutdown of the plant.
- a seismometer e.g. a strong motion seismometer (accelerometer) which can detect vibration acceleration of the plant and, if a certain level is reached, e.g. 0.5 G, send a respective signal which triggers an alarm and/or an automatic shutdown of the plant.
- All pipes connecting the cells and connected to the cells must be electrically isolated, e.g. by means of spacers between flanges.
- the floor must be electrically isolating, too.
- all process skids are comprised in an enclosed space.
- the skid module for HF storage comprises at least one HF (hydrogen fluoride) storage tank which serves to store HF and to deliver it to the electrolytic cells.
- the storage tanks for HF are generally hollow bodies which optionally can be mounted on wheels or which can be transported e.g. by a forklift.
- the skid comprises several storage tanks, more preferably, 2, 3, 4, 5 or 6 storage tanks.
- the HF is stored in liquid form in the tank.
- Skid 1 is connectable to a tank comprising pressurized N 2 .
- the liquid HF is pressurized with N 2 and delivered to an evaporator where it is evaporated.
- the resulting gaseous phase containing HF is delivered to the electrolytic cell or cells. If desired, for each electrolysis cell an evaporator can be installed.
- the evaporator preferably contains a heating, e.g. an electrical heating or a heat exchanger using the heat of hot cooling water, to generate the
- skid 1 suitably further comprises at least one interspace vent valve in connection with one or more closed isolation space.
- the interspace vent valve is generally operable to remove optionally present hydrogen fluoride from the closed isolation space. Removal can be carried out, for example, by applying vacuum. In another aspect, removal can be carried out, for example, by flushing the closed isolation space with an inert gas and/or a pressurized purging gas such as for example anhydrous air or, preferably, nitrogen.
- the removal is carried out continuously.
- the removal is carried out discontinuously, in particular when an HF storage container is connected to and/or disconnected from the supply line.
- Gases recovered from the closed isolation space are suitably vented to an HF destruction unit, for example a scrubber in skid 6.
- parts thereof which are supposed to be in contact with gas such as e.g., if appropriate, hollow bodies, valves and lines for charging and/or discharging gas are suitably made of or coated with material resistant to molecular fluorine.
- gas e.g., if appropriate, hollow bodies, valves and lines for charging and/or discharging gas
- material resistant to molecular fluorine examples include Monel metal, stainless steel, copper, and, preferably, nickel.
- the hydrogen fluoride storage containers are contained in an enclosed space having at least a closeable gate allowing for entering into or removing from the enclosed space a hydrogen fluoride storage container.
- the enclosed space contains the hydrogen fluoride storage containers and the connections to the hydrogen fluoride supply line.
- the enclosed space contains in addition an evaporator for evaporation of liquid HF.
- the enclosed space suitably comprises an HF sensor capable to trigger connection of the enclosed space to a scrubber described below.
- Skid 1 generally has at least a liquid line and a gas line.
- the liquid line can be connected, if appropriate to the hydrogen fluoride supply line, for example by means of a flange connection.
- the gas line can additionally be connected to an inert gas (e.g. anhydrous air, nitrogen, etc.) supply line which allows to pressurize the hydrogen fluoride storage containers.
- an inert gas e.g. anhydrous air, nitrogen, etc.
- each hydrogen fluoride storage container has generally a capacity of from 10 to 5000 liters, often 500 liters to 4000 liters, preferably from 500 to 3000 liters.
- Particular examples of hydrogen fluoride storage containers are tanks approved by RID/ADR - EVIDG - of UN T22 or, preferably, UN T20 type. Such tanks are commercially available.
- Each HF storage container in skid 1 can be suitably connected to the hydrogen fluoride supply line through a manifold.
- Each HF storage container in skid 1 is preferably individually isolatable from the hydrogen fluoride supply line.
- the HF storage containers in skid 1 can generally be isolated from the hydrogen fluoride supply line by a remotely controlled device, preferably a remotely controlled valve. More preferably each storage container is equipped with a remotely controlled device, preferably a remotely controlled valve, allowing isolating that container from the hydrogen fluoride supply line.
- remotely controlled valves When remotely controlled valves are present, manual valves are suitably installed in addition.
- the remotely controlled valves allow for example to operate the HF-storage-containers from a remote control-room.
- the HF storage containers comprise an automatic HF level sensor.
- the HF storage containers can be installed on weighing scales.
- a process control system in particular an automatic process control system is operable to closes the remotely controlled valve of a first, empty HF container and to open the remotely controlled valve of another second HF-containing hydrogen fluoride storage container. This embodiment is particularly effective to avoid manual handling of HF valves and to ensure a continuous HF supply.
- valves are operable to close automatically in case of abnormal operation state, such as for example a process-interruption in a process-equipment connected to the HF supply line.
- valves are operable to close automatically in case of an HF leakage in skid 1.
- HF leakage can for example be caused by a leakage of optional flange-connections inside the HF storage-container there is the possibility to close these valves via remote control. This avoids in particular the necessity to approach the hydrogen fluoride supply unit in this case.
- the skid also contains valves to shut down the supply of HF and nitrogen.
