WO2014166781A1 - Procédé et dispositif de séparation de dioxyde de carbone d'un effluent gazeux contenant du dioxyde de carbone - Google Patents

Procédé et dispositif de séparation de dioxyde de carbone d'un effluent gazeux contenant du dioxyde de carbone Download PDF

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Publication number
WO2014166781A1
WO2014166781A1 PCT/EP2014/056553 EP2014056553W WO2014166781A1 WO 2014166781 A1 WO2014166781 A1 WO 2014166781A1 EP 2014056553 W EP2014056553 W EP 2014056553W WO 2014166781 A1 WO2014166781 A1 WO 2014166781A1
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WO
WIPO (PCT)
Prior art keywords
solvent
carbon dioxide
amino acid
absorption
gas
Prior art date
Application number
PCT/EP2014/056553
Other languages
German (de)
English (en)
Inventor
Tobias Jockenhoevel
Ralph Joh
Rüdiger Schneider
Henning Schramm
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 WO2014166781A1 publication Critical patent/WO2014166781A1/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
    • B01D53/1406—Multiple stage absorption
    • 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
    • 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
    • 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 method for separating carbon dioxide from a carbon dioxide-containing exhaust gas
  • the invention also relates to a separation device for separating carbon dioxide from a carbon dioxide-containing exhaust gas for a fossil-fired power plant.
  • carbon dioxide can be separated from the exhaust gas in a separation device.
  • various methods are generally known. On an industrial scale, the separation of carbon dioxide has been established in an absorption desorption process with a detergent.
  • the gas containing carbon dioxide is contacted in egg ⁇ ner absorption column with a selective solvent as a detergent. Carbon dioxide is bound by a chemical or physical process in the detergent.
  • the purified exhaust gas is discharged from the absorption column for further processing or discharge.
  • the loaded with carbon dioxide solvent is passed to remove the carbon dioxide and regeneration of Lö ⁇ sungsmittels in a desorption.
  • the Abtren ⁇ voltage in the desorption column can take place thermally.
  • a gas-vapor mixture of gaseous carbon dioxide and vaporized solvent is expelled from the loaded solvent.
  • the evaporated solvent is then separated from the gaseous carbon dioxide.
  • the carbon dioxide can now be compressed and cooled in several stages. In liquid or frozen state, the carbon dioxide can then be stored or recycled.
  • the regenerated solvent is re-gelei ⁇ tet to the absorber column, where it can absorb carbon dioxide from the exhaust gas containing carbon dioxide again.
  • amino acid-containing solvent can be increased.
  • amino acid ⁇ so that the amino acid salt is crystallized in solid form. Due to the crystallization of
  • Amino acid salt from the solvent is the concentration of already absorbed carbon dioxide in the solvent redu ⁇ benefits, which increases the driving force for the further absorption of carbon dioxide. This allows more carbon dioxide to be bound by the same amount of solvent.
  • An object of the invention is to propose a method for separating carbon dioxide from a carbon dioxide-containing exhaust gas, which enables a high separation efficiency with low own energy requirement.
  • Another object of the invention is to provide a
  • the object directed to a method is achieved according to the invention with a method for separating carbon dioxide from a carbon dioxide-containing exhaust gas, wherein in an absorption process in a pre-cleaning step, carbon dioxide-containing exhaust gas is brought into contact with a partially loaded amino acid-containing solvent, wherein a part of the
  • Auskristalli ⁇ Siert amino acid salt or its reaction products so that a partially purified exhaust gas and a suspension of loaded solvent, and amino acid salt, or their reaction products are formed and in which in an end ⁇ cleaning step, the partially purified exhaust gas with a
  • amino acid-containing solvent is brought into contact, wherein carbon dioxide is taken up by the solvent, and wherein the amino acid remains in solution, so that a gerei ⁇ required exhaust gas and a partially laden amino Textre restrooms Lö ⁇ sungsstoff is formed.
  • the invention is based on the idea of using known methods from the chemical industry for the solution of the problem. From the abundance of different proven and mature processes, it is important to select those that do not compensate for or even overcompensate for their positive properties in their interaction with each other and in connection with the power plant process. Essence of the invention is, the procedures in such a way to kombinie ⁇ ren together such that the positive effects of the process can be largely offset each other. The combination of both methods creates new common advantages that minimize the disadvantages of the individual processes. Surprisingly, one arrives just in the combination of these methods to the discovery that the intrinsic energy consumption of the separator can be significantly reduced, and also the overall efficiency of the power plant process with Koh ⁇ dioxide separation systems can be significantly increased at ⁇ . This drastically reduces the cost of the carbon dioxide capture process.
  • the preliminary cleaning step first a part of a ⁇ be already partially loaded amino acid-containing solvent in amino acid salt, or their reaction products is transferred, wherein a pre-purified carbon dioxide-containing flue gas and a
  • the invention makes use of the fact that thereby carbon dioxide from the flue gas beyond the limits of chemical equilibrium out in the
