WO2011012470A1 - Process for removing harmful substances from liquid carbon dioxide and apparatus for performance thereof - Google Patents

Process for removing harmful substances from liquid carbon dioxide and apparatus for performance thereof 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
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Prior art keywords
carbon dioxide
pollutant
liquid carbon
pollutants
mercury
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PCT/EP2010/060335
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German (de)
French (fr)
Inventor
Manfred Baldauf
Carsten Graeber
Marc Hanebuth
Gerhard Zimmermann
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Siemens Aktiengesellschaft
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Priority to EP10734117A priority Critical patent/EP2459293A1/en
Priority to CN201080032593.XA priority patent/CN102470287B/en
Priority to CA2769495A priority patent/CA2769495C/en
Priority to RU2012107387/05A priority patent/RU2551510C2/en
Priority to AU2010277760A priority patent/AU2010277760B2/en
Priority to BR112012001719A priority patent/BR112012001719A2/en
Priority to US13/384,616 priority patent/US20120144860A1/en
Publication of WO2011012470A1 publication Critical patent/WO2011012470A1/en

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    • 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.

Abstract

A process for removing harmful substances from a gas stream which comprises essentially carbon dioxide CO2, and also comprises substances of value, such as at least one of the gases hydrogen H2, carbon monoxide CO, nitrogen N2 or noble gases, and harmful substances such as a substance from the group of mercury, sulphur, mercury compounds or sulphur compounds, wherein a carbon dioxide condensation is performed in order to obtain liquid carbon dioxide, adsorptive removal of the harmful substances from the condensed carbon dioxide is performed to remove the harmful substances from the carbon dioxide, and a process temperature of less than -30°C but greater than -70°C is maintained.

Description

Beschreibung description
Verfahren zur Schadstoffentfernung aus Kohlendioxid und Vorrichtung zur dessen Durchführung Process for pollutant removal from carbon dioxide and apparatus for carrying it out
Die Erfindung betrifft ein Verfahren sowie eine Vorrichtung zur Abtrennung von Schadstoffen aus einem Kohlendioxidstrom. Beispiele für Schadstoffe sind Schwefel- oder Quecksilberverbindungen . The invention relates to a method and a device for separating pollutants from a carbon dioxide stream. Examples of pollutants are sulfur or mercury compounds.
Aufgrund des sogenannten Treibhauseffektes und dem damit verbundenen globalen Temperaturanstieg wird die Emission von treibhausaktiven Gasen in die Atmosphäre zunehmend kritisch beurteilt. Ein beträchtlicher Anteil des Treibhauseffektes wird dem Kohlenstoffdioxid CO2 zugeschrieben, welches bei der Verbrennung fossiler Brennstoffe entsteht. Due to the so-called greenhouse effect and the associated global increase in temperature, the emission of greenhouse gases into the atmosphere is increasingly critically assessed. A significant proportion of the greenhouse effect is attributed to the carbon dioxide produced by the burning of fossil fuels.
Zurzeit besteht ein gesellschaftlicher Konsens darüber, dass eine Abtrennung von Kohlenstoffdioxid aus Kraftwerksabgasen einer Zunahme des Treibhauseffektes entgegenwirken kann. Aus diesem Grund sollen entsprechende Weiterentwicklungen Anlagen mit wenig oder gar keiner Kohlendioxidemission ermöglichen. Neueste Konzepte für kohlendioxidemissionsarme bzw. kohlendi- oxidemissionsfreie Kraftwerke sind damit in der Entwicklung. Sämtliche Konzepte verfolgen das gemeinsame Ziel, das Kohlenstoffdioxid möglichst vollständig und in hoher Reinheit bei niedrigem Energieaufwand abzutrennen. There is currently a social consensus that separating carbon dioxide from power plant emissions can counteract an increase in the greenhouse effect. For this reason, appropriate developments are to allow plants with little or no carbon dioxide emission. The latest concepts for low-carbon or low-carbon dioxide emission-free power plants are thus under development. All concepts have the common goal of separating the carbon dioxide as completely as possible and in high purity with low energy consumption.
