WO2011012470A1 - Procédé d'élimination de polluants à partir de dioxyde de carbone liquide et dispositif pour sa mise en œuvre - Google Patents

Procédé d'élimination de polluants à partir de dioxyde de carbone liquide et dispositif pour sa mise en œuvre Download PDF

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Publication number
WO2011012470A1
WO2011012470A1 PCT/EP2010/060335 EP2010060335W WO2011012470A1 WO 2011012470 A1 WO2011012470 A1 WO 2011012470A1 EP 2010060335 W EP2010060335 W EP 2010060335W WO 2011012470 A1 WO2011012470 A1 WO 2011012470A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon dioxide
pollutant
liquid carbon
pollutants
mercury
Prior art date
Application number
PCT/EP2010/060335
Other languages
German (de)
English (en)
Inventor
Manfred Baldauf
Carsten Graeber
Marc Hanebuth
Gerhard Zimmermann
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
Priority to CA2769495A priority Critical patent/CA2769495C/fr
Priority to BR112012001719A priority patent/BR112012001719A2/pt
Priority to US13/384,616 priority patent/US20120144860A1/en
Priority to AU2010277760A priority patent/AU2010277760B2/en
Priority to CN201080032593.XA priority patent/CN102470287B/zh
Priority to RU2012107387/05A priority patent/RU2551510C2/ru
Priority to EP10734117A priority patent/EP2459293A1/fr
Publication of WO2011012470A1 publication Critical patent/WO2011012470A1/fr

Links

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
    • B01D53/002—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 condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/416—Further details for adsorption processes and devices involving cryogenic temperature treatment
    • 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 and a device for separating pollutants from a carbon dioxide stream.
  • pollutants are sulfur or mercury compounds.
  • State-of-the-art power plant concepts present framework conditions that show state-of-the-art emissions separation in accordance with state-of-the-art technology.
  • pollutants are generated in power plants, such as sulfur or mercury compound removed directly from the gas phase.
  • the separation of hydrogen sulfide takes place by means of gas scrubbing.
  • the gas stream is passed through an absorber in which a liquid medium absorbs the pollutants.
  • Liquid absorber media are, for example, aqueous alkanolamine solutions, especially aqueous methyldiethanolamine, or, for example, cold methanol used in the rectisol process.
  • Such methods with liquid absorber media are known and established in various technologies.
  • the object of the invention is to describe an energy-saving possibility for pollutant removal in power plants with essentially fossil firing. Furthermore, an easy-to-use device for carrying out the method should be specified.
  • the invention is based on the fact that in a gas mixture which consists largely of carbon dioxide CO2 and contains portions of valuable gases and pollutants, especially in a condensation of carbon dioxide, the pollutants preferably accumulate in the liquid carbon dioxide. This finding is exploited to the effect that the separation of the pollutants from the liquid phase of the carbon dioxide at low Temperatures through the use of adsorber materials / adsorbents, preferably solid adsorber materials occurs. It is particularly advantageous that the energy balance of pollutant removal at low temperatures is positive, that is, it takes less energy overall.
  • the separation of the pollutants from the liquid phase can be done very advantageously at low temperatures by Adsorberma- materials, since the materials used here have large surfaces that are available for the absorption of pollutants available.
  • the process for the separation of pollutants from a gas stream consisting essentially of carbon dioxide is combined with a process in which carbon dioxide is already present in liquid form, synergistic effects can be achieved in the overall energy balance. It is particularly advantageous to set and maintain the process temperature less than -30 ° C. It does not make sense to apply temperatures below -70 0 C, because at such low temperatures carbon dioxide is in a solid phase.
  • the process pressure must always be above the triple point of carbon dioxide according to the temperature / pressure diagram. He is at least 5 bar.
  • a temperature range also applicable for the process temperature starts at -5 ° C and extends in the direction of lower temperature.
  • the use of the method for separating pollutants from a gas mixture which consists essentially of carbon dioxide can be realized particularly advantageously in so-called coal-dioxide-free power plants.
  • the separation of the carbon dioxide can be carried out cryogenically.
  • the carbon dioxide is brought to a low temperature, liquefied and separated.
  • the liquid Phase is very well suited for the adsorptive removal of pollutants, as these preferentially accumulate in the liquid carbon dioxide.
  • low temperatures favor adsorption, so that, for example, a previously provided gas scrubbing is eliminated.
  • Adsorbers for the adsorption of pollutants is advantageous because it uses solids with a high surface area. These are in particular alumina (alumina), activated carbon, silica gel, zeolites or polymers with a large surface area.
  • FIG. 1 schematically illustrates a fixed-bed adsorber through which liquid carbon dioxide laden with pollutants is passed, the pollutants being adsorbed in the fixed-bed adsorber.
  • FIG. 2 shows adsorbers connected in parallel, which can be switched by appropriate valves individually or in groups between the operating states of adsorption and regeneration.
  • the adsorption of pollutants takes place in fixed bed adsorbers, as shown in Figures 1 and 2.
  • the adsorbents must be regenerated after a certain lifetime. This is done by a pressure reduction, a temperature increase or by passing a gas or vapor, or a combination thereof. For this reason, there are several adsorbers that are alternately in operation or can be regenerated.
  • An arrangement for three festivals bed adsorber is shown in FIG. Analog configurations for two or more than three adsorbers are possible.
  • the temperature range for operating the process can be- seen -5 ° C and -70 0 C.
  • the lower temperature limit is in the range of solidification of carbon dioxide from the liquid phase, so that solids can block the process. In general, it must be ensured that the fixed-bed adsorbers are kept open for the liquid reaction stream. However, the energy balance of the whole process shows that temperatures from -30 0 C and lower advantageous for the separation of pollutants are.
  • FIG. 1 shows a fixed-bed adsorber 1 into which a liquid carbon dioxide stream 2 is charged laden with pollutants. At the outlet of the fixed-bed adsorber 1, a liquid carbon dioxide stream 3 appears without pollutants.
  • FIG. 2 shows three fixed-bed adsorbers 1 in parallel connection.
  • the liquid carbon dioxide stream 2 is supplied at the top, pollutants are retained in the fixed-bed adsorbers 1 and on the underside of the liquid carbon dioxide stream 3 without pollutants can be removed.
  • For regeneration 4 individual fixed-bed adsorber 1 can be switched in each case.
  • a direct catalytic reaction may be due to the low temperatures associated with a favorable equilibrium position, but has a very unfavorable kinetics. It would require very large amounts of catalysts which would probably be deactivated very quickly by the presence of sulfur.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

