Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B17/00—Sulfur; Compounds thereof
  • C01B17/02—Preparation of sulfur; Purification
  • C01B17/0232—Purification, e.g. degassing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/0005—Degasification of liquids with one or more auxiliary substances
  • B01D19/001—Degasification of liquids with one or more auxiliary substances by bubbling steam through the liquid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/0042—Degasification of liquids modifying the liquid flow
  • B01D19/0047—Atomizing, spraying, trickling
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B17/00—Sulfur; Compounds thereof
  • C01B17/02—Preparation of sulfur; Purification

Definitions

• the invention relates to a process for degassing liquid sulfur in a container having two contiguous regions, a first region of the liquid sulfur container and a second region of the container being flooded with a gas, and a gas stream being injected into the first region As well as a device for degassing of liquid sulfur using the method according to the invention.
• Liquid sulfur contains gaseous impurities, in particular in the form of H 2 S (hydrogen sulphide), H 2 S x (polyhydric hydrogens), SO 2 (sulfur dioxide) and, if appropriate, other gaseous sulfur compounds.
• H 2 S hydrogen sulphide
• H 2 S x polyhydric hydrogens
• SO 2 sulfur dioxide
• H 2 S is a very dangerous compound as it is toxic in the air at a concentration of less than 10 ppm by volume and is lethal at a concentration of some 100 ppm by volume.
• hydrogen sulfide when reaching a concentration of> 3.4 vol .-% hydrogen sulfide in the air form an explosive mixture.
• H 2 S tends to leach out of the liquid sulfur when it is shaken and cooled, especially during handling, storage and transport. The dangerous gas then accumulates in the gaseous phase of the storage and transport containers.
• H 2 S and SO 2 also naturally come from the sulfur.
• non-degassed liquid sulfur thus provides a source of volatile H 2 S and SO 2 - Emission in the storage areas and thus not only causes pollutant pollution and environmental pollution but is also a significant security risk. For all these reasons, it is necessary to remove the H 2 S by degassing from the raw sulfur produced in order to prevent all risks of toxicity, fire and the risk of explosion during handling, storage and transport.
• WO 03/106335 A1 describes a process for the removal of hydrogen sulfide from liquid sulfur, in which liquid sulfur is introduced from top to bottom into a container and flows via an outlet on the lower side of the device into an outer ring which gasses with air becomes.
• Part of the SO2 is found in the stripping air together with the degassed H 2 S, which contributes to the sulfur losses of the overall process.
• the transition conditions for the gas diffusion from the liquid to the gaseous phase are now promoted in such a way that the gas-liquid interfaces are increased on the one hand overall with respect to the contact surface, on the other hand, however. which differ in particular with regard to the respective concentration.
• three types of interfaces are created, namely
• H 2 S but also SO 2 can be reliably removed from the liquid sulfur with this method.
• a combination of H 2 S and SO 2 removal is also possible.
• H 2 S exists in two forms: free physically dissolved H 2 S and H 2 S X (sulfanes or polysulfuric substances).
• H 2 S X sulfanes or polysulfuric substances.
• the total content of H 2 S in both forms is between 250 and 500 ppm by weight, based on the total sulfur content.
• the devolatilization is to remove the purpose of the free H 2 S and the felwasserstoffen in the form of H 2 S present Polyschwe-.
• the ratio between hydrogen sulphide and polyhydrocarbons within the liquid suspension Rock varies depending on the temperature, increasing with increasing temperature (20:80 wt% at 130 ° C, 50:50 wt% at 150 ° C).
• the decrease of the hydrogen sulfide partial pressure promotes the degradation of the sulfanes, which is aimed at by the gas stripping of the sulfur. Due to the chemical balance, the degradation kinetics of the polyhydric hydrocarbons becomes the most important parameter limiting the effectiveness of the degassing process. This parameter is particularly critical for the duration of the degassing process.
• the chemical composition of the stripping gas used in the first zone and of the gas flowing in the second zone has an influence on the degradation kinetics of the H 2 S X.
• Two different types of gas can be used independently in both areas:
• Inert gases are gases of the first type, ie gases which do not undergo a chemical reaction with the sulfur and the impurities contained therein.