Hier steht zunächst die Abtrennung des Kohlenstoffdioxids im Mittelpunkt. Darüber hinaus liegen jedoch weitere unerwünschte Substanzen vor, die je nach Art des Brennstoffes auftreten und entfernt werden müssen. Die Stoffe Schwefel, Quecksilber oder deren Verbindungen sind dabei die mengenmäßig häufigsten . Here, the focus is initially on the separation of the carbon dioxide. In addition, however, there are other undesirable substances that occur depending on the type of fuel and must be removed. The substances sulfur, mercury or their compounds are the quantitatively most frequent.
Neueste Kraftwerkkonzepte weisen Rahmenbedingungen auf, die jeweils nach dem aktuellen Stand der Technik modernste Schadstoffabtrennungen vorweisen. Bisher werden Schadstoffe die in Kraftwerken anfallen, wie Schwefel oder Quecksilberverbindung direkt aus der Gasphase entfernt. So erfolgt beispielsweise die Abtrennung von Schwe- felwasserstoff mit Hilfe von Gaswäschen. Dabei wird der Gasstrom durch einen Absorber geleitet in dem ein flüssiges Medium die Schadstoffe absorbiert. Flüssige Absorbermedien sind beispielsweise wässrige Alkanolaminlösungen, speziell wässri- ges Methyl-Diethanolamin, oder beispielsweise kaltes Metha- nol, eingesetzt beim Rectisol-Prozess . Derartige Verfahren mit flüssigen Absorbermedien sind bekannt und in verschiedenen Technologien etabliert. 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. So far, pollutants are generated in power plants, such as sulfur or mercury compound removed directly from the gas phase. For example, 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.
Nachteile im Stand der Technik bestehen vor allem darin, dass Verfahren zur Gaswäsche einen erhöhten Energiebedarf mit sich bringen, da sie mit Verfahrensschritten wie Kompression und/oder Kühlung verbunden sein können. Disadvantages in the prior art are, in particular, that gas scrubbing processes entail an increased energy requirement, since they can be associated with process steps such as compression and / or cooling.
Die Regeneration von Absorbermedien geschieht destillativ wo- mit ein wesentlicher Energieaufwand verknüpft ist. The regeneration of absorber media is done by distillation, which means that a considerable amount of energy is needed.
Weiterhin ist der Aufbau für derartige Verfahren relativ kompliziert was im Bezug auf Verfahrensdurchführung und Investitionskosten nachteilige Auswirkungen aufweist. Furthermore, the structure of such methods is relatively complicated, which has adverse effects in terms of process performance and investment costs.
Aufgabe der Erfindung ist eine energiesparende Möglichkeit zur Schadstoffentfernung in Kraftwerken mit im Wesentlichen fossiler Befeuerung zu beschreiben. Weiterhin soll eine leicht zu bedienende Vorrichtung zur Durchführung des Verfah- rens angegeben werden. 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.
Die Erfindung beruht darauf, dass bei einem Gasgemisch, welches zum Großteil aus Kohlendioxid CO2 besteht und Anteile von Wertgasen und Schadstoffen aufweist, gerade bei einer Kondensation des Kohlendioxids, die Schadstoffe sich vorzugsweise im flüssigen Kohlendioxid anreichern. Diese Erkenntnis wird dahingehend ausgenutzt, dass die Abtrennung der Schadstoffe aus der flüssigen Phase des Kohlendioxids bei tiefen Temperaturen durch den Einsatz von Adsorbermaterialien/ Ad- sorbentien, vorzugsweise festen Adsorbermaterialien, erfolgt. Dabei ist es besonders vorteilhaft, dass die Energiebilanz der Schadstoffabtrennung bei niedrigen Temperaturen positiv ausfällt, d.h. es wird insgesamt weniger Energieaufwand notwendig. 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.
Die Abtrennung der Schadstoffe aus der flüssigen Phase kann bei niedrigen Temperaturen sehr vorteilhaft durch Adsorberma- terialien geschehen, da die hier eingesetzten Materialien große Oberflächen aufweisen, die zur Absorption der Schadstoffe zur Verfügung stehen. 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.