  • the pre-purified exhaust gas is brought into contact with a solvent which is largely free of carbon dioxide, so that a largely purified flue gas and a partially loaded solvent are formed.
  • the absorption process is controlled so that crystallization or precipitation of amino acid salt or its reaction products is avoided in the final purification step.
  • the combination according to the invention surprisingly compensates for the disadvantages of the two individual methods.
  • the separation efficiency is increased.
  • the combination of the two methods according to the present invention also increases the overall efficiency when integrated into a power plant process to the same extent.
  • no additional energy is required. Due to the high loading of the solvent with carbon dioxide is saved in the subsequent regeneration of the solu ⁇ means by desorption considerably in energy in the form of heating steam. It is also necessary to achieve the higher loading of the Lö ⁇ sungsstoffs less solvent is the same surface regeneration performance. Since less solvent in the solvent cycle of the deposition process must be ge ⁇ promotes energy thereby saved.
  • the partially loaded amino acid-containing solvent is sprayed in the pre-cleaning step.
  • the suspension is passed largely residue-free through the process.
  • Injection is achieved for a short time a maximum interaction ⁇ surface between the carbon dioxide-containing flue gas and the solvent. This promotes the rapid crystallization of amino acid salt or its reaction products.
  • ⁇ surface is either waived internals, or it come internals are used, which ensure the residue-free passage.
  • a possible ⁇ lichste large interaction surface between carbon dioxide and the amino acid-containing solvent so ⁇ that a good mass transfer is achieved in the final purification step is provided.
  • the large interaction surface will it aims ⁇ through corresponding fixtures.
  • ordered or unordered packing columns are available in which the large interaction surface is achieved by a broadly wettable surface. Soil columns are also conceivable.
  • the suspension is heated in a heat exchanger process so that the amino acid salt or its reaction products go into solution, forming a liquid loaded solvent.
  • the liquid-laden solvent is fed to a phase separation process, wherein a gas-vapor mixture of gaseous carbon dioxide and vaporous solvent and a liquid, charged solvent are separated.
  • the phase separation process is preferably carried out at a pressure P, the pressure P being set to a different pressure than the pressure in a desorption process connected downstream of the phase separation process.
  • the gas-vapor mixture is preferably fed to a condensation process in which water condenses.
  • the carbon dioxide separation process is part of a power plant process of a fossil-fired Steam power plant or a combined gas and steam turbine power plant.
  • the object directed to a device is achieved by a separation device for separating carbon dioxide from a carbon dioxide-containing exhaust gas, with an absorption unit for receiving carbon dioxide from the exhaust gas, wherein the absorption unit has at least a first absorption region and a second absorption region connected to the first absorption region In the first absorption region, internals are arranged for enlarging the phase boundary surfaces for the passage of a fluid, and no internals are provided in the second absorption area, or internals are arranged for the passage of a suspension.
  • the invention is based on the idea of using in particular interconnections known from the chemical industry for the solution of the problem. From the abundance of different tried and tested interconnections, it is important to select those that do not compensate for or even overcompensate for their positive properties, even when interacting with each other and integrated into a power plant. It is the essence of the invention to combine the interconnections in such a way that the positive effects of the interconnections can largely be offset against one another. The combination of both interconnections creates new common advantages that minimize the disadvantages of individuals.
  • the second absorption region is connected downstream of the first absorption region.
  • the first absorbent portion has internals through which a fluid istleitbares receives the highest possible interactions ⁇ kung surface. Such internals may be ordered or disordered packages. Also by floors as built-in th is an enlargement of the interaction surface he ⁇ reichbar.
  • the second absorption area on the other hand, either has no internals or internals specially designed for the passage of a suspension. Built these specific inputs are characterized in that they ensure a residue ⁇ loose passage of a suspension, such as floors.
  • the inventive combination of absorption area for a long residence time and an absorption area for a short residence time and the disadvantages of the two individual interconnections are surprisingly compensated.
  • the separation efficiency is increased. It is particularly surprising that also increases the overall efficiency of integration into a power plant to the same extent by the inventions ⁇ tion proper combination of the two interconnections. Due to the high loading of the solvent with carbon dioxide, the subsequent regeneration of the solvent by desorption considerably saves energy in the form of heating steam. In addition, due to the high loading of the solvent less solvent required to achieve the same regeneration performance. Since less solvent in the solvent cycle of the deposition must be ge ⁇ promoted, this additional energy is saved.
  • a heat exchanger is connected between the first absorption region and the second absorption region, so that a cooled solvent can be supplied to the second absorption region during operation of the separation device.