• Typical inert gases are N 2 , CO 2 or residual gases from a sulfur production plant (eg Claus units, connected residual gas treatment), under the condition that these gases do not contain more than about 5,000 ppm by volume of residual sulfur compounds such as H 2 S.
• Steam may also be used, but is preferably mixed with inert gases.
• the efficiency of stripping is determined solely by the physical conditions of the diffusion of hydrogen sulfide through the gas-liquid separation layer.
• hydrogen sulfide can be withdrawn from the system more quickly, resulting in the decomposition of poly (hydrogen sulfide) to form new hydrogen sulfide.
• reactive gases which, in addition to the stripping action, are reaction partners with the sulfur and / or the impurities contained therein.
• the most effective and at the same time cheapest stripping gas here is air.
• direct oxidation reactions of H 2 S and H 2 S X occur , shifting the equilibrium more towards the downstream side. The concept of reactive stripping builds on these reactions.
• the gas stream introduced into the liquid sulfur of the first region differs in its nature from the gas stream flowing through the second region.
• liquid sulfur sprayed into the second region is from the first region and is pumped from it into the device for spraying. This creates a flow within the liquid sulfur, which ensures a thorough mixing of the system and thus a homogeneous degassing.
• the second gas-flooded area is flowed through by a gas stream, wherein this through-flow should, in a particularly preferred manner, take place mainly parallel to the surface of the liquid sulfur. This will ensure that the concentration gradient is maximized both in terms of the boundary area between the two areas and in terms of the interface created by the spraying of the sulfur, and hydrogen sulfide contained in the gas phase does not pass back into the liquid sulfur.
• the total degassing time of such a sulfur batch is typically 6 to 12 hours, depending on the design of the systems, in particular depending on the recirculation capacity of the pump for pumping around the sulfur, the fürperl-stripping and a possible additionally used catalyst.
• the process according to the invention can also be carried out as a continuous process.
• the process is carried out in the same way as the batch process, but raw sulfur is constantly fed into the degassing vessel and an appropriate amount of treated sulfur is removed.
• the degassing in several, preferably two chambers, wherein the raw sulfur enters the first chamber, in which it is continuously atomized.
• the liquid sulfur flows into a second chamber.
• the sulfur is kept in motion by a circulation pump, whereby the atomization of the raw sulfur takes place in the gas region of the second chamber. From the second chamber and the degassed sulfur is then withdrawn continuously.
• the bubbling can take place both in two chambers or in only one chamber, preferably the second chamber. If only one chamber is bubbled through, the amount of oxygen introduced can also be minimized here by using air as the stripping gas.
• the gas flow flowing in the gas flooded area does not need to be pumped separately, but it is sufficient to provide it at atmospheric pressure, because in the second region of the first chamber by the continuous removal of the gas creates a negative pressure.
• the rinsing and bubbling gases mix above the sulfur in the first flooded area and are stripped off with the degassing products, mainly H 2 S.
• the degassing products mainly H 2 S.
• such gases are conducted to a combustion plant (a combustion chamber or a reaction furnace of the Claus unit assigned to the process).
• the most effective catalysts are compounds which are characterized by their chemical base function, namely nitrogen compound from the amino type in general, in particular ammonia, urea, secondary and tertiary structures äramine (weak bases), heterocyclic nitrogen compounds, quinoline (C9H 7 N) and Morpholines (C 4 H 9 NO), or alumina-based solid catalysts (Al 2 O 3), in particular activated aluminas, with Fe, Ni, Ti salts doped aluminas.
• chemical base function namely nitrogen compound from the amino type in general, in particular ammonia, urea, secondary and tertiary structures äramine (weak bases), heterocyclic nitrogen compounds, quinoline (C9H 7 N) and Morpholines (C 4 H 9 NO), or alumina-based solid catalysts (Al 2 O 3), in particular activated aluminas, with Fe, Ni, Ti salts doped aluminas.
• Another decisive parameter for the course of the process according to the invention is the temperature of the liquid sulfur.