- skid 1 comprises 3 to 10 HF containers ; especially preferably, it comprises 4, 5, 6, 7 or 8 containers.
- 4 HF containers are suitable for a productivity of 150 tons F 2 /year.
- the tanks must be made from or at least lined with material resistant to HF.
- the walls should be sufficiently thick ; preferably, they have a 10 mm IMDG code (international maritime dangerous goods code) equivalent thickness.
- skid 1 comprises, preferably permanently, at least one HF emergency container.
- HF emergency container is preferably an empty HF storage container as described herein which is preferably connected to the HF supply line.
- the HF emergency container is generally operable to receive HF from a leaking HF storage container.
- the HF emergency container is suitably kept under pressure of an inert gas or under vacuum.
- the tanks are preferably portable so that they can be transported by trucks and/or can be handled by a fork lift.
- Skid 1 comprises a ventilation system, and the ambient air is preferably permanently ventilated to a scrubber, especially the ERS scrubber for HF and F 2 removal (as described below).
- Skid 2 The skid comprising the electrolytic cell or 2 or more cells (skid 2) is now described 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 skid 2 with 8 electrolytic cells is very suitable. The skid preferably is constructed such that if desired, additional electrolytic cells can be added if the demand for fluorine gas is rising. The cells comprise jackets through which cooling water can be circulated. If desired, skid 2 can be provided in the form of separate sub-skids 2A, 2B and so on. In these sub-skids, a certain number of electrolytic cells are assembled.
- the separate sub-skids 2A and 2B are attached together to form one cell room.
- the cell room will contain 4, 6 or more cells, for example, 8 cells or even more.
- the advantage of providing several electrolytic cells is that the shut-off of one or even more cells for maintenance or repair can be compensated by raising the output other cells.
- To assemble several sub-skids has the advantage that dimensions can be kept within permissible maximum dimensions for usual road transport.
- the electrolytic cells are connected to collectors for the F 2 and the H 2 produced. It has to be noted that each cell may comprise 1 or more anodes. Typically, each cell comprises 20 to 30 anodes.
- the number of anodes in each of the electrolytic cells may be greater than 30 ; each cell may, for example, have more than 60 anodes, up to 70 or even up to 80 anodes.
- a cable connects each of the anodes with the rectifier.
- Each cell cathode is connected through one copper or aluminium bus bar to the rectifier.
- One rectifier can supply current to one or more cells. It is preferred to apply one rectifier per anode. The advantage is that the intensity at each individual anode can be fine tuned depending on the specific anode characteristics, abnormal situations at a specific anode (e.g.
- skid 2 preferably comprises at least 4 electrolytic cells with a multitude of anodes wherein each of a multitude of rectifiers in skid 8 is allocated to a single anode, or wherein each of a multitude of dual rectifiers in skid 8 is allocated to two anodes.
- Skid 2 includes a cooling water circuit (fed by or connected to cooling water circuits of skid 5) supplying cooling water to the jackets of the cells.
- Skid 2 also comprises settling boxes ; preferably, a settling box for F 2 and a settling box for H 2 are connected with each of the cells.
- the settling boxes serve to reduce the gas velocity of the F 2 and H 2 produced in the cell to avoid electrolyte dust to be carried over.
- the settling boxes comprise a vibrator and a heating to melt the separated electrolyte dust for easy removal.
- the collectors collecting the produced F 2 are connected by a pipe with skid 3
- the collectors for produced H 2 are connected by a pipe with a scrubber for H 2 in skid 6B (this will be described in detail below).
- skid 2 also comprises a ventilation system to treat accidental releases of F 2 and/or H 2 .
- the ambient air of skid 2 is ventilated to a scrubber, especially the ERS scrubber for safety reasons (the scrubber is described below).
- Skid 3 it comprises means for the purification of the produced F 2 . It comprises a cooler wherein the F 2 is pre-cooled. Skid 3 also comprises an HF washer wherein the pre-cooled F 2 is contacted with HF which is kept at a very low temperature. The HF washer contains a cooling jacket through which a coolant is circulating. Skid 3 further comprises a buffer tank, a compressor, e.g. a diaphragm compressor, an HF condenser operated at low temperature and at least one HF absorber column, preferably containing NaF as absorbent for HF. Preferably, at least two absorber columns are contained in the skid 3.
- a compressor e.g. a diaphragm compressor
- an HF condenser operated at low temperature
- at least one HF absorber column preferably containing NaF as absorbent for HF.
- at least two absorber columns are contained in the skid 3.
- the absorber columns are redundant so that one set is in absorption mode, the other set can be regenerated.
- the absorber columns comprise a heating.
- a further set of absorber columns may be present in skid 3 or on the site for reloading of absorbent.
- the HF condenser is connected via pipes to the electrolysis skid 2.
- at least one set of columns is mounted on a wheeled trolley to keep them (re-)movable from the skid.
- the HF condenser may be cooled to a temperature where HF condenses to form a liquid or even a solid. It is preferred if it is condensed to form liquid HF. Cooling the trap to a temperature of -60°C to -80°C, preferably to about -70° is very suitable.
