WO2014191160A1 - Dispositif et procédé de séparation de dioxyde de carbone d'avec un courant gazeux - Google Patents

Dispositif et procédé de séparation de dioxyde de carbone d'avec un courant gazeux Download PDF

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Publication number
WO2014191160A1
WO2014191160A1 PCT/EP2014/059082 EP2014059082W WO2014191160A1 WO 2014191160 A1 WO2014191160 A1 WO 2014191160A1 EP 2014059082 W EP2014059082 W EP 2014059082W WO 2014191160 A1 WO2014191160 A1 WO 2014191160A1
Authority
WO
WIPO (PCT)
Prior art keywords
washing medium
desorber
carbon dioxide
gas stream
return line
Prior art date
Application number
PCT/EP2014/059082
Other languages
German (de)
English (en)
Inventor
Björn Fischer
Ralph Joh
Diego Andres KUETTEL
Rüdiger Schneider
Original Assignee
Siemens Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2014191160A1 publication Critical patent/WO2014191160A1/fr

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Classifications

    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20494—Amino acids, their salts or derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the invention relates to a separator for carbon dioxide from a gas stream, in particular from a flue gas stream. Furthermore, the invention relates to a method for the separation of carbon dioxide from a gas stream, in particular from a flue gas stream.
  • the flue gas is brought into contact with a suitable washing medium after combustion, whereby gaseous carbon dioxide contained in the flue gas is dissolved in the washing medium or absorbed in the chemical sense.
  • the exhaust gas freed of carbon dioxide is finally released into the atmosphere.
  • the carbon dioxide-loaded washing medium can be obtained by desorption of the absorbent regenerated carbon dioxide and used again for the absorption of carbon dioxide from the flue gas.
  • Common chemical washing media are based on amines, which react selectively but reversibly with the carbon dioxide contained in the intoxicating gas and thus remove it from the flue gas.
  • desulfurization units for removing S0 X and so-called DeNO x plants can be used to remove N0 X , which remove the pollutants from the flue gas before entering the separation device.
  • N0 X which remove the pollutants from the flue gas before entering the separation device.
  • the whereabouts of a residual proportion, in particular of nitrogen oxides, in the flue gas can not be ruled out.
  • amine wash One way to remove nitrosamines formed in the wash medium is in the amine wash.
  • Conventional amine washes provide for an evaporator, in which the amine evaporated and the interfering impurities, ie degradation products and so-called “heat-stable salts (HSS)" can be separated as evaporation residue.
  • HSS heat-stable salts
  • a method can be used in which the pure amino acid can be recovered by crystallization.
  • the nitrosamine is the determining factor for the interpretation of the crystallization process and associated with a correspondingly high cost.
  • a method can be used which makes use of the low thermal stability of nitrosamines.
  • the washing medium is taken from an absorber of a separator and fed to a nitrosamine reduction process.
  • the nitrosamines are decomposed at temperatures above 200 ° C, so that the nitrosamine content in the washing medium can be regulated and significantly reduced.
  • a first object of the invention to provide a carbon dioxide separation device which, while retaining the capacity of the washing medium, enables effective separation of nitrosamines contained in the washing medium.
  • a second object of the invention is to specify a method for the deposition of carbon dioxide which allows the purification of a nitroso-contaminated washing medium.
  • the first object of the invention is achieved by a separator for carbon dioxide from a gas stream, in particular from a flue gas stream, comprising an absorber for separating carbon dioxide from the gas stream by means of a washing medium, and a via a return line fluidly coupled to the absorber desorber for releasing Carbon dioxide absorbed in the washing medium, the desorber being fluidly connected to a treatment device which is set up and designed to remove nitrosamines contained in the washing medium.
  • the invention is based on the fact that nitrosamines must necessarily be removed from a washing medium due to their harmful effects in order to prevent discharge into the atmosphere.
  • the methods used to date for this purpose are only conditionally suitable for removing the nitrosamines in order to obtain the washing medium or while ensuring the concentration of the active components in a washing medium.
  • the temperature-induced degradation and thus the loss of the washing medium proves to be problematic.
