EP3601498B1 - Procédé et appareil à désulfurer un courant de gaz contenant de l'hydrogène sulfuré - Google Patents

Procédé et appareil à désulfurer un courant de gaz contenant de l'hydrogène sulfuré Download PDF

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Publication number
EP3601498B1
EP3601498B1 EP18725749.8A EP18725749A EP3601498B1 EP 3601498 B1 EP3601498 B1 EP 3601498B1 EP 18725749 A EP18725749 A EP 18725749A EP 3601498 B1 EP3601498 B1 EP 3601498B1
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Prior art keywords
gas
stage
oxygen
regeneration
catalyst
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German (de)
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EP3601498A1 (fr
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Ralph Joh
Jenny Larfeldt
Christoph Starke
Rüdiger Schneider
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Siemens Energy Global GmbH and Co KG
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Siemens Energy Global GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/544—Extraction for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/56—Specific details of the apparatus for preparation or upgrading of a fuel
    • C10L2290/562—Modular or modular elements containing apparatus

Definitions

  • the invention relates to a method for desulfurization of a gas stream containing hydrogen sulfide, in particular a gas stream that can be used for combustion in a gas turbine.
  • the invention also relates to a device for desulfurizing a gas stream containing hydrogen sulfide.
  • Natural gas is a fossil fuel with a comparatively low level of carbon dioxide (CO 2 ) emissions and comparatively low emissions of other waste products when burned. Its contribution as one of the most important energy resources in the world continues to grow. Against the background of the scarcity of raw materials, the steadily increasing energy demand and rising prices of high-quality fossil fuels, the use of non-specification fuels is becoming increasingly important. There is growing interest, for example, in the direct emission of acidic gases. In the field of gas exploration (acidic natural gases) or in the field of gas processing, there is often a need for electrical energy, especially to cover the internal requirements of machines such as compressors or beyond.
  • CO 2 carbon dioxide
  • gas turbines are used worldwide - alone or in combination with heat recovery steam generators, water-steam cycles and steam turbines (combined cycle power plants) - to provide mechanical and electrical energy.
  • raw natural gas is sometimes only possible to a limited extent due to the acidic components it contains, such as hydrogen sulfide (H 2 S) in particular.
  • H 2 S hydrogen sulfide
  • the trouble-free and energy-efficient operation of gas turbines requires a limitation of the sulfur content in the fuel gas, on the one hand to avoid it or at least to reduce high-temperature corrosion, on the other hand, in order to meet the globally tightened emission limit values with regard to sulfur oxides (SO x ). Therefore, fuel gases containing hydrogen sulfide, and especially acidic natural gases, must be treated accordingly.
  • H 2 S and CO 2 are usually scrubbed out of the natural gas by means of absorption-desorption processes. Because of its toxicity, the separated H 2 S is often converted into elemental sulfur using the so-called Claus process. In order to separate inert gas such as N 2 and also hydrocarbons, additional process steps such as low-temperature condensation processes are necessary. Since these process steps are associated with a high outlay in terms of equipment and are correspondingly complex, the respective systems can only be operated economically if they are able to process very large quantities of natural gas.
  • liquid redox processes are particularly suitable for separating H 2 S from a fuel gas. These liquid redox processes are based on the concept of reactive absorption, in this case a combination of absorption and oxidation.
  • reactive absorption in this case a combination of absorption and oxidation.
  • To separate the hydrogen sulfide from the respective gas it is brought into contact with a scrubbing medium and the hydrogen sulfide contained in the gas is chemically or physically bound to an active substance in the scrubbing medium.
  • the fuel gas which has been cleaned of hydrogen sulfide, can then be burned or converted into electricity directly in a gas turbine.
  • the scrubbing medium containing the hydrogen sulfide is then processed by a catalyst (also known as catalytically active components or redox agents) which converts the hydrogen sulfide contained in the scrubbing medium into elemental sulfur and thus removes the hydrogen sulfide from the scrubbing medium.
  • a catalyst also known as catalytically active components or redox agents
  • the catalyst itself is reduced during the oxidation of the hydrogen sulfide (H 2 S conversion).