Falls das Verfahren zur Abtrennung von Schadstoffen aus einem im Wesentlichen aus Kohlendioxid bestehenden Gasstrom mit einem Verfahren kombiniert wird in welchem Kohlendioxid bereits flüssig vorliegt, so lassen sich in der Gesamtenergiebilanz synergistische Effekte erzielen. Es ist besonders vorteilhaft die Verfahrenstemperatur geringer als -30°C anzusetzen und zu halten. Es ist nicht sinnvoll Temperaturen unter -700C anzuwenden, da bei so niedrigen Temperaturen Kohlendioxid in fester Phase vorliegt. Der Verfahrensdruck muss grundsätzlich oberhalb des Tripel- punktes von Kohlendioxid entsprechend dem Temperatur/Druckdiagramm liegen. Damit beträgt er mindestens 5 bar. Ein ebenfalls für die Verfahrenstemperatur anwendbarer Temperaturbereich beginnt bei -5°C und erstreckt sich in Richtung niedrigerer Temperatur. If 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.
Der Einsatz des Verfahrens zur Abtrennung von Schadstoffen aus einem Gasgemisch, das im Wesentlichen aus Kohlendioxid besteht lässt sich besonders vorteilhaft in sogenannten koh- lendioxidfreien Kraftwerken realisieren. Bei diesen Kraftwerken kann die Abtrennung des Kohlendioxids kryogen durchgeführt werden. Hierbei wird das Kohlendioxid auf eine niedrige Temperatur gebracht, verflüssigt und abgetrennt. Die flüssige Phase eignet sich sehr gut für die adsorptive Abtrennung von Schadstoffen, da diese sich vorzugsweise im flüssigen Kohlendioxid anreichern. Weiterhin begünstigen niedrige Temperaturen eine Adsorption, so dass beispielsweise eine bisher vor- gesehene Gaswäsche entfällt. Der Einsatz von Festbett-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. In these power plants, the separation of the carbon dioxide can be carried out cryogenically. Here, 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. Furthermore, low temperatures favor adsorption, so that, for example, a previously provided gas scrubbing is eliminated. The use of fixed bed
Adsorbern für die Adsorption von Schadstoffen ist vorteilhaft, da hier Feststoffe mit großer Oberfläche eingesetzt werden. Dies sind insbesondere Tonerde (Aliminiumoxid), Aktivkohle, Kieselgel, Zeolithe oder Polymere mit großer Ober- fläche. 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.
Da die Oberfläche der Adsorbentien im Laufe des Verfahrens mit Schadstoffen belegt wird, wird vorteilhaft eine wiederkehrende Regeneration einzelner Festbett-Adsorber vorgesehen. Since the surface of the adsorbents is coated with pollutants in the course of the process, it is advantageous to provide a recurrent regeneration of individual fixed-bed adsorbers.
Im Folgenden wird anhand von schematischen begleitenden Figuren Ausführungsbeispiele beschrieben: Exemplary embodiments will be described below with reference to schematic accompanying figures:
Die Figuren zeigen im Einzelnen: The figures show in detail:
Figur 1 stellt schematisch einen Festbett-Adsorber vor durch den flüssiges Kohlendioxid welches mit Schadstoffen beladen ist hindurchgeleitet wird, wobei die Schadstoffe im Festbett-Adsorber adsorbiert werden. 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.
Figur 2 stellt parallel geschaltete Adsorber vor, die durch entsprechende Ventile einzeln oder in Gruppen zwischen den Betriebzuständen Adsorption und Regeneration umschaltbar sind. 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.
Die Adsorption von Schadstoffen läuft in Festbett-Adsorbern ab, wie sie in Figuren 1 und 2 dargestellt sind. Die Adsorbentien müssen nach einer bestimmten Standzeit regeneriert werden. Dies geschieht durch eine Druckerniedrigung, eine Temperaturerhöhung oder indem ein Gas oder Dampf durchgeleitet wird, oder mit einer Kombination daraus. Aus diesem Grund existieren mehrere Adsorber, die abwechselnd im Betrieb sind oder regeneriert werden können. Eine Anordnung für drei Fest- bett-Adsorber ist in Figur 2 dargestellt. Analoge Konfigurationen für zwei oder mehr als drei Adsorber sind möglich. 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.