• the content of dissolved in liquid sulfur H 2 S and H 2 S X depends strongly on the temperature. Because of the chemical equilibrium between the sulfanes and the hydrogen sulfide, this dependence does not follow the normal physical law of absorption. As the sulfanes increase, the amount of total H 2 S increases with temperature. If both substances are in equilibrium, the weight ratio H 2 S X to H 2 S at 150 ° C is about 50:50, but at 130 ° C only about 20:80. The cooling of the sulfur while reducing the Sulfananteils thus facilitates the degassing.
• this cooling can be included in the proposed process.
• the sulfur is preferably brought to a temperature between 130 and 135 ° C. Cooling also preferably takes place during the recirculation of the sulfur, so that the sulfur is cooled when it is pumped from region 1 to region 2 for atomization.
• the sulfur degassing with air produces a different amount of SO 2 , with some of the SO 2 remaining in the sulfur in the dissolved state (about 100 ppm by weight).
• Sulfur dioxide is a very toxic, dangerous and polluting product. It causes volatile emissions and accumulations of sulfur dioxide in the vicinity of liquid and solid sulfur plants, which means that these plants must be equipped with suitable ventilation systems and devices to control this emission. This applies in particular to systems for storing granular solid sulfur. The same problem also occurs with means of transport. For these environmental reasons and depending on the use of sulfur further requirements, it may be necessary borrowed to minimize the sulfur dioxide in addition to the hydrogen sulfide in the liquid sulfur.
• the inventive method makes it possible to remove in an additional and final degassing step of the sulfur treatment after H 2 S degassing with air and the SO 2 by degassing.
• the removal of SO2 by degassing follows the same principle as the degassing with respect to H 2 S.
• sulfur is atomized within a gas-flooded area and the area of liquid sulfur adjacent to this gas area is bubbled with stripping gas.
• Inert gas is used as the stripping gas.
• a residual gas from a sulfur production plant or a connected residual gas treatment plant preferably residual gases from a TGT plant type SCOT or LTGT, the purged with amines and completely SO2-free residual gases with a H 2 S content of about 100 to 300 ppm by volume deliver
• the stripping inert gas from the removal of SO2, after SO2 removal may be directed as a gas stream containing the removed SO2 into the gas flooded second portion of the upstream H 2 S removal.
• the process can be optimized with respect to the removal of SO2 in such a way that the sulfur is heated, thus reducing the solubility of the sulfur dioxide. xids is lowered.
• a heating to a maximum temperature of 160 ° C an acceptable for the viscosity of liquid sulfur limit
• preferably 150 to 160 ° C take place. It has proved to be advantageous to carry out such a heating of the sulfur as part of the recirculation of the sulfur to the atomizers.
• the total degassing of the sulfur can be carried out so successfully that residual values of the cumulative H 2 S + SO 2 content are between 10 and 20 ppm by weight.
• the invention further comprises a device suitable for carrying out the method according to the invention with the features of claim 7.
• a device suitable for carrying out the method according to the invention with the features of claim 7.
• Such a device has a container in which two adjoining regions are located. The first of these areas is flooded with liquid sulfur and the second area is flooded with a gas.
• a gas stream is injected.
• the injection is carried out by a plurality of nozzles, so that a bubbling of the sulfur with stripping gas takes place.
• the second area opens a device for spraying liquid sulfur, wherein the spraying should be such that the liquid sulfur passes finely atomized into this gas phase.
• the device is thus designed so that the diffusion of H 2 S from the liquid phase to the gas by improving the transition conditions at the gas-liquid interface and by increasing the gas Liquid total contact area is favored.
• the stripping device consists of three combined and integrated contact systems:
• a contact system by bubbling with stripping gas in the sulfur mass by means of diffusers, preferably steel diffusers, which are preferably arranged at the bottom of the chamber.
• the gas is dispersed in the form of bubbles in the liquid sulfur which forms the continuous phase of the system.
• the contact gas / sulfur takes place in countercurrent.
• a contact system by atomizing the sulfur in the gas phase.
• the sulfur is dispersed in the form of droplets into the gas that forms the permanent phase.
• the gas phase flows through the mist of atomized sulfur.
• the contact systems are arranged in a sulfur recirculation loop which is activated by a pump which sequentially transports the sulfur to the atomization and bubbling systems.
• the pump absorbs the sulfur, preferably near the bottom of the container, and promotes him to the atomizer.