  • H 2 S conversion oxidation of the hydrogen sulfide
  • the washing medium to be regenerated and containing the reduced catalyst is used in a process step following the H 2 S separation in a corresponding regeneration stage (for example a bubble column as a contact device) brought into intensive contact with air.
  • a corresponding regeneration stage for example a bubble column as a contact device
  • Contact with the oxygen-containing gas causes the catalyst (and thus also the scrubbing medium) to be regenerated oxidatively.
  • the oxygen-containing gas required for catalyst regeneration is usually supplied via blowers specially set up for this purpose or by gassing with externally supplied, previously compressed oxygen-containing air.
  • the energy required for blowing in the air makes a significant contribution to the operating costs incurred in the context of the liquid redox process. Therefore, these processes are usually designed in such a way that the required fans have to overcome the smallest possible pressure difference.
  • the catalyst regeneration is generally not carried out at pressures above 1 or 2 bar absolute. This in turn means that the container volumes for catalyst regeneration are comparatively large or cannot be reduced in size, which makes the use of liquid redox processes, for example for offshore applications, unattractive.
  • the patent application WO2016 / 180555 describes a method and a device for desulfurization of a gas stream containing sulfur water for combustion in a gas turbine.
  • the invention is therefore based on the object of specifying a possibility that allows an efficient and cost-effective conversion of gases and in particular natural gases into electricity.
  • the gas stream for absorption of the hydrogen sulfide and with the formation of elemental sulfur is contacted with a scrubbing medium containing a catalyst, the catalyst during the formation of the elementary Sulfur is reduced.
  • the scrubbing medium with the reduced catalyst is fed to a regeneration stage in which the reduced catalyst is regenerated by oxidation with an oxygen-containing gas fed to the regeneration stage, the oxygen-containing gas being fed to the regeneration stage from a compression stage of a gas turbine.
  • the gas depleted of oxygen during the regeneration of the catalyst is fed to at least one turbine stage downstream of the compression stage of the gas turbine in terms of flow technology.
  • the method according to the invention enables economical catalyst regeneration even under high pressure through the targeted integration of gas conditioning and the gas turbine process.
  • a small partial flow of the compressed combustion air is taken from a suitable compression stage (compressor stage) of the gas turbine and then passed through the regeneration stage (contact apparatus) for the catalyst regeneration.
  • the oxygen-depleted gas i.e. the exhaust air
  • the supply takes place specifically to one of the compression stage or the pressure stage of the gas turbine which corresponds to the pressure of the exhaust air flow.
  • the exhaust air from the regeneration stage is fed into a turbine stage connected downstream in the flow direction of the combustion air flowing through the gas turbine.
  • the main advantage of this connection variant is that the necessary adjustments to the turbine design are minimal.
  • the highly optimized flow conditions in the respective compression stage of the gas turbine are not influenced.
  • a suitable compression stage that is to say a compressor stage, is understood in the context of the invention to be, in particular, a compression stage which allows the oxygen-containing gas to be withdrawn at a pressure level which allows the gas to be used directly in the regeneration stage allowed.
  • expansion of the oxygen-containing gas before entering the regeneration stage can be dispensed with.
  • the compression stages of a gas turbine also work with high energy efficiency. Since the extracted air from the gas turbine is hot, that is to say taken at a high temperature level, cooled and fed back into the gas turbine at this lower temperature level, there is an efficiency advantage for the gas turbine.
  • the exhaust air i.e. the gas depleted in oxygen during the regeneration of the catalytic converter, which leaves the regeneration stage, still has a high pressure level when it exits and can thus be fed to a turbine stage downstream of the compression stage.
  • a preferred embodiment provides that the oxygen-containing gas of the regeneration stage is fed from the cooling air system of the gas turbine. It is particularly advantageous to remove the oxygen-containing gas from the highest possible pressure level of the cooling air system.
  • Oxygen-depleted gas is particularly preferably fed to the combustion chamber of the gas turbine.