  • the invention recognizes that, despite the above-described problem with respect to the degradation of the washing medium on the removal of nitrosamines can be accessed by thermal decomposition, if the washing medium to be purified from nitrosamines not removed at the absorber, but instead at the desorber and thermal accordingly is treated.
  • the desorber is a treatment device fluidically connected, which is set up and designed to remove contained in the washing medium nitrosamines.
  • the scrubbing medium to be cleaned is hereby removed at one point of the separating device, namely at the outlet of the desorber, and fed to the processing device.
  • the CO 2 loading of the washing medium which promotes undesired degradation and in particular the carbamate polymerization of the washing medium, is particularly low.
  • removal from the desorber can effectively remove nitrosamines from the wash medium without degrading the active component of the wash medium due to excessive CO 2 loading. In this way, on the one hand, the amount to be used
  • the temperature at the outlet of the desorber is higher than at an absorber outlet, so that less heating of the washing medium requires less energy than is the case when the washing medium is removed from the absorber. This lower energy requirement also has a positive effect on the operating costs.
  • the treatment device thus fulfills the requirements for effective separation of nitrosamines contained in the washing medium and at the same time makes it possible to maintain the concentration of the active washing component in the washing medium.
  • the treatment device may additionally comprise, in particular, those device components which serve to further reduce the CO 2 loading of the detergent.
  • the return line of the desorber advantageously comprises a branch line, which is fluidically coupled to a supply line of the treatment device.
  • the washing medium can also be fed into the treatment device via a line which is connected to the outlet of the desorber and which is not fluidically coupled to the return line of the desorber.
  • the treatment device comprises a flash vessel, which is set to remove a carbon dioxide contained in the washing medium.
  • a flash tank is an evaporator that uses the
  • the washing medium taken from the return line of the desorber is introduced into the flash tank at atmospheric pressure.
  • the flash container is thus used for degassing of the washing medium prior to the thermal decomposition of the nitrosamines.
  • the C0 2 loading of the washing medium before the thermal destruction of the nitrosamines can be further reduced.
  • the degradation of the washing medium as a result of carbamate polymerization is thus significantly reduced.
  • the carbon dioxide separated off from the washing medium in the flash container is fed via a discharge line connected to the flash container to a utilization device which serves for processing and transferring the carbon dioxide into further products.
  • a utilization device which serves for processing and transferring the carbon dioxide into further products.
  • the carbon dioxide can be compressed to allow for transport to a storage location where it can be finally stored.
  • the flash tank is preceded by a preheater fluidly, so that the washing medium has the desired temperature for the flash evaporation on entering the flash tank. Due to the already increased temperature of the washing medium after removal from the desorber in this case only a small preheating is necessary in particular, so that the preheater can be made small.
  • the flash container is followed by a reaction chamber for the decomposition of nitrosamines contained in the washing medium downstream of the fluid.
  • the reaction chamber is in this case designed, in particular, as a tubular reactor, it being understood that the use of other reaction vessels is also possible.
  • the washing medium flowing out of the flash container and largely freed of carbon dioxide flows into the reaction chamber.
  • the reaction chamber Within the reaction chamber is the
  • Washed medium so that the nitrosamines contained in the washing medium are thermally destroyed. Since unwanted carbon dioxide has already been removed in the flash vessel upstream of the reaction chamber, thermal degradation of the washing medium as a result of carbamate polymerization can be prevented.
  • reaction chamber downstream of the cooling of the treated washing medium, a heat exchanger downstream. So the washing medium on the for the Separation process and the subsequent absorption of carbon dioxide required temperatures are cooled down.
  • the treatment device For recycling the washing medium, the treatment device comprises a return line, which is fluidically coupled to the return line of the desorber.
  • the desorber is fluidly coupled via its return line to a supply line of the absorber.
  • the scrubbing medium purified in the desorber of carbon dioxide can be supplied to the absorber.