• the two systems are thus arranged in a single sulfur recirculation loop.
• the design and dimensioning of the system depends on the method of industrial implementation of the process.
• the design parameters are: The sulfur volume in the degassing tank; this determines in a continuous process the required residence time of the sulfur for the reactions and in particular the degradation of the polysulfuric hydrocarbons (whose kinetics are slower and therefore a limiting factor for the degassing performance)
• the degassing takes place in a closed room, usually a shaft made of acid-proof concrete and stone or a steel container.
• the device according to the invention in such a way that a continuous course of the process is possible. It has been found to be particularly advantageous to divide the container into at least two chambers, wherein in the first chamber raw sulfur is constantly supplied and from the last, preferably the second chamber, a corresponding amount of treated sulfur is constantly dissipated.
• Each chamber is equipped with a pumping system consisting of a recirculation pump and a sputtering system.
• the discharged, for example, from a Claus plant raw sulfur enters the first chamber, where it is continuously attracted by the pumping system and atomized in the second area. Through an opening in the partition, at the bottom of the room, the sulfur can enter the second chamber.
• the second chamber there is an identical pumping system. Through a partial flow of the recirculation pump, the degassed sulfur is continuously withdrawn.
• the stripping gas is preferably introduced simultaneously through two different systems. On the one hand through the inlet and outlet, which each open into the second, gas-flooded area, and on the other hand by a blower for stripping by gas injection.
• a blower for stripping by gas injection there is a corresponding device in the liquid sulfur mass, which are preferably nozzle / jet apparatus devices, which are conveniently arranged at the bottom of the respective chambers.
• the degassing products are withdrawn from the chambers together with the rinsing and bubbling gases, in which case a steam jet system is preferably used.
• the degassing can be carried out particularly successfully at temperatures between 130 and 150 ° C, which is why a device according to the invention is preferably equipped with at least one cooling device. It has proven to be particularly favorable to arrange at least one cooling device between the pump and the injection and thus to cool the sulfur within the recirculation process.
• a catalyst which is introduced, for example, by means of an injection device on the suction side of the pump.
• the container is a downstream chamber (in the use of originally two chambers, the third chamber) for the removal of SO2 has.
• This third chamber adjoins the second chamber and is separated by a partition which, however, is open in the preferred lower part, so that a continuous promotion of the sulfur between the second and the third chamber is made possible.
• gas-flooded area is provided that the partition does not flush, so that an open, preferably located in the upper part area is present, so that an incoming gas flow from the third chamber in the second and first chamber can flow.
• Each camera thus has a first region of liquid sulfur and a second region of gas flooded.
• the inventive method and apparatus for carrying out this method are used in particular for liquid sulfur, the dissolved impurities in the form of H 2 S, H 2 S X , SO 2 and other possibly occurring sulfur compounds.
• the process is applied to sulfur produced in sulfur recovery plants, which originates from the acid gases produced during the desulphurisation of natural gas and refined petroleum.
• the sulfur production plants or Claus production units
• TGT residual gas treatment plant
• These plants are commonly referred to as "Claus plants” or "sulfur plants”.
• the sour gases processed in these plants consist essentially of H 2 S, CO2 and small amounts of hydrocarbons.
• a portion of the sour gas may also contain ammonia, which is the case with the sour gas produced by stripping the sour liquor.
• the liquid sulfur produced and collected in these Claus plants contains 250 to 500 ppm by weight of dissolved total hydrogen sulfide in bound form as hydrogen sulfide and polyhydric hydrogens.
• the invention is applied to the so-called "FRASCH" sulfur, an elemental sulfur extracted from mines, which is obtained from natural deposits with the aid of the FRASCH process in the liquid state.
• This sulfur which may also contain traces of H 2 S in the order of 100 to 200 ppm by weight, is also suitable for this degassing process.
• FIG. 2 schematically shows an embodiment of a batch reactor according to the invention
• Fig. 4 shows schematically an inventive embodiment of a continuous process with integrated SO2 degassing.
• FIG. 1 shows the reactions and transport processes in a degassing process.
• a gas phase GAS located above the liquid sulfur S (Iq.).