- As cooling medium well-known cooling liquids operable at the desired low temperature are suitable. It is preferred to apply a N 2 gas which was obtained by mixing liquid N 2 and gaseous N 2 in appropriate amounts. This way of cooling is very reliable.
- skid 3 comprises lines to deliver and to withdraw cooling medium.
- the ambient air of skid 3 is ventilated to a scrubber, especially the ERS scrubber (described below) for safety reasons.
- Skid 4 this skid serves for storage of fluorine gas and the delivery of fluorine gas to the point of use.
- Skid 4 comprises filters to remove any remaining entrained solids.
- the F 2 produced in the electrolytic cells may comprise entrained solid electrolyte from the cell, usually, adducts of KF and HF.
- the filter is preferably constructed from material resistant to HF and fluorine ; stainless steel, copper, Monel metal and especially nickel are especially suitable. Filters made from sintered particles of these metals comprising a pore diameter in the nanometer range to provide semiconductor grade F 2 , e.g. with a pore diameter of equal to or less than 5 nm, and more preferably, with a pore diameter of equal to or smaller than 3 nm, are very suitable.
- skid 4 comprises a pre-filter to remove from the F 2 coarser particles with a pore diameter of equal to or less than 1 ⁇ .
- Skid 4 may also comprise a single-cell FT-IR.
- this single-cell FT-IR the purified F 2 which is ready for storage or delivery to the point of use, may be analyzed. In this case, it is not necessary to provide the UV spectrometer and/or the multi-cell FT-IR in skid 7.
- Skid 4 preferably comprises means for the storage of fluorine gas. It may, for example, contain a buffer tank for fluorine gas.
- skid 4 may comprise a permanent or temporary fluorine gas storage unit in the form of a plurality of hollow bodies to store the F 2 .
- the storage unit is connectable to other skids.
- Permanent fluorine gas storage unit is understood to denote in particular a fluorine gas storage unit which is integrated into the fluorine plant.
- the fluorine gas storage unit can be a transportable or preferably fixed unit which is present in skid 4 throughout operation of the fluorine plant.
- the permanent fluorine gas storage unit is designed to contain more than 90 wt % more preferably more than 95 wt %, most preferably
- Skid 4 is further able to convey fluorine gas from skid 2 to the point of use.
- Possible components of skid 4 include but are not limited to supply lines, compressors, mixers and buffer tanks.
- connectionable is understood to denote in particular that the permanent fluorine gas storage unit is equipped to be able to be connected to a component of skid 4.
- the permanent fluorine gas storage unit is equipped to be able to be connected to a fluorine gas supply line.
- the fluorine gas storage unit is connected to a component of skid 4, in particular a fluorine gas supply line throughout operation of the fluorine gas plant.
- the fluorine gas storage unit is directly connected to a component of skid 4.
- Suitable equipment for connecting the fluorine gas storage unit connected to a component of skid 4 includes a manifold connected to each hollow body of the fluorine gas storage unit through a line and preferably having a shut-off valve in each line allowing to individually isolate each hollow body and said manifold is further connected to a component of skid 4.
- Skid 4 preferably comprises from 4 to 25 hollow bodies, more preferably from 5 to 8 hollow bodies.
- the hollow bodies are preferably of substantially identical shape and dimensions. Cylindrically shaped hollow bodies (tubes) are preferred.
- Each hollow body of the fluorine gas storage has preferably a shut-off valve.
- the hollow bodies of the fluorine gas storage unit can be suitably fixed together by means of an appropriate frame.
- Particular frame geometries include triangular, square, and rectangular geometries.
- the fluorine gas storage means are generally able to contain or contains fluorine gas at a pressure of at least 25 psig (about 1.72 barg). Often this pressure is equal to or greater than 35 psig (about 2.4 barg), preferably equal to or greater than 40 psig
- the fluorine gas storage means is generally able to contain or contains fluorine gas at a pressure of at most 400 psig (about 27.6 barg), preferably, equal to less than 75 psig
- this pressure is equal to or lower than 65 psig
- the hollow bodies of the fluorine gas storage unit are generally able to contain or contain fluorine gas at the aforesaid pressures. It is
- the hollow bodies contain fluorine gas at the aforesaid pressures.
- the ratio of the molecular F 2 stored in the fluorine storage means to the daily molecular F 2 producing capacity of the fluorine gas plant is generally from 0.1 to 1, preferably from 0.1 to 0.25.
- each of the hollow bodies can be shut off from the plant separately ; this improves safety.
- the fluorine leaving skid 4 is transported preferably through double-walled pipes to the point of use. Fluorine gas is transported in the inner tube ; the outer double wall envelope comprises nitrogen.
- the piping contains a pressure sensor to analyze the nitrogen pressure in the outer double wall envelope.
- the walls of the pipes are thicker than commonly used for transporting gases, i.e. preferably, they are thicker than 1 mm, preferably, thicker than 4 mm ; a wall thickness of equal to or greater than 5 mm is especially preferred ; pipes classified as "schedule 80" are very suitable. This serves to improve the safety. Welded piping with radiographic inspection is very suitable.
- the storage container or containers can be mounted on wheels or are transportable by a forklift.
- the ambient air of skid 4 is ventilated to a scrubber, especially the ERS scrubber described below (for safety reasons).