  • the gas taken from the gas turbine that is to say the exhaust air, which is still under high pressure when it emerges from the regeneration stage, is thus preferably fed directly into the combustion process of the gas turbine within the combustion chamber.
  • the combustion chamber is expediently downstream of the compression stage from which the gas used for the regeneration of the catalyst was withdrawn in the flow direction of the combustion air flowing through the gas turbine.
  • the low-oxygen gas flow has to be compressed in order to be able to be fed into the combustion chamber.
  • a significantly smaller air volume flow must be compressed than if the pressure increase required for regeneration had to be achieved by a separate compressor.
  • This configuration also represents a particularly preferred use of the exhaust air from a structural point of view, since only one additional connector is required for this.
  • emissions can be reduced because the possibly contaminated exhaust air from the regeneration stage passes through the combustion process of the gas turbine instead of simply being blown out, for example.
  • gas depleted in oxygen is used to cool the turbine blades of the gas turbine.
  • a supply makes it possible to dispense with a separate air compressor, since here the feed can take place in a correspondingly lower pressure level or compression level.
  • the supply of oxygen-depleted gas to the combustion chamber and its use for cooling the turbine blades of the gas turbine are possible both separately and jointly according to the invention.
  • the supply of the exhaust air to alternative or additional turbine stages is also possible according to the invention, if necessary.
  • the oxygen-containing gas removed from the compression stage is cooled before entering the regeneration stage.
  • the heat released during the cooling of the oxygen-containing gas is expediently used further.
  • the heat released during the cooling of the oxygen-containing gas is fed to a processing device for processing the washing medium used.
  • the invention provides for the heat released to be fed into the desulfurization process of the gas stream.
  • the cooled oxygen-containing gas removed from the compression stage is then brought into contact with the scrubbing medium containing the reduced catalyst within the regeneration stage.
  • the oxygen contained in the gas passes from the gas phase into the scrubbing medium.
  • the oxygen-containing gas is depleted of oxygen.
  • the catalyst which was previously reduced during sulfur formation, is oxidized, and the catalyst is regenerated or recovered.
  • the scrubbing medium containing the regenerated catalyst is then available again for separating off hydrogen sulfide and for its subsequent oxidation.
  • the washing medium - containing the reduced catalyst and elemental sulfur - is preferably depressurized before being fed to the regeneration stage.
  • a so-called flash container in which the washing medium is degassed is traditionally used as the expansion stage.
  • methane (CH 4 ) dissolved in the washing medium in particular is removed.
  • the resulting gas stream is preferably combined with the purified gas and thus fed to the combustion chamber. After relaxation, it is essentially methane-free Washing medium is then fed to the regeneration stage in particular.
  • the washing medium In addition to degassing the washing medium before it enters the regeneration stage, it is desirable to separate off the elemental sulfur contained in the washing medium.
  • at least a partial flow of the washing medium which, in addition to the reduced catalyst, contains the precipitated elemental sulfur is preferably separated off.
  • the precipitated sulfur can be separated off at various points. Preference is given to separating the elemental sulfur before the washing medium enters the regeneration stage.
  • the partial flow can take place here, for example, either before the pressure in the washing medium is released in the flash container or afterwards.
  • sufficient sulfur is preferably removed that the concentration of the precipitated sulfur in the washing medium after separation is about 5%.
  • the sulfur contained in the substream is expediently separated from it.
  • the separation takes place preferably by means of common separation units, such as for example by means of a cyclone.
  • the sulfur itself is expediently sent for further utilization.
  • the partial stream of the scrubbing medium which has been cleaned of sulfur is preferably fed to the regeneration stage in order to regenerate the reduced catalyst still present in the scrubbing medium.
  • An amino acid salt solution is preferably used as the washing medium.
  • An aqueous amino acid salt solution is useful here. Mixtures of different amino acid salts can also be used as washing medium.
  • a metal salt is preferably used as the catalyst.
  • those metal salts are suitable whose metal ions can be present in several oxidation states.
  • the salts of the metals iron, manganese or Copper used.