• Dissolved in the liquid sulfur H 2 S can be transported by diffusion through three different exchange surfaces in the gas phase, namely 1: the stripping of the liquid sulfur with gas bubbles, 2: the sputtering of liquid sulfur in the above the liquid phase arranged gas phase and 3: at the interface between liquid and gaseous phase.
• H 2 S from the gas phase into the liquid phase via the gas / liquid interface.
• SO2 can be transferred from the liquid phase to the gas phase in the same way.
• FIG. 1 shows the embodiment of the device according to the invention as in its design for a batch process in a batch reactor.
• This reactor has a container 1 which divides into the two regions 2 and 3. In this case, the region 2 is flooded with liquid sulfur as the first region, while the second region 3 is flooded with gas.
• first area 2 leads a line 1 1, through which a system for injection of stripping gas is fed with the stripping gas.
• This injection device 12 has a plurality of nozzles to produce a fine dispersion of strip gas in the liquid sulfur.
• the second region 3 is flushed with gas, which flows in via a line 13 and escapes via line 14.
• the gas flows essentially parallel to the surface of the liquid sulfur.
• the gas withdrawn via line 14 also carries off the gaseous sulfur compounds withdrawn from the liquid sulfur.
• the container is filled with liquid sulfur. This filling is not continuous, but at the beginning of the process.
• liquid sulfur can be withdrawn from the first region via lines 22 and 24 and fed to a spraying device 25.
• This atomizing device opens into the second region 3 and atomizes there the liquid sulfur from the first region 2 into the second region 3 flooded with a gas mixture.
• the liquid sulfur can be pumped out of the container 1 via line 22 and line 23 with the aid of the pump 21.
• Figure 3 shows the embodiment of a system according to the invention for carrying out a continuous process. The process takes place in a container 1, which has a flooded with liquid sulfur first region 2 and a gas-flooded second region 3.
• the container 1 is divided by a partition wall 4 into two chambers a, b, wherein the partition wall 4 is not flush, so that both below and above the partition wall 4, the two chambers a, b are connected to each other via openings.
• the opening near the bottom allows the sulfur to flow continuously from chamber a to chamber b;
• the purge gas preferably in countercurrent, can flow from chamber b to chamber a via the opening above the dividing wall.
• a stripping gas is fed to the injection device 12, through which stripping gas is blown into the second chamber with a plurality of nozzles.
• the injection for the stripping gas is provided at the bottom of the second chamber, but it is also possible to perform the injection in the first chamber or in both chambers.
• the embodiment shown has the advantage that in the first chamber, the amounts of dissolved hydrogen sulfide and the Polyschwefelwasserstoffe have been lowered and only to achieve the legally prescribed limit of remaining H 2 S in the degassed sulfur in the second chamber, the additional sparging is made. As a result, the number of required naturalperlungsvorraumen is reduced, registered as little oxygen in the system when using air and simultaneously achieved a sufficiently good result.
• a gas stream is further introduced into the second gas-flooded area 3, which flows from the second chamber b in countercurrent to the flow direction of the liquid sulfur in the first chamber a, from which it is withdrawn via line 14.
• the withdrawal takes place via a corresponding extraction device, preferably a steam jet, which is fed via line 15.
• the contained mixture of the gas streams and gaseous H 2 S is then discharged via line 17.
• Liquid sulfur is continuously introduced via line 20 into the first chamber a of the liquid sulfur flooded first region 2.
• a pump 21 which deducted via line 22 from the first region 2 liquid sulfur and this the atomizing device 25 supplies.
• This sputtering device 25 is located in the gas-flooded second region 3 of the first chamber.
• the partially vented in chamber a liquid sulfur then flows in through the arranged near the bottom opening of the partition wall 4 in the chamber b.
• a pump 21 ' which removes via line 22' liquid sulfur from the first region 2 of the second chamber.
• This is partially supplied via line 24 'to a second atomizing device 25' which atomizes liquid sulfur in the gas phase 3 of the second chamber.
• liquid sulfur is withdrawn via line 23 from the system, wherein the withdrawn amount corresponds to the amount supplied.
• a control device for example a level control valve 26, the withdrawn amount of liquid sulfur from the area 2 of the container can be controlled so that the removal amount is so small that the total residence time of sulfur sufficient to meet the required statutory specification of ⁇ 10 ppm by weight H 2 S to achieve.