- the point of use can be connected to a further manufacturing plant, for example a chemical plant or, in particular a plant using fluorine gas for surface treatment.
- the point of use is often connected to a semiconductor manufacturing plant, preferably a manufacture of photovoltaic devices or flat panel displays.
- skid 4 comprising the fluorine gas storage unit is an enclosed space.
- the enclosed space generally comprises a fluorine sensor capable to trigger connection of the enclosed space to skid 6.
- the enclosed space is connected to skid 6 through a suction line connected to a fan which is operable to transport gas from the enclosed space of skid 4 to skid 6.
- the fluorine gas plant according to the invention further comprises a mixer, preferably a static mixer, said mixer being preferably capable to receive fluorine from skid 4 and to receive inert gas, such as preferably argon and/or nitrogen, from an inert gas supply line.
- a mixer preferably a static mixer, said mixer being preferably capable to receive fluorine from skid 4 and to receive inert gas, such as preferably argon and/or nitrogen, from an inert gas supply line.
- a pressure control loop adjusts, generally reduces the pressure of fluorine gas supplied to the point of use to a desired value.
- Skid 5 provides for cooling or heating of parts of the plant by means of cooling water. It is preferably located close to the electrolytic skid 2 or sub-skids 2A and 2B or any additional sub-skids 2X, more preferably, it is located above the skids. Skid 5 comprises at least one circuit which serves to heat the electrolyte cells to melt the electrolyte salt when the reaction is started, and to cool the cells when the reaction is running.
- the circuit is filled with cooling water which may be tap water or distilled water.
- the circuit includes a buffer tank, a pump which is preferably redundant, and a dry cooler with fans with variable speed drives.
- the cooling water, during operation, is preferably kept at 75 to 95°C to avoid solidification of the electrolyte in the cells.
- Another circuit comprised in skid 5 serves to cool other heat exchangers of the apparatus. It contains a cooling liquid, preferably a mixture of water and ethylene glycol, more preferably, water comprising 40 % by weight of ethylene glycol. Also this circuit comprises a buffer, a pump which preferably is redundant, and a dry cooler.
- the cooling circuits include detectors to measure the temperature of the cooling water, means to heat the cooling water, e.g.
- the plant comprises a steam generator to provide steam or hot cleaning water.
- the steam generator may be a portable one.
- the hot steam may be, for example, used to provide hot water in which electrolyte salt may be dissolved, if necessary. Consequently, skid 5 preferably contains at least two cooling water circuits.
- Skid 6 comprises at least one scrubber each for F 2 and H 2 .
- the scrubber pumps are redundant.
- the skids of the plant (especially skids 1, 2, 3, 4 and 7) include a ventilation system to ventilate the ambient air of the skid enclosures permanently through scrubbers in skid 6.
- skid 6 comprises an F 2 scrubber for destruction of any F 2 or FIF vent required for safety reasons or maintenance operations.
- F 2 and FIF from the ventilated air from the skids are treated in a scrubber for emergency
- the scrubbers are preferably jet scrubbers and provide the suction.
- the scrubbers may be mounted on sub-skids, e.g. a sub-skid 6A which comprises at least one scrubber for emergency response (ERS), a sub-skid 6B which serves to scrub produced H 2 with the purpose to remove HF entrained therein, and a scrubber to remove HF and/or F 2 in waste gas originating from ventilating the ambient atmosphere from skids as explained below.
- a sub-skid 6A which comprises at least one scrubber for emergency response (ERS)
- a sub-skid 6B which serves to scrub produced H 2 with the purpose to remove HF entrained therein
- a scrubber to remove HF and/or F 2 in waste gas originating from ventilating the ambient atmosphere from skids as explained below.
- the capacity of the regular F 2 scrubber corresponds at least to the expected amount of F 2 to be removed during regular operation.
- F 2 is removed by contact with an abatement solution.
- This scrubber preferably comprises a jet scrubber and a packed column to provide a high contact area between the abatement solution and F 2 .
- the gas leaving the regular F 2 scrubber is passed through the back-up scrubber of the ERS scrubber.
- the ERS scrubber serves as back-up of the regular F 2 scrubber used for removal of F 2 or HF from ventilated air, and for the emergency treatment of ventilated air which contains HF and/or F 2 after a leakage.
- the capacity of the ERS scrubber (optionally mounted in sub-skid 6A) corresponds preferably at least to the amount of fluorine and HF to be removed in cases for emergency, for example, in the very improbably case of pipe breaking, an accident with one of the tubes containing fluorine or an HF storage tank.
- the ERS scrubber comprises 2 units for scrubbing to achieve a high destruction and removal efficiency ; redundant pumps are fed by normal and emergency power supply. It preferably comprises a jet scrubber and a packed column to achieve a good contact between the gas to be treated and the abatement solution.
- the other unit serving for emergency treatment may comprise a packed column, but preferably, it comprises two jet scrubbers in series.
- the F 2 removal can be performed with agents known to remove F 2 .
- a KOH solution or NaOH optionally comprising an alkali metal thiosulfate, e.g. sodium thiosulfate or potassium thiosulfate is used as abatement solution and is pumped through the scrubber or scrubbers and the column, if present, as decomposing agent for F 2 .