  • These metal salts can be purchased inexpensively and have the desired catalytic properties.
  • Metal chelate complexes which have a sufficiently high solubility in the aqueous formulation are particularly advantageous.
  • a complexing agent such as EDTA (ethylenediamine tetraacetate), HEDTA (hydroxyethyl ethylenediamine tetraacetate), DTPA (diethylenetriamine pentaacetate) and / or NTA (nitrile triacetate) is expediently added to the washing medium.
  • the device according to the invention for desulfurizing a gas stream containing hydrogen sulfide, in particular a fuel gas stream usable for combustion in a gas turbine comprises an absorber for the absorption of hydrogen sulfide from the gas stream with the formation of elemental sulfur by means of a scrubbing medium containing a catalyst, as well as a regeneration stage fluidically coupled to the absorber for Regeneration of the catalyst reduced during the sulfur formation by means of an oxygen-containing gas, the regeneration stage for supplying the oxygen-containing gas being fluidically coupled with a compression stage of a gas turbine.
  • the regeneration stage for removing the oxygen-depleted gas is fluidically coupled to at least one compression stage of the downstream turbine stage of the gas turbine.
  • the hydrogen sulfide contained in the gas stream is removed from a gas stream by absorption in the scrubbing medium.
  • An amino acid salt solution is preferably used as the washing medium.
  • the absorbed hydrogen sulphide reacts within the absorber by means of a catalyst contained in the washing medium to form elemental sulfur and is itself reduced in the process.
  • a metal salt which is contained in the washing medium is preferably used as the catalyst. The use of metal chelate complexes as catalyst is particularly preferred.
  • the scrubbing medium is fed to the regeneration stage downstream of the absorber in the flow direction of the scrubbing medium.
  • the absorber expediently comprises a discharge line which is fluidically coupled to a supply line of the regeneration stage.
  • the regeneration stage is expediently connected to a further supply line which is fluidically coupled to the discharge line of a compression stage of the gas turbine. Via this fluidic coupling, oxygen-rich gas is fed to the regeneration stage starting from the compression stage.
  • the coupling of the regeneration stage with the highest possible pressure stage or the highest possible compression stage of the compressor of the gas turbine is particularly advantageous.
  • the feed line of the regeneration stage is expediently coupled in terms of flow to the discharge line of the compression stage of the compressor of the gas turbine.
  • the gas depleted in oxygen in the course of the reaction is fed back to the gas turbine.
  • the oxygen-depleted gas is preferably fed directly into the combustion process of the gas turbine.
  • the regeneration stage is expediently coupled to a combustion chamber of the gas turbine that is downstream of the compression stage in terms of flow.
  • the combustion chamber is fluidically downstream of the compression stage in the flow direction of the combustion air flowing through the gas turbine.
  • the regeneration stage expediently includes a discharge line, which is fluidically coupled to a supply line of the combustion chamber of the gas turbine.
  • the regeneration stage is coupled to a cooling system downstream of the compression stage for cooling the turbine blades.
  • the regeneration stage expediently comprises a discharge line which is fluidically coupled to a supply line of the cooling system.
  • a relaxation stage a so-called flash stage, is connected in terms of flow between the absorber and the regeneration stage.
  • the expansion stage the washing medium flowing out of the absorber, which contains the precipitated sulfur and the reduced catalyst, is expanded.
  • methane is desorbed, preventing it from being carried over into the regeneration stage.
  • An enrichment in the washing medium will only take place to a certain extent, since the washing medium is continuously freed of methane during regeneration by stripping with air.
  • the expansion stage is expediently switched into the discharge line of the absorber and thus downstream of the absorber in terms of flow in the direction of flow of the washing medium.
  • the essentially methane-free washing medium is drawn off via a discharge line connected to the expansion stage and fed to the regeneration stage.
  • a withdrawal line for withdrawing a partial flow of the washing medium is preferably included.
  • the extraction line can in principle be connected to different positions of the device, with extraction from the expansion stage designed as a flash container being preferred. Accordingly, the extraction line is expediently connected to the expansion stage. In this way, some of the oxidation elemental sulfur precipitated from the hydrogen sulfide is separated from the scrubbing medium.