• FIG. 4 shows a continuous process for the simultaneous degassing of H 2 S and SO 2. This process is also carried out in a container 1 which has a sulfur-flooded first region 2 and a gas-flooded second region 3.
• the container is divided by two partitions 4 and 5 into three chambers a, b and c, the first two chambers a and b being used for the H 2 S removal and the third chamber c being intended for SO 2 removal.
• the partitions 4 and 5 are mounted so that openings below and above the partitions arise by no delimitation available and so a free flow of gas or sulfur is possible, with sulfur and gas are preferably conducted in countercurrent.
• a first stripping gas preferably air
• the injection device 12 conveniently a plurality of nozzles supplied.
• This introduction of the stripping gas takes place in the second chamber b.
• a gas stream is blown into the second gas-filled area 3 via line 13.
• the total flow of gases which are introduced via lines 1 1 and 13, then flows through the region 3 of the chamber a and is discharged via line 14 again from the container 1 and thereby carries the deducted from the liquid sulfur H 2 S from.
• This line 14 opens into a discharge device 16, which is preferably designed as a steam jet or ejector, which is fed by line 15 with the propellant. Via line 17 then the total amount of gas of the process can be finally discharged.
• a liquid, to be degassed sulfur is introduced into the first chamber a.
• This sulfur is recirculated in the first chamber a via the pump 21 in line 22, which opens into an atomizing device 25.
• This atomizing device 25 is located in the second region 3 of the first chamber a.
• the same apparatus for recirculating and atomizing the sulfur is also found in the second can b, where a pump 21 'supplies liquid sulfur via line 22' to a nebulizer 25 'which controls the liquid slurry in the second gas-flooded area 3 of the second chamber b atomized.
• the device according to the invention also includes a third chamber c for the removal of SO2, which in the same way is equipped with a sputtering and recirculation pump 21 "which feeds the sputtering device 25" via line 22 "and line 24.
• the sputtering device 25 is provided in the gas phase 3 of the third chamber c. At the same time can be withdrawn from the container 1 via line 22 "and 23 parts of the liquid sulfur, which is now degassed.
• the flow of degassed sulfur, which is withdrawn, corresponds to the amount of supplied via line 20 raw sulfur. This can be done via a control device such as the level control valve 26 in the outlet line 23. This control valve continuously adjusts the level in the container 1 so that the residence time is set, which is necessary to achieve the legally prescribed specifications of remaining residual H 2 S and -SO2.
• a stripping gas is introduced into a injection device 31 in the third chamber c via line 30.
• This injection device 31 is equipped with a plurality of nozzles at the bottom of the liquid phase and thus ensures a suitable dispersion of the stripping gas through the sulfur mass.
• this stripping gas is inert gas, such as nitrogen, while air is blown in through the fan 10 and the line 11.
• the gas stream introduced via the line 13 is preferably air.
• the strip gas of the chamber c is introduced via line 30. After bubbling the liquid sulfur in chamber c, it enters the gas phase of chamber b. There it mixes with the introduced via line 1 1 flowing up strip gas chamber b and the introduced via line 13, preferably in countercurrent purge gas. The resulting gas mixture is then passed to the gas phase of the chamber a.
• the total flow of the gases introduced into the container is withdrawn via a suitable extraction device 16, this extraction device 16 is preferably designed as a steam jet, which is fed via line 15 with steam.
• the entire gas mixture containing the removed H 2 S and SO 2 is then removed via line 17.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Degasification And Air Bubble Elimination (AREA)
• Gas Separation By Absorption (AREA)
• Treating Waste Gases (AREA)
• Physical Water Treatments (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Filling Or Discharging Of Gas Storage Vessels (AREA)

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• 2011
  • 2011-12-23 PL PL11290609T patent/PL2607304T3/pl unknown
  • 2011-12-23 ES ES11290609.4T patent/ES2539368T3/es active Active
  • 2011-12-23 EP EP11290609.4A patent/EP2607304B1/de not_active Not-in-force
• 2012
  • 2012-03-20 DE DE102012005450A patent/DE102012005450B4/de not_active Expired - Fee Related
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