- a cooler may be foreseen to cool the KOH solution.
- one emergency scrubber serves to treat HF and F 2 .
- the scrubber of skid 6 serving for the HF abatement of the H 2 gas stream may be mounted in sub-skid 6B.
- Sub-skid 6B includes preferably a jet scrubber operated with aqueous HF solution to reduce the content of HF in the H 2 .
- the concentration of HF may be in a range between 1 and 10 % by weight.
- the scrubber further comprises a packed column wherein fresh water is given on top of the column to reduce the HF content.
- Skid 6B also includes a line which allows the dilution of H 2 by nitrogen which was used as cooling medium in skid 3.
- skid 6 preferably comprises also one or more retention pits for liquid in case of accidental leakages.
- Skid 7 concerns the apparatus used for the analysis of the produced F 2 . It is preferably installed near skids 2A and 2B ; very preferably, it is located above the skids 2 A and 2B. Skid 7 is, for example, an analyzer shelter. The ambient atmosphere around it is preferably ventilated to the ERS. The analyzer contains analyzing means suitable to determine the content of the main impurities of the produced F 2 .
- a UV spectrometer which analyses the UV spectrum
- multi-input, multi-cell FT-IR spectrometer Fourier-Transform Infra-Red spectrum
- both raw F 2 taken from the cells and purified F 2 may be sent to a single-cell FT-IR or a multi-cell FT-IR.
- a multi-cell FT-IR one channel is analyzed at a given time.
- the amount of HF, CF 4 , C 2 F 6 and COF 2 can, for example, be measured by FT-IR while the content of F 2 is analyzed by UV.
- UV spectroscopy can be used as a direct measurement tool for fluorine which shows a sharp decrease in fluorine concentration when an anode burn occurs ; an enormous increase of CF 4 is observed at the same time in the FT-IR. Therefore the burn can be detected easily by the sharp decrease of the F 2 concentration during the burn, during which impurities are formed (mainly CF and C 2 F 6 ).
- the result of this burn (the produced F 2 contains more CF , C 2 F 6 , COF 2 , HF than when working regularly) is not only the alteration of impurities' contents but also a sharp decrease in the content of fluorine monitored by a detector system, especially, in the present invention, by UV spectroscopy. During the measurements using UV
- the whole UV spectrum can be used.
- particular UV spectroscopy between 200 and 400 nm, more preferred 250 to 330 nm, most preferred between 270 to 290 nm, even at about 280 nm is used for measuring, because it is more or less the maximum of the UV absorption of F 2 .
- the FTIR and UV measurements are also used to control the purity of the purified F 2 .
- the analysis serves to detect anode burns by measuring the raw F 2 by UV and CF by FT-IR and to document and control the purity of the purified F 2 .
- the raw F 2 of all cells and the purified F 2 are continuously sampled and analyzed.
- Current FT-IR can accept up to 9 samples.
- the purified F 2 and the raw F 2 of up to 8 electrolysis cells can be analyzed with one multi-cell FTIR of the current generation of apparatus.
- the analysis of the fluorine produced is performed only with a single-cell FT-IR ; a UV spectrometer is not applied.
- the single-cell FT-IR is used for the analysis of the purified F 2 (final analysis).
- Skid 8 contains the rectifiers, the BPCS (basic process control system), the ESD (emergency shutdown system), the F&G (fire and gas system) panel which registers fire alarms and gas alarms, small motor starters, lighting distribution and other means to provide electricity and to control electric means of the plant. Skid 8 is installed near skids 2A and 2B ; preferably, it is located above them.
- Each electrolytic cell as mentioned above, usually has at least one, but often a multitude of anodes, e.g. 26.
- the term "multitude of anodes" may denote any figure which is equal to or greater than 2. The number of anodes is limited only by practical considerations, e.g.
- the cell or cell unit (constituted of several cells) should not be unreasonably large. Often, the number of anodes is equal to or lower than 80, preferably, equal to or lower than 70.
- One rectifier could provide current to one, two or more anodes. Preferably, each anode is supplied by a rectifier. Rectifiers are available on the market which can provide current separately to several anodes. For example, if 26 anodes are present in a cell, it is preferred to provide 26 rectifiers or 13 dual rectifiers which separately provide current to 2 anodes.
- the rectifiers are preferably assembled in rectifier cabinets installed in air-conditioned enclosure.
- rectifier cabinets are bolted on a fixed frame for seismic protection.
- Skid 8 comprises walls and a roof. It includes preferably also a fire detection system, especially a VESDA (very early smoke detection apparatus) and a fire extinguishing system operating, e.g. with HFC-227ea or with Inergen ® , a mixture of inert gases (nitrogen, argon and carbon dioxide).
- a fire detection system especially a VESDA (very early smoke detection apparatus) and a fire extinguishing system operating, e.g. with HFC-227ea or with Inergen ® , a mixture of inert gases (nitrogen, argon and carbon dioxide).