  • the preferred concentration of the precipitated sulfur remaining in the washing medium after the separation is around 5%.
  • the sulfur is preferably separated off from the washing medium in a separation unit connected in terms of flow in the flow direction of the partial flow withdrawn from the withdrawal line.
  • FIG 1 a device 1 for desulfurizing a gas flow 3 and in particular for desulfurizing a fuel gas flow for a gas turbine is shown.
  • the gas stream 3 is fed to an absorber 5 via a feed line 6 connected to it and is brought into contact within the absorber 5 with an aqueous amino acid salt solution as a washing medium 7.
  • an aqueous amino acid salt solution as a washing medium 7.
  • hydrogen sulfide 9 contained in the gas stream 3 is absorbed in the scrubbing medium 7.
  • the gas purified of hydrogen sulfide 9 is taken from the absorber 5 via a discharge line 11 and fed to the combustion in a gas turbine process.
  • the hydrogen sulfide 9 absorbed in the washing medium 7 is oxidized to elemental sulfur 15 by a catalyst 13 contained in the washing medium 7, in the present case complexed Fe (III) ions.
  • the catalyst 13 is reduced to Fe (II) ions during the oxidation of the hydrogen sulfide 9.
  • the sulfur 15 precipitates as a solid, which is formed by the reduction Fe (II) ions remain in solution and are masked by EDTA as a complexing agent added to the washing medium 7.
  • the washing medium 21 containing the reduced catalyst 17 and the elemental sulfur 15 is then fed to an expansion stage (flash stage) 23 downstream of the absorber 7 in terms of flow.
  • the supply takes place via a fluidic coupling of a discharge line 25 connected to the absorber 5 with a supply line 27 of the expansion stage 23.
  • the washing medium 21 is expanded and methane contained therein is desorbed.
  • the desorbed methane is fed to a gas turbine 31 via a discharge line 29 connected to the expansion stage 23.
  • the discharge line 29 is coupled to a supply line 33 of the gas turbine 31.
  • a partial flow 35 of the washing medium 21 is withdrawn via a withdrawal line 37 connected to the expansion stage 23.
  • the concentration of precipitated sulfur 15 in the washing medium 21 is reduced to a concentration of approximately 5%.
  • the partial flow 35 withdrawn from the washing medium 21 is fed to a separation unit 39 designed as a filter, in which the sulfur 15 is separated from the washing medium 21.
  • the sulfur itself is fed to further utilization.
  • the washing medium 21, which has been cleaned of sulfur 15, is returned.
  • a return line 41 of the separation unit 39 is fluidically coupled to a discharge line 43 of the expansion stage 23.
  • the washing medium 21 from which sulfur has been removed is combined with the main flow 45 of the washing medium 21 via this coupling.
  • the degassed washing medium 21, which has been cleaned of sulfur 15, is then fed to the regeneration stage 49 via a feed line 47 coupled to the discharge line 43 of the expansion stage 21 whose head 51 is fed.
  • the washing medium 21 is contacted with an oxygen-containing gas 53, which flows into the regeneration stage 49 via a feed line 57 connected to the regeneration stage 49 at its base 55.
  • the oxygen-containing gas 53 is taken from a compression stage 59, that is to say from a compressor of the gas turbine 31.
  • the oxygen-containing gas 53 is supplied via the fluidic coupling of a discharge line 61 of the compression stage 59, in this case the cooling air system 60 of the gas turbine 31 with the supply line 57 of the regeneration stage 49. Via this fluidic coupling, the oxygen-containing gas 53 taken from the compression stage 59 can be transferred to the regeneration stage 49 flow and are used there to regenerate the reduced catalyst 17 contained in the washing medium 21. At the same time, the washing medium 21 is regenerated.
  • the oxygen-containing gas 53 that is to say the air taken from the gas turbine 31, flows into the regeneration stage 49 in a flow direction 65 that is opposite to the flow direction 63 of the washing medium 21.