  • the absorption of carbon dioxide into the solvent is favored. It is expedient that the solvent from the first absorption area in the second absorption area can be transferred, since no high-purity solvent is required for the pre-cleaning in the second absorption area.
  • a injection device is arranged in the second absorption region, through which a fluid can be injected during operation of the separation device.
  • the injector is connected to the heat exchanger or to the first absorption area.
  • the injection device may consist of one or more individual nozzles which are suitable for the passage of a solvent, in particular an amino acid salt solution.
  • the absorption unit is a phase separation device nachge ⁇ switched, wherein the phase separation device has a discharge for gas and a discharge for liquids, and wherein the discharge for liquids with a desorption unit is connected.
  • the phase separator a first separation of carbon dioxide from the Lö ⁇ solvents already taken place. This relieves the downstream desorption unit. It is advantageous if the Phasentrennvorrich ⁇ tion is beheitzbar, or in a heat exchanger between the separator and the phase separator, a heat exchanger is connected to the entry of heat, so that during operation of the separator of the separator, a heated solvent can be fed.
  • Separating device is the desorption after a Kondensa ⁇ gate downstream, and connected the outlet for gas with the Kon ⁇ capacitor.
  • the phase separation device separated carbon dioxide can be conducted directly into the condenser, whereby the desoception unit is relieved.
  • the separation device is part of a steam power plant, which further comprises a fossil-fired steam generator and a steam turbine, or part of a combined cycle power plant further comprising a gas turbine and a gas turbine exhaust side nachge switched ⁇ heat recovery steam generator, which is connected in the water-steam circuit of a steam turbine is included.
  • FIG. 2 shows a schematic diagram of an absorption process with a pre-cleaning and a final cleaning step
  • FIG. 3 shows a schematic diagram of a separation device with an absorption unit and a desorption unit 4 shows a schematic diagram of an alternative execution ⁇ form a separator with an absorption unit and a desorption unit
  • Fig. 1 the actual inventive idea of the inventions ⁇ inventive method is illustrated. Is shown the absorption process 1.
  • the absorption process 1 consists We ⁇ sentlichen from a precleaning step 2 and a Endrei- nists Colour 7.
  • the pre-cleaning step 2 a coal dioxid condominiums exhaust gas 3 and a partially loaded
  • amino acid-containing solvent 4a, 4b fed.
  • Transferred suspension 6 which is passed from the absorption process 1 from ⁇ .
  • Carbon dioxide from the carbon dioxide-containing off ⁇ gas 3 is bound beyond the limits of chemical Gleichge ⁇ weight out in the amino acid-containing solvent.
  • a partially purified exhaust gas 5 is formed.
  • the partially purified exhaust gas 5 is now passed into the final cleaning step 7.
  • Fig. 2 shows an over the Fig. 1 extended embodiment of the invention. Shown is also the ex ⁇ sorption 1, the essential components of the pre- cleaning step 2 and the final cleaning step 7 are.
  • the absorption process 1 will he ⁇ supplemented here continues by ei ⁇ NEN process heat exchanger 11, the step between the Final Cleaning ⁇ 7 and is connected to the pre-cleaning step. 2
  • the heat exchange process 11 is the partially laden amino acid-containing exhaust gas 4a, 4b removed from the final purification step 7 heat and cooled to the pre-cleaning step 2 supplied ⁇ leads.
  • the absorption process in the pre- purification step 2 is advantageously favored, since the loading capacity of solvent by carbon dioxide increases with decreasing temperature.
  • the separation device 20 shown in FIG. 3 has an absorption unit 21 and a desorption unit 33. It serves to separate carbon dioxide from a carbon dioxide-containing exhaust gas 3 by means of the absorption unit 21.
  • the absorption unit 21 has at least one first absorption region 22 and a second absorption region 23 connected to the first absorption region 22.
  • internals 24 are provided for enlarging the phase interfaces for the passage through tion of a fluid arranged.
  • the second absorption region 23 is in this case in comparison free of internals, or as shown herein, has baffles 26, which are suitable respectively for fürlei ⁇ tung a suspension 27 is formed.
  • a heat exchanger 28 is connected between the first absorption region 22 and the second absorption region 23, so that when operating the separation device 20, the two ⁇ th absorption region 23 is a cooled solvent
  • a injection device 29 is further arranged, through which a fluid 25 can be injected during operation of the separation device 20.
  • phase separation device 30 Downstream of the absorption unit 21 is a phase separation device 30, wherein the phase separation device 30 has a discharge for gas 31 and a discharge for liquids 32.
  • the discharge for liquids 32 is connected to a desorption unit 33.
  • a heat exchanger 34 is further connected, so that during operation of the
  • the desorption unit 33 is followed by a capacitor 35, wherein in particular the discharge for gas 31 is connected to the capacitor 35.
  • Fig. 4 shows a further embodiment of the invention shown SEN separator 20 which substantially tion unit an absorption desorption unit 21 and has a 33rd
  • the embodiment shown in FIG. 4 differs from the embodiment shown in FIG. 3 in that the phase separation device 30 connected downstream of the absorption unit 21 has a discharge for gas 31, which is connected to the desorption unit 33 in the upper head area and not the Capacitor 35 is supplied. 10