  • the washing medium is then again available for the absorption of carbon dioxide and, depending on the configuration of the absorber for cooling, expediently flows through one or more cooling units.
  • a discharge line is connected to the desorber, which opens into a utilization device.
  • the recycling facility serves to prepare and transfer the desorbed carbon dioxide into further products.
  • the remaining C0 2 -rich gas stream can be compressed in order to enable transport to a storage location where the C0 2 can finally be stored.
  • an amino acid salt solution is used as the washing medium.
  • An aqueous amino acid salt solution is useful here.
  • an amino acid salt having a carbon substituent selected from the group consisting of hydrogen, an alkyl, a hydroxyalkyl and an aminoalkyl More preferably, an amino acid salt is used which has a nitrogen substituent from the group which contains hydrogen, an alkyl, a hydroxyalkyl and a haloalkyl.
  • a single amino acid salt such as a potassium salt of glycine or other amino acids may be used.
  • mixtures of different amino acid salts can be used as the absorbent. More preferably, the amino acid salt is a salt of a metal, especially an alkali metal.
  • the desorber is preferably connected to a reboiler.
  • the reboiler supplies the necessary heat of regeneration for the separation of absorbed CO 2 from the washing medium.
  • the loaded washing medium is in this case regenerated by steam, which is generated in the reboiler. To generate the steam within the reboiler this is usually heated with imported steam, for example from a connected steam power plant.
  • the second object of the invention is achieved according to the invention by a method for separating carbon dioxide from a gas stream, in particular from a flue gas stream, in which a gas stream is brought into contact with the washing medium in an absorber of a separating device while separating carbon dioxide contained in the gas stream. and the laden washing medium for releasing the carbon dioxide is fed to a desorber of the separating device, wherein the washing medium after the separation of the carbon dioxide in the desorber is supplied to a recycling device coupled to a return line of the desorber, in which nitrosamines contained in the washing medium are removed.
  • the method is used to purify a contaminated with nitrosamines washing medium in a deposition process for carbon dioxide.
  • the washing medium can be effectively cleaned of unwanted and interfering nitrosamines before it is returned to the absorption process while maintaining the concentration of the active washing component.
  • the washing medium is expediently fed to the treatment device via a branch line connected to the return line of the desorber.
  • the washing medium is fed to a flash tank in the treatment device.
  • the C0 2 load of the washing medium is further reduced, thus creating optimal conditions for the thermal decomposition of the nitrosamines.
  • the scrubbing medium is fed to a reaction chamber for the decomposition of nitrosamines after it leaves the flash vessel.
  • the largely freed of carbon dioxide washing medium can be purified here and finally returned to the deposition process.
  • the liberated from nitrosamines wash medium is expediently cooled after exiting the reaction chamber.
  • the washing medium preferably flows via a return line of the treatment device into the return line of the desorber.
  • separated carbon dioxide is fed to a utilization device in the desorber.
  • the carbon dioxide separated in the flash container is also supplied to this utilization device, so that the utilization device can be used in common for both C0 2 gas streams.
  • effluent washing medium is fed to a reboiler. It is advantageous if an amino acid salt solution is used as the washing medium, the amino acid salt can react selectively but reversibly with carbon dioxide contained in the flue gas and can thus remove it from the flue gas. Further advantageous embodiments of the method for
  • FIG. 1 shows a separation device for carbon dioxide with a schematic treatment device for the removal of nitrosamines from a washing medium
  • FIG. 2 shows a detailed representation of the treatment device according to FIG. 1
  • the separation device 1 shows a separation device 1 for carbon dioxide from a flue gas stream.
  • the separation device 1 comprises an absorber 3 and a desorber 5 fluidically coupled thereto.
  • the flue gas is introduced into the C0 2 - separator 1.
  • the flue gas is supplied to the absorber 3 via a flue gas line 7.
  • an aqueous amino acid salt solution which is used to separate the carbon dioxide contained in the flue gas.
  • the flue gas in the absorber 3 is brought into contact with the washing medium 9 and the Carbon dioxide contained in the flue gas absorbed in the washing medium 9.
  • the cleaned of carbon dioxide gas stream is discharged from the absorber 3 at the absorber head 11.