L'invention porte sur un procédé de séparation de polluant à partir d'un courant gazeux, qui comprend essentiellement du dioxyde de carbone CO2, ainsi que de substances valorisables telles qu'au moins l'un des gaz hydrogène H2, monoxyde de carbone CO, azote N2 ou des gaz rares, et des polluants tels qu'une substance parmi le groupe comprenant le mercure, le soufre, des composés du mercure ou du soufre. Dans ce procédé on réalise une condensation du dioxyde de carbone pour produire du dioxyde de carbone liquide, on réalise une séparation par adsorption des polluants à partir du dioxyde de carbone condensé pour éliminer les polluants du dioxyde de carbone et on respecte une température de procédé inférieure à -30°C mais supérieure à -70°C.
PCT/EP2010/060335 2009-07-30 2010-07-16 Procédé d'élimination de polluants à partir de dioxyde de carbone liquide et dispositif pour sa mise en œuvre WO2011012470A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA2769495A CA2769495C (fr) 2009-07-30 2010-07-16 Procede d'elimination de polluants a partir de dioxyde de carbone liquide et dispositif pour sa mise en oeuvre
BR112012001719A BR112012001719A2 (pt) 2009-07-30 2010-07-16 processo para remover substâncias nocivas de dióxido de carbono e aparelho para o desempenho do mesmo
US13/384,616 US20120144860A1 (en) 2009-07-30 2010-07-16 Process for removing harmful substances from liquid carbon dioxide and apparatus for the performance thereof
AU2010277760A AU2010277760B2 (en) 2009-07-30 2010-07-16 Process for removing harmful substances from liquid carbon dioxide and apparatus for performance thereof
CN201080032593.XA CN102470287B (zh) 2009-07-30 2010-07-16 从液态二氧化碳中去除有害物质的方法及用于实施该方法的装置
RU2012107387/05A RU2551510C2 (ru) 2009-07-30 2010-07-16 Способ удаления вредных веществ из диоксида углерода и устройство для его осуществления
EP10734117A EP2459293A1 (fr) 2009-07-30 2010-07-16 Procédé d'élimination de polluants à partir de dioxyde de carbone liquide et dispositif pour sa mise en uvre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009035389A DE102009035389A1 (de) 2009-07-30 2009-07-30 Verfahren zur Schadstoffentfernung aus Kohlendioxid und Vorrichtung zur dessen Durchführung
DE102009035389.5 2009-07-30

Publications (1)

Publication Number Publication Date
WO2011012470A1 true WO2011012470A1 (fr) 2011-02-03

Family

ID=42628433

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/060335 WO2011012470A1 (fr) 2009-07-30 2010-07-16 Procédé d'élimination de polluants à partir de dioxyde de carbone liquide et dispositif pour sa mise en œuvre

Country Status (10)

Country Link
US (1) US20120144860A1 (fr)
EP (1) EP2459293A1 (fr)
KR (1) KR20120055576A (fr)
CN (1) CN102470287B (fr)
AU (1) AU2010277760B2 (fr)
BR (1) BR112012001719A2 (fr)
CA (1) CA2769495C (fr)
DE (1) DE102009035389A1 (fr)
RU (1) RU2551510C2 (fr)
WO (1) WO2011012470A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011092106A1 (fr) * 2010-01-28 2011-08-04 Siemens Aktiengesellschaft Procédé pour séparer un gaz utile purifié d'un mélange gazeux et dispositif permettant de mettre en oeuvre ce procédé

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US9458022B2 (en) 2014-03-28 2016-10-04 L'Air Liquide Société Anonyme Pour L'Étude Et L'Exploitation Des Procedes Georges Claude Process and apparatus for separating NO2 from a CO2 and NO2—containing fluid
US11135542B2 (en) * 2016-10-28 2021-10-05 Uop Llc Processes and apparatuses for removing contaminants from hydrogen streams

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US20030161780A1 (en) * 2001-10-17 2003-08-28 Praxair Technology, Inc. Recycle for supercritical carbon dioxide
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011092106A1 (fr) * 2010-01-28 2011-08-04 Siemens Aktiengesellschaft Procédé pour séparer un gaz utile purifié d'un mélange gazeux et dispositif permettant de mettre en oeuvre ce procédé

Also Published As

Publication number Publication date
KR20120055576A (ko) 2012-05-31
BR112012001719A2 (pt) 2016-04-12
CA2769495A1 (fr) 2011-02-03
CN102470287B (zh) 2015-09-30
CN102470287A (zh) 2012-05-23
AU2010277760B2 (en) 2015-02-19
RU2012107387A (ru) 2013-09-10
AU2010277760A1 (en) 2012-02-02
RU2551510C2 (ru) 2015-05-27
US20120144860A1 (en) 2012-06-14
DE102009035389A1 (de) 2011-02-03
EP2459293A1 (fr) 2012-06-06
CA2769495C (fr) 2018-05-22

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