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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 procédé de séparation de dioxyde de carbone d'un effluent gazeux (3) contenant du dioxyde de carbone, selon lequel dans un processus d'absorption (1), a) dans une étape de lavage préalable (2), l'effluent gazeux contenant du dioxyde de carbone est mis en contact avec un solvant (4a) contenant de l'acide aminé et partiellement chargé, une partie du sel d'acide aminé ou de ses produits de réaction étant cristallisée, de manière à obtenir un effluent gazeux (5) en partie lavé et une suspension (6) composée de solvant chargé et de sel d'acide aminé ou de ses produits de réaction, b) dans une étape de lavage final (2), l'effluent gazeux en partie lavé est mis en contact avec un solvant (8) contenant de l'acide aminé, le dioxyde de carbone étant absorbé par le solvant et l'acide aminé restant en solution, de manière à former un effluent gazeux (10) lavé et un solvant (4b) contenant de l'acide aminé et partiellement chargé.
PCT/EP2014/056553 2013-04-11 2014-04-02 Procédé et dispositif de séparation de dioxyde de carbone d'un effluent gazeux contenant du dioxyde de carbone WO2014166781A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013206370 2013-04-11
DE102013206370.9 2013-04-11

Publications (1)

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WO2014166781A1 true WO2014166781A1 (fr) 2014-10-16

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060117954A1 (en) * 2002-05-08 2006-06-08 Nederlandse Organisatie Voortoegepastnatenschappel Ijk Onderzoek Tno Method for absorption of acid gases
US20090263302A1 (en) * 2006-04-07 2009-10-22 Liang Hu Self-Concentrating Absorbent for Acid Gas Separation
EP2311545A1 (fr) * 2009-10-15 2011-04-20 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Procédé d'absorption de gaz d'acide
EP2409755A1 (fr) * 2010-07-22 2012-01-25 Siemens Aktiengesellschaft Procédé et dispositif de traitement d'un solvant alkalin d'un sel d'un acide aminé contaminé
EP2514507A1 (fr) * 2011-04-20 2012-10-24 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Procédé pour supprimer un gaz acide d'un courant de gaz avec une solution d'acide aminé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060117954A1 (en) * 2002-05-08 2006-06-08 Nederlandse Organisatie Voortoegepastnatenschappel Ijk Onderzoek Tno Method for absorption of acid gases
US20090263302A1 (en) * 2006-04-07 2009-10-22 Liang Hu Self-Concentrating Absorbent for Acid Gas Separation
EP2311545A1 (fr) * 2009-10-15 2011-04-20 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Procédé d'absorption de gaz d'acide
EP2409755A1 (fr) * 2010-07-22 2012-01-25 Siemens Aktiengesellschaft Procédé et dispositif de traitement d'un solvant alkalin d'un sel d'un acide aminé contaminé
EP2514507A1 (fr) * 2011-04-20 2012-10-24 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Procédé pour supprimer un gaz acide d'un courant de gaz avec une solution d'acide aminé

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