- Skid 9 is preferably a pre-fabricated room with concrete walls or similar to a container, made from metal shields. It contains means for connection to electric current and to transform it from medium to low voltage. Preferably, it contains the "electric sub-stations" sub-skids 9A and 9B. Skid 9A preferably contains the MV (medium voltage) cells for incoming and outgoing current and bypass current and the transformers to transform the medium voltage current into low voltage current. It is adaptable to the local network ; for example, the transformers are selected such that they fit to the local voltage which may, for example, be 380 V or 400 V (50 Hz) or 440 V (60 Hz). Skid 9 includes preferably also a fire detection system, especially a VESDA (very early smoke detection apparatus) and a fire extinguishing system operating, e.g.
- VESDA very early smoke detection apparatus
- HFC-227ea or with Inergen ® , a mixture of inert gases (nitrogen, argon and carbon dioxide).
- Skid 9B also is preferably a pre-fabricated concrete room having walls and a roof.
- This substation houses the low voltage switchgears (LVCS) and a diesel generator. It is interconnected by cables to the skids which need a low voltage power supply, e.g. via a cable trench.
- LVCS low voltage switchgears
- It includes preferably also a fire detection system, especially a VESDA (very early smoke detection apparatus) and a fire extinguishing system operating, e.g. with HFC-227ea or with Inergen ® , a mixture of inert gases (nitrogen, argon and carbon dioxide).
- Skid 9B preferably also comprises a battery charger station for a forklift. Skid 9B must be interconnected to the process skids, especially with the rectifiers in skid 8.
- Skid 10 comprises utilities for the personal, for example, a control room, a laboratory and a rest room. Preferably, it is divided into sub-skid 10A and sub-skid 10B.
- Sub-skid 10A contains the control room and the laboratory.
- the laboratory which may be small includes a fume hood with good ventilation, e.g. up to 500 m 3 /h and even more, which hood is preferably made from acid- resistant materials and can be used for analytical titrations, a safety cabinet for reagents and samples, a wash basin and a chemical sink wherein chemical waste can be collected, preferably in a drum made from acid resistant material.
- the laboratory preferably has a gas detector installed in a fresh air intake and a closing mechanism which closes the air intake in case of a gas alarm.
- Sub-skid 10A preferably is kept under a slight overpressure to prevent gas ingress. Skid 10A preferably comprises air-conditioning.
- the control board of the control room is preferably connected online to a remote control board which may be located on another facility. This allows operating several fluorine gas production plants remotely from one single control room.
- Sub-skid 10B contains the rest room. It contains installations useful for the control room personal. It preferably includes lockers, a changing room, a toilet, a shower, and cabinets for chemical gowning (gloves, capes etc).
- the plant safety shower includes eye-shower systems and is preferably located close to the outside of sub-skid 10B because it must be fed with warm potable water.
- Skid 10 preferably comprises ventilation and heating.
- the plant will include further equipment useful to operate it.
- Compressors are needed to provide pressurized fluorine gas. They must be resistant to fluorine gas. Compressors which are used for fluorine gas handling in the nuclear industry are very suitable. They are preferably diaphragm type compressors. Such compressors are available on the market. The diaphragms are made from F 2 resistant material, especially from Monel metal, stainless steel, copper or nickel. The membranes are 3 -layer membranes so in case of a membrane break the break will be detected by pressure measurement, and no F 2 will leave the compressor membrane to the outside area.
- the plant also will need instruments and valves for operation.
- the process step of mixing the gases includes mass flow meters for F 2 and the gas or gases to be mixed with it, installed control valves with dedicated programmed control loops and interlocks to ensure an appropriate and safe mixing of the gases, e.g. the inert gas or inert gases, with F 2 .
- the plant has means to analyze certain parameters (e.g., mass flow control of fluorine gas or inert gas) for its operation.
- mass flow controllers are preferably used. With such mass flow controllers, the amount of fluorine gas can be controlled which passes through lines carrying it for example, to the FTIR and UV analyzers.
- the mass flow controllers ought to be "low ⁇ type” controllers causing only a low pressure drop.
- Such flow meters, as well as tubes, pipes, and fittings used to transport gas to the analyzers which must be suitable for fluorine gas transport, are also available on the market. Valves should be bellow sealed heavy duty valves.
- a PLC programmable logic controller
- BPRS basic process control system
- windows made from AgCl are preferably applied, for the analysis of raw F 2 , e.g. raw F 2 from the sampling lines of the electrolytic cells, A1 2 0 3 windows can be applied.
- a single cell FT-IR is located in skid 4. It serves to perform a final analysis of the F 2 .
- a multi-cell FT-IR and optionally, a UV analyzer is located in skid 7.
- a single-cell FT-IR is located in skid 4, and a multi-cell FT-IR and optionally, a UV analyzer is located in skid 7.
- the first alternative is the cheapest solution.
- the second alternative is more expensive than the first alternative ; but it allows a quick reaction if the F 2 production in one or more cells is disturbed. It also allows to identify the cell operating irregularly.
- the third alternative is the most expensive one ; it allows, at the same time, a quick reaction and to identify faulty cells, and it allows to check the purity of the final F 2 .
- the plant includes safety installations.
- the plant comprises a safety panel with switches for an emergency shutdown (ESD), for alarms, and for overriding automatic processing.