Bei der Kohlendioxidkondensation tritt automatisch eine we- sentliche Anreicherung von in einem Gasgemisch enthaltenen Schadstoffen im flüssigen Kohlendioxid ein. Dies konnte anhand von Simulationsrechnungen am Beispiel von Schwefelwasserstoff H2S, sowie Carbonylsulfid COS, gezeigt werden. Danach kann die Abtrennung der Schadstoffe aus flüssiger Phase bei niedrigen Temperaturen mittels Adsorbermaterialien erfolgen . During carbon dioxide condensation, there is an automatic accumulation of pollutants contained in a gas mixture in the liquid carbon dioxide. This was demonstrated by simulation calculations using the example of hydrogen sulfide H 2 S, as well as carbonyl sulfide COS. Thereafter, the separation of the pollutants from the liquid phase can be carried out at low temperatures by means of adsorber materials.
Vorteilhaft ist die im Gesamtkonzept energiesparende Abtrennung der Schadstoffe bei niedrigeren Temperaturen. Mit einem Kraftwerkskonzept das die kryogene Kohlendioxidabtrennung bereits vorsieht, lässt sich ein Verfahren entsprechend der Erfindung ausgezeichnet kombinieren. Advantageous in the overall concept energy-saving separation of pollutants at lower temperatures. With a power plant concept that already provides for cryogenic carbon dioxide removal, a process according to the invention can be excellently combined.
Der Temperaturbereich zum Betrieb des Verfahrens kann zwi- sehen -5°C und -700C liegen. Die untere Temperaturgrenze liegt im Bereich der Erstarrung von Kohlendioxid aus flüssiger Phase, so dass Feststoffe das Verfahren blockieren können. Allgemein muss dafür gesorgt werden, dass die Festbett- Adsorber für den flüssigen Reaktionsstrom offengehalten wer- den. Die Energiebilanz des gesamten Verfahrens zeigt jedoch, dass Temperaturen von -300C und tiefer vorteilhaft für die Schadstoffabtrennung sind. 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.
Die im Verfahren unter Umständen im gasförmigen oder flüssi- gen Strom vorhandenen Wertgase wie Wasserstoff, Kohlenmono- xid, Stickstoff oder Edelgase werden bei der beschriebenen Verfahrensweise nicht adsorbiert. Schadstoffe wie Quecksilber, Schwefel oder deren Verbindungen, die sich im Wesentlichen in dem flüssigen Kohlendioxidstrom befinden, werden durch die Adsorbentien in den Festbett-Adsorbern oberflächlich angelagert, also adsorbiert, und somit in den Festbett- Adsorbern zurückgehalten. Ein weiterer Schadstoff der auf diese Weiser abgetrennt werden kann, ist Carbonylsulfid COS. Die Figur 1 zeigt einen Festbett-Adsorber 1, in den ein flüssiger Kohlendioxidstrom 2 mit Schadstoffen beladen eingeleitet wird. Am Austritt des Festbett-Adsorbers 1 erscheint ein flüssiger Kohlendioxidstrom 3 ohne Schadstoffe. The value gases such as hydrogen, carbon monoxide, nitrogen or noble gases present in the process under certain circumstances in the gaseous or liquid stream are not adsorbed in the procedure described. Pollutants such as mercury, sulfur or their compounds, which are essentially in the liquid carbon dioxide stream, are superficially deposited by the adsorbents in the fixed bed adsorbers, so adsorbed, and thus retained in the fixed bed adsorbers. Another pollutant that can be separated in this way is carbonyl sulfide COS. 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.
Die Figur 2 zeigt drei Festbett-Adsorber 1 in Parallelschaltung. Der flüssige Kohlendioxidstrom 2 wird an der Oberseite zugeführt, Schadstoffe werden in den Festbett-Adsorbern 1 zu- rückgehalten und an der Unterseite ist der flüssige Kohlendioxidstrom 3 ohne Schadstoffe entnehmbar. Zur Regeneration 4 können einzelne Festbett-Adsorber 1 jeweils umgeschaltet werden . Eine direkte katalytische Umsetzung kann aufgrund der niedrigen Temperaturen mit einer günstigen Gleichgewichtslage verbunden sein, weist jedoch eine sehr ungünstige Kinetik auf. Es wären sehr große Mengen an Katalysatoren notwendig, die durch vorhandenen Schwefel wahrscheinlich sehr schnell deak- tiviert werden würden. 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.