  • the absorber 3 is fluidly coupled to a feed line 15 of the desorber 5, so that the loaded with carbon dioxide washing medium 9 can be pumped via these two lines 13, 15 with temperature increase by means of a pump 17 in the desorber 5.
  • the loaded washing medium 9 passes through a heat exchanger 19, in which the heat of the regenerated scrubbing medium 9 flowing from the desorber 5 to the absorber 3 is transferred to the laden scrubbing medium 9 supplied to the desorber 5 by the absorber 3.
  • the heat exchanger 19 thus uses the waste heat of the desorber 5 to preheat the washing medium 9 from the absorber 3 before entering the desorber 5.
  • the carbon dioxide absorbed in the washing medium 9 is thermally desorbed.
  • the desorber 5 is connected to a discharge line 21, which opens into a utilization device 23.
  • the desorbed C0 2 -rich gas stream can be compressed in order, for example, to enable transport to a storage site.
  • the desorber 5 is connected to a treatment device 25 in terms of flow technology.
  • the fluidic coupling in this case takes place via a return line 27 connected to the desorber 5.
  • the return line 27 comprises a branch line 29, which in turn is fluidically coupled to a supply line 31 of the treatment device 25.
  • the preparation device 25 comprises a preheater 33, a flash tank 35 downstream of the preheater, and a reaction chamber 37.
  • the C0 2 charge of the scrubbing medium 9 supplied to the treatment device 25 can be further developed in a first step be reduced.
  • nitrosamines contained in the washing medium 9 can be removed by thermal decomposition.
  • the treatment device 25 comprises a return line 39, which is fluidically coupled to the return line 27 of the desorber 5.
  • the return line 27 of the desorber 5 in turn is fluidically coupled to a feed line 41 of the absorber 3.
  • the regenerated in the desorber 5 washing medium 9 is returned via the fluidic connection between the return line 27 and the feed line 41 by means of a pump 43 in the absorber 3 and is there to re-absorption of C0 2 from the flue gas available.
  • the desorber 5 is connected to a reboiler 45.
  • the loaded washing medium 9 is in this case regenerated by steam, which is generated in the reboiler 45.
  • the reboiler 45 is heated with imported steam, for example from a connected steam power plant, which is not shown here.
  • FIG. 2 shows a detailed illustration of the processing device 25.
  • the treatment device 25 serves to remove nitrosamines contained in the washing medium.
  • the treatment device 25 as already designated in the description of FIG. 1, comprises a flash container 35.
  • the flash container 35 is a flash evaporator, to which the washing medium 9 withdrawn from the desorber 5 is supplied via a supply line 47.
  • the washing medium 9 in this case passes through a filter 49 and a pump 51.
  • the washing medium 9 is preheated before entering the flash tank 35 in the preheater 33, so that the washing medium 9 has the desired temperature for the flash evaporation.
  • the flash tank 35 9 is still contained in the washing medium
  • the desorber 5 removed washing medium 9 is introduced into the flash tank 35 at atmospheric pressure. In the flash evaporation, superheating of the washing medium 9 occurs here. A residual fraction of carbon dioxide dissolved in the desorber 5 during desorption in the washing medium 9 evaporates and can thus be removed from the washing medium 9.
  • the flash container 35 is thus used to degas the washing medium 9 prior to the thermal decomposition of the nitrosamines.
  • the carbon dioxide separated off from the washing medium 9 in the flash container 35 is connected via a flash container 35
  • Outlet line 53 of the utilization device 23 is supplied, in which also the carbon dioxide-rich gas stream is discharged from the desorber 5.
  • both gas streams can be combined and compacted and transported to a storage site.
  • the thermal decomposition itself then takes place in the reactor chamber 37 designed as a tubular reactor Flash tank 35 flowing, largely freed from carbon dioxide washing medium 9 flows into the tube reactor 37 and is heated there.
  • the nitrosamines contained in the washing medium 9 can be thermally destroyed. Since unwanted carbon dioxide has already been removed in the flash tank 35 upstream of the reaction chamber 37, thermal degradation of the washing medium 9 as a result of carbamate polymerization can be prevented.
  • a heat exchanger 55 downstream of flow can be cooled down to the temperatures required for the deposition process and the subsequent absorption of carbon dioxide in the absorber 3.
  • the scrubbing medium purified by nitrosamines is returned via the return line 39 to the treatment device 25 to the deposition process in the separating device 1, where it is again available for absorbing carbon dioxide from a flue gas stream.