  • a heat exchanger 67 is arranged, which cools the gas 53 before it enters the regeneration stage 49.
  • the heat dissipated here can be fed into the process at a suitable point.
  • the regression of the catalyst 13 takes place through the contact of the scrubbing medium 7 with the oxygen-containing gas 53.
  • the oxygen contained in the gas 53 passes from the gas phase into the liquid phase.
  • the Fe (II) ions previously reduced during sulfur formation are oxidized to Fe (III) ions and the catalyst 13 is thus recovered.
  • the scrubbing medium 7 is also recovered, which - containing the original catalyst 13 - is again available for separating hydrogen sulfide 9 from a gas stream 3.
  • the regenerated Washing medium 7 is withdrawn via a discharge line 69 connected to the bottom 55 of the regeneration stage 49 and fed to the absorber 5 via a fluidic coupling of the discharge line 69 with a supply line 71 of the absorber 5.
  • the oxygen-depleted gas 73 produced during the regeneration of the catalytic converter 13 within the regeneration stage 49, that is to say the exhaust air, is now returned to the gas turbine process.
  • the oxygen-depleted gas 73 of the regeneration stage 49 is withdrawn via a discharge line 75 connected to it and fed to a turbine stage 77 downstream of the compression stage 59 of the gas turbine 31 in terms of flow.
  • discharge line 75 of regeneration stage 49 is fluidically coupled to a supply line 79 of turbine stage 77.
  • the turbine stage 77 is the combustion chamber 81 of the gas turbine 31, so that the low-oxygen gas 73 flows directly into the combustion process of the gas turbine 31.
  • the low-oxygen gas 73 can be used to cool the turbine blades of the gas turbine 31.
  • the exhaust air i.e. the gas 73 depleted in oxygen during the regeneration of the catalytic converter 17, which leaves the regeneration stage 49 again, still has a high pressure level when it exits and can thus be fed to a turbine stage 77 downstream of the compression stage 59 in terms of flow.
  • the combustion of the low-oxygen gas 73 that is to say of the exhaust air discharged from the regeneration stage 49, reduces undesirable emissions.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Industrial Gases (AREA)

Claims (15)

  1. Procédé de désulfuration d'un courant (3) gazeux contenant de l'hydrogène sulfuré (9), notamment d'un courant (3) de gaz combustible pouvant être utilisé pour la combustion dans une turbine (31) à gaz, dans lequel on met le courant (3) gazeux, pour l'absorption de l'hydrogène sulfuré (9) et avec formation de soufre (15) élémentaire, en contact avec un fluide (7) de lavage contenant un catalyseur (13), dans lequel on réduit le catalyseur (13) lors de la formation du soufre (15) élémentaire, dans lequel on envoie le fluide (21) de lavage contenant le catalyseur (17) réduit à un étage (49) de régénération, dans lequel on reforme le catalyseur (17) réduit par oxydation par un gaz (53) contenant de l'oxygène envoyé à l'étage (49) de régénération, dans lequel on envoie le gaz (53) contenant de l'oxygène à l'étage (49) de régénération à partir d'un étage (59) de compression de la turbine (31) à gaz, et dans lequel on envoie le gaz (73), appauvri en oxygène lors de la régénération du catalyseur (17), au moins à un étage (77) de la turbine (31) à gaz, en aval, en technique fluidique, de l'étage (59) de compression.
  2. Procédé suivant la revendication 1, dans lequel on envoie le gaz (53) contenant de l'oxygène à l'étage (49) de régénération à partir du système (60) d'air de refroidissement de la turbine (31) à gaz.
  3. Procédé suivant la revendication 1 ou 2, dans lequel on envoie du gaz (73) appauvri en oxygène à la chambre de combustion (81) de la turbine (31) à gaz.
  4. Procédé suivant l'une des revendications précédentes, dans lequel on utilise du gaz (73) appauvri en oxygène pour refroidir les aubes de la turbine (31) à gaz.
  5. Procédé suivant l'une des revendications précédentes, dans lequel on refroidit du gaz contenant de l'oxygène prélevé de l'étage (59) de compression avant l'entrée dans l'étage (49) de régénération.