- ESD emergency shutdown
- Detectors for F 2 , HF and, where appropriate, H 2 are installed, for example, in ventilation ducts to the ERS scrubber and at the emission points.
- Gas alarm signals are sent to the ESD for safety functions.
- the plant includes warning lights which are activated, i.e., if gas alarm signals are sent to the ESD.
- the alarms must also be detectable in the control room of skid 10.
- the plant comprises a Fire & Gas panel in the control room of skid 10 to show all fire and gas alarms, and failure of ventilation.
- the plant includes smoke detectors and VESDA detectors.
- the process skids e.g. skids 1, 2, 3, 4 and 7, comprise means to stop the F 2 production manually, e.g. emergency push buttons, and/or to actuate fire extinction apparatus.
- CC TV closed circuit television
- CC TV can be used to supervise the plant. It can be used to monitor access to the plant, unloading of materials (e.g. of HF portable tanks or KOH solution).
- Safety Instrument Systems comprising sensors, ESD system and safety actuators are included in this plant.
- the SIS are designed to achieve a Safety Integrity Level "2".
- safety Integrity Level 2 In particular, where electrical motors or electrical loads were needed to be included as a part of a safety instrumented function, alternate and independent means of tripping these motors/loads are considered, e.g. by tripping the upstream breaker if the contactor or circuit breaker dedicated to the motor/electric load fails to open.
- An emergency generator preferably a diesel generator supplying lOOkVA is preferably contained in the plant if external power supply is interrupted.
- control room comprises a "dead man" detection for the operator working alone.
- control room provides data for wind direction and wind speed.
- the footprint of the assembled process skids for a plant with a capacity of 150 t/year is 30 m -9.2 m. With skids for utilities, personnel areas and access clearance for maintenance and servicing, the overall size is about 39 m-23 m.
- the height of the skids may be higher than standard (standard height is
- Skid 6 A comprising the emergency scrubber has often not the standard footprint but must be adapted to the specific need of the respective plant.
- the skid structure is a painted steel frame on which all equipments are fixed ; they are designed for outdoor installation. Panels, doors and roofs, if fixed on the external structure of the skid, imply that the external skid dimensions exceed the standard sea container dimensions. If necessary, such skids are prefabricated and panels, doors and the roof, respectively, are assembled to the skids on site.
- the skids are anchored on an existing concrete slab or by or on specific foundations.
- skids are manufactured, piped, wired and assembled together before shop testing. It is preferred if they are constructed such that the interfaces between the skids are minimized and that all parts in the respective skid are accessible as easily as possible for maintenance, inspection or repair.
- the advantage of the skids is the safety aspect, a reliable F 2 production for 24 h and 7 days a week of high purity F 2 .
- skids as described above are assembled in a workshop ; in one embodiment, the electrolytic cells of skid 2 already are supplied filled with the electrolyte salt. This improves safety.
- the skids are preliminarily tested in the workshop and then shipped to the facility where the F 2 produced by them is needed. On the facility, it is preferred if a concrete slab had been built sufficiently beforehand upon which the F 2 production plant can be erected.
- Skid 2 comprises 6 electrolytic cells forming one cell room.
- Each electrolytic cell in this case, comprises 26 anodes ; other multitudes, e.g. up to 80 anodes and even more, would be possible, if desired.
- they are blocked to the ground as an earth quake or bad weather precaution measure.
- Skid 13 serves as storage room for chemicals needed, e.g. thiosulfate, hydroxide and/or electrolyte salt.
- Operability of the built-in parts is preferably tested then.
- a plant with 6 cells is provided.
- the nominal capacity of this plant if run 24 h for 7 days a week, is about 100 tons/year of pure F 2 (12 kg/h, peak 20 kg/h).
- the capacity could be expanded by adding two further electrolysis cells and rectifiers or rectifier racks.
- the expansion of capacity to 300 t/year would be possible by adding further skids (additional cell room and rectifiers, additional cooling skid, additional analyzers).
- Tanks preferably with an inner volume of 1 to 20 m 3 , most preferably in a size of 1 to 3 m 3 , filled with HF, are assembled in skid 1 and connected to the electrolytic cells.
- Electrolyte salt of the rough composition KF-2HF had already been filled into the cells before the final assembly of the plant.
- the content of the electrolytic cells is heated to about 80 - 120°C to be molten therein.
- FIF coming from the evaporator from skid 1 is fed into the electrolytic cell.
- medium voltage is supplied to skid 9B, transformed to low voltage direct current with a voltage in the range of 8 to 12 V, and current is passed through the molten composition of HF and the molten electrolyte salt which is kept in a temperature range between 80 and 120°C.
- One rectifier may be allocated to each cell ; preferably, one rectifier is allocated to each anode. It is especially preferred to apply dual rectifiers ; such a dual rectifier can serve two anodes.
- 13 dual rectifiers may be applied to provide electric current to the anodes.
- the cells are operated at as pressure higher than ambient pressure (e.g., at 7 to 10 mbarg). Elemental fluorine (F 2 ) and elemental hydrogen (H 2 ) form in the respective electrode compartments in skid 2.