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

Abstract

L'invention concerne un dispositif (1) de séparation de dioxyde de carbone d'avec un courant gazeux, en particulier un courant de gaz brûlés, comprenant un absorbeur (3), qui sert à séparer le dioxyde de carbone du courant gazeux au moyen d'un agent de lavage (9), ainsi qu'un désorbeur (5), en liaison fluidique avec l'absorbeur (3) par le biais d'une conduite de retour (27), qui sert à libérer le dioxyde de carbone absorbé dans l'agent de lavage (9). Le désorbeur (5) est en liaison fluidique avec un dispositif de traitement (25) qui est conçu et adapté pour éliminer les nitrosamines contenues dans l'agent de lavage (9). L'invention concerne en outre un procédé de séparation de dioxyde de carbone d'avec un courant gazeux, en particulier un courant de gaz brûlés.
PCT/EP2014/059082 2013-05-28 2014-05-05 Dispositif et procédé de séparation de dioxyde de carbone d'avec un courant gazeux WO2014191160A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013209886 2013-05-28
DE102013209886.3 2013-05-28

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WO2014191160A1 true WO2014191160A1 (fr) 2014-12-04

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107427760A (zh) * 2015-04-02 2017-12-01 西门子公司 用于从气体流中分离二氧化碳的设备和方法
EP3246082A4 (fr) * 2015-01-07 2018-09-12 Mitsubishi Hitachi Power Systems, Ltd. Procédé et dispositif pour traiter un composé nitrosé
US11439950B2 (en) 2018-07-02 2022-09-13 Universiity of Kentucky Research Foundation Electrochemical cell, method and apparatus for capturing carbon dioxide from flue gas and decomposing nitrosamine compounds

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2481466A1 (fr) * 2011-01-31 2012-08-01 Siemens Aktiengesellschaft Dispositif et procédé de nettoyage d'un produit d'une installation de processus contaminé par de la nitrosamine
EP2559473A1 (fr) * 2011-08-18 2013-02-20 Siemens Aktiengesellschaft Procédé et dispositif de nettoyage d'un produit d'une installation de processus contaminé par de la nitrosamine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2481466A1 (fr) * 2011-01-31 2012-08-01 Siemens Aktiengesellschaft Dispositif et procédé de nettoyage d'un produit d'une installation de processus contaminé par de la nitrosamine
EP2559473A1 (fr) * 2011-08-18 2013-02-20 Siemens Aktiengesellschaft Procédé et dispositif de nettoyage d'un produit d'une installation de processus contaminé par de la nitrosamine

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3246082A4 (fr) * 2015-01-07 2018-09-12 Mitsubishi Hitachi Power Systems, Ltd. Procédé et dispositif pour traiter un composé nitrosé
US10434459B2 (en) 2015-01-07 2019-10-08 Mitsubishi Hitachi Power Systems, Ltd. Method and device for treating nitroso compound
CN107427760A (zh) * 2015-04-02 2017-12-01 西门子公司 用于从气体流中分离二氧化碳的设备和方法
US11439950B2 (en) 2018-07-02 2022-09-13 Universiity of Kentucky Research Foundation Electrochemical cell, method and apparatus for capturing carbon dioxide from flue gas and decomposing nitrosamine compounds

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