  6. Procédé suivant l'une des revendications précédentes, dans lequel on détend le fluide (21) de lavage avant de l'envoyer à l'étage (49) de régénération.
  7. Procédé suivant l'une des revendications précédentes, dans lequel on sépare au moins un courant (35) partiel du fluide (21) de lavage.
  8. Procédé suivant l'une des revendications précédentes, dans lequel on envoie le fluide (7) de lavage régénéré à un absorbeur (5).
  9. Procédé suivant l'une des revendications précédentes, dans lequel on utilise une solution de sel d'acide aminé, comme fluide (7) de lavage.
  10. Procédé suivant l'une des revendications précédentes, dans lequel on utilise un sel métallique, comme catalyseur (13).
  11. Installation (1) de désulfuration d'un courant (3) gazeux contenant de l'hydrogène sulfuré, notamment d'un courant (3) de gaz combustible pouvant être utilisé pour la combustion dans une turbine (31) à gaz, comprenant un absorbeur (5) pour l'absorption de l'hydrogène sulfuré (9) du courant (3) gazeux avec formation de soufre (15) élémentaire au moyen d'un fluide (7) de lavage contenant un catalyseur (13), ainsi qu'un étage (49) de régénération communiquant fluidiquement avec l'absorbeur (5) pour la régénération, au moyen d'un gaz (53) contenant de l'oxygène, du catalyseur (17) réduit lors de la formation de soufre, l'étage (49) de régénération communiquant, pour l'envoi du gaz (53) contenant de l'oxygène, fluidiquement avec un étage (59) de compression d'une turbine (31) à gaz, et dans lequel l'étage (49) de régénération communique, pour l'évacuation du gaz (73) appauvri en oxygène, fluidiquement avec au moins étage (77) de turbine de la turbine (31) à gaz en aval fluidiquement de l'étage (59) de compression.
  12. Installation (1) de désulfuration suivant la revendication 11, dans laquelle l'étage (49) de régénération communique, pour l'envoi du gaz (53) contenant de l'oxygène, fluidiquement avec la système (60) d'air de refroidissement de la turbine (31) à gaz.
  13. Installation (1) de désulfuration suivant la revendication 11 ou 12, dans laquelle l'étage (49) de régénération communique avec une chambre de combustion (81) montée en aval fluidiquement de l'étage (59) de compression.
  14. Installation (1) de désulfuration suivant l'une des revendications 11 à 13, dans laquelle l'étage (49) de régénération communique avec un système de refroidissement des aubes de la turbine monté en aval fluidiquement de l'étage (59) de compression.
  15. Installation (1) de désulfuration suivant l'une des revendications 11 à 14, dans laquelle un étage (23) de détente est monté fluidiquement entre l'absorbeur (5) et l'étage (49) de régénération.
EP18725749.8A 2017-05-09 2018-04-16 Procédé et appareil à désulfurer un courant de gaz contenant de l'hydrogène sulfuré Active EP3601498B1 (fr)

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PCT/EP2018/059620 WO2018206228A1 (fr) 2017-05-09 2018-04-16 Procédé et dispositif de désulfuration d'un flux gazeux contenant de l'hydrogène sulfuré

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CN114073992B (zh) * 2020-08-14 2024-05-31 中国石油化工股份有限公司 一种氧化还原脱硫工艺的富氧再生装置和方法及应用

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KR20150140817A (ko) * 2013-04-15 2015-12-16 지멘스 악티엔게젤샤프트 흡수제, 흡수제의 제조 방법, 및 산성 가스로부터 황화수소를 분리하기 위한 방법 및 장치
EP3271046B1 (fr) * 2015-05-12 2020-02-12 Siemens Aktiengesellschaft Procédé et dispositif de désulfuration d'un flux de gaz

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EP3601498A1 (fr) 2020-02-05
CN110621764A (zh) 2019-12-27
WO2018206228A1 (fr) 2018-11-15
US10941364B2 (en) 2021-03-09

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