- the skid containing the electrolytic cell or cells also includes sensors which determine the temperature in the cell, the level of liquid in the cell or cells, the pressures and pressure differences, the anode currents and voltages and gas temperatures.
- the cells are cooled with cooling water having a temperature of about 75 to 95°C, preferably 75 to 85°C.
- H 2 formed is passed to skid 6B and is contacted in a jet scrubber with an aqueous solution comprising 0 up to about 5 % by weight of HF in water.
- Gas leaving the scrubber is passed to the bottom of a packed column and contacted therein with fresh water sprayed on top of the column.
- Gas leaving the packed column is diluted with nitrogen and passed into the atmosphere.
- the plant produces about 415 kg/day of F 2 .
- F 2 produced in the cells is first pre-purified by removing particles (mainly, entrained re-solidified electrolyte salt). The stream of raw F 2 is then cooled down whereby a part of entrained HF condenses and can be removed. Then, the raw F 2 is compressed with a diaphragm compressor to a pressure of
- the redundant pairs of NaF towers are installed on trolleys to keep them movable, especially for the case that the NaF pellets need to be exchanged completely (when further regeneration is not possible any longer).
- the compressed F 2 is then passed through a trap and cooled therein to
- the F 2 gas stream leaving the two NaF towers is passed through two filters to remove any solids, especially NaF ; the filters are preferably made from Monel metal, and the second filter has a pore diameter of 3 nm.
- the temperature of the first tower is about 100°C, the temperature of the second tower is about 30 - 40°C.
- the purified F 2 is continuously sampled.
- samples are sent to a multi-cell FT-IR and to a UV analyzer, as described above.
- a single-cell FT-IR is applied for the analysis selectively of the purified F 2 .
- Analytical data are sent online to a control board in the control room in skid 10A. If the analysis of the samples shows that one or more of the cells produces F 2 too impure to be useful for semiconductor manufacturing purposes, for example, containing too much CF 4 or higher homologues which indicates a cell failure, the respective sample or samples and the F 2 produced by the electrolytic cell are passed to the F 2 scrubber in skid 5 and the emergency scrubber for destruction by means of a KOH solution including sodium thiosulfate. Alternatively, the impure F 2 could be collected to be used for purposes for which the degree of purity is sufficient. If the samples show that the F 2 produced corresponds to the desired purity, the samples are returned to the F 2 product line. The F 2 is then passed to a storage means which includes
- each of the cylinders can be opened and shut off individually by shut-off valves.
- the pressure of the produced F 2 is lowered to about 1.5 barg by a pressure control loop and is then passed to the point of use, a flat panel display manufacturing plant using F 2 for chamber cleaning.
- a double-walled pipe is used, wherein the space between the inner and the outer tube contains nitrogen, and the F 2 is passed through the inner tube of it.
- shut-off valves are open and the pressure difference between the F 2 storage unit and the point of use provides a buffer allowing a smooth control of the delivered fluorine gas flow, even for variable consumption patterns at the point of use or during interruption of the production of the F 2 generating unit.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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KR1020137009437A KR101819779B1 (en) | 2010-09-15 | 2011-09-12 | Plant for fluorine produciton |
JP2013528630A JP2013540895A (en) | 2010-09-15 | 2011-09-12 | Fluorine production plant |
US13/822,455 US20130175161A1 (en) | 2010-09-15 | 2011-09-12 | Plant for fluorine production and a process using it |
CN2011800475289A CN103140607A (en) | 2010-09-15 | 2011-09-12 | Plant for fluorine production |
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US38320410P | 2010-09-15 | 2010-09-15 | |
US61/383,204 | 2010-09-15 | ||
US38353310P | 2010-09-16 | 2010-09-16 | |
US61/383,533 | 2010-09-16 |
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WO2012034978A1 true WO2012034978A1 (en) | 2012-03-22 |
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PCT/EP2011/065773 WO2012034978A1 (en) | 2010-09-15 | 2011-09-12 | Plant for fluorine production |
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US (1) | US20130175161A1 (en) |
JP (2) | JP2013540895A (en) |
KR (1) | KR101819779B1 (en) |
CN (1) | CN103140607A (en) |
TW (1) | TWI586842B (en) |
WO (1) | WO2012034978A1 (en) |
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WO2013024041A1 (en) | 2011-08-17 | 2013-02-21 | Solvay Sa | Electrolytic process for the manufacture of fluorine and an apparatus therefor |
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WO2014037485A1 (en) * | 2012-09-10 | 2014-03-13 | Solvay Sa | A chamber cleaning method using f2 and a process for manufacture of f2 for this method |
US8871174B2 (en) | 2010-03-26 | 2014-10-28 | Solvay Sa | Method for the supply of fluorine |
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Also Published As
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TWI586842B (en) | 2017-06-11 |
JP2013540895A (en) | 2013-11-07 |
TW201224218A (en) | 2012-06-16 |
KR101819779B1 (en) | 2018-01-17 |
US20130175161A1 (en) | 2013-07-11 |
KR20140009143A (en) | 2014-01-22 |
JP2017218678A (en) | 2017-12-14 |
CN103140607A (en) | 2013-06-05 |
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