Claims

Patentansprüche claims
1. Verfahren zur Abtrennung von mindestens einem Schadstoff aus einem Gasgemisch, welches im Wesentlichen Kohlendioxid CO2, sowie mindestens einen Wertstoff aufweist, wobei eineAnspruch [en] A process for separating at least one pollutant from a gas mixture which comprises essentially carbon dioxide, CO2 and at least one valuable substance, one of which
Kohlendioxidkondensation durchgeführt wird, um flüssiges Kohlendioxid zu erzeugen und abzutrennen, dadurch gekennzeichnet, dass Carbon dioxide condensation is carried out to produce and separate liquid carbon dioxide, characterized in that
- eine adsorptive Abtrennung des mindestens einen Schadstoffs aus dem flüssigen Kohlendioxid zur Entfernung des mindestens einen Schadstoffs aus dem flüssigen Kohlendioxid durchgeführt wird, und  - An adsorptive separation of the at least one pollutant from the liquid carbon dioxide to remove the at least one pollutant from the liquid carbon dioxide is performed, and
- eine Verfahrenstemperatur im Bereich von -300C bis -700C eingestellt wird. - A process temperature in the range of -30 0 C to -70 0 C is set.
2. Verfahren nach Anspruch 1, 2. The method according to claim 1,
dadurch gekennzeichnet, dass der im Gasgemisch enthaltene mindestens eine Wertstoff, ausgewählt ist aus der Gruppe der Stoffe, wie Wasserstoff H2, Kohlenmonoxid CO, Stickstoff N2 oder Edelgas. characterized in that the at least one valuable substance contained in the gas mixture is selected from the group of substances such as hydrogen, carbon monoxide CO, nitrogen N 2 or noble gas.
3. Verfahren nach Anspruch 1 oder 2, 3. The method according to claim 1 or 2,
dadurch gekennzeichnet, dass der im Gasgemisch enthaltene mindestens eine Schadstoff, ausgewählt wird aus der Gruppe der Stoffe, wie Schwefel, Quecksilber, Schwefel- und/oder Quecksilberverbindungen . characterized in that the at least one pollutant contained in the gas mixture is selected from the group of substances such as sulfur, mercury, sulfur and / or mercury compounds.
4. Verfahren nach Anspruch 1,2 oder 3, 4. The method according to claim 1,2 or 3,
dadurch gekennzeichnet, dass als Adsorbens für die adsorptive Abtrennung des mindestens einen Schadstoffs zumindest eincharacterized in that at least one adsorbent for the adsorptive separation of the at least one pollutant
Stoff ausgewählt wird aus der Gruppe der Stoffe Aktivkohle, Zeolith, Kieselgel, Tonerde oder mindestens ein Polymer mit großer Oberfläche. Substance is selected from the group of activated carbon, zeolite, silica, alumina or at least one polymer with a large surface area.
5. Verwendung des Verfahrens nach einem der Ansprüche 1 - 4, dadurch gekennzeichnet, dass die Abtrennung von mindestens einem Schadstoff aus kryogenem Kohlendioxid in kohlendioxidarmen oder -freien Kraftwerken geschieht. 5. Use of the method according to any one of claims 1 - 4, characterized in that the separation of at least one pollutant from cryogenic carbon dioxide is done in low-carbon or -free power plants.
6. Vorrichtung zur Abtrennung von mindestens einem Schadstoff, insbesondere Quecksilber, Schwefel oder jeweils deren Verbindungen, aus einem Gasgemisch, welches im Wesentlichen Kohlendioxid aufweist, sowie mindestens einen Wertstoff, insbesondere Wasserstoff, Kohlenmonoxid, Stickstoff oder ein Edelgas, wobei zur Erzeugung von flüssigem Kohlendioxid eine Kohlendioxidkondensationseinheit vorhanden ist, dadurch gekennzeichnet, dass 6. An apparatus for separating at least one pollutant, in particular mercury, sulfur or their compounds, from a gas mixture which comprises essentially carbon dioxide, and at least one valuable material, in particular hydrogen, carbon monoxide, nitrogen or a noble gas, wherein for the production of liquid carbon dioxide a carbon dioxide condensation unit is present, characterized in that
- zur adsorptiven Abtrennung des mindestens einen Schadstoffs aus flüssigen Kohlendioxid zur Entfernung der Schadstoffe daraus mindestens ein Festbett-Adsorber (1) vorhanden ist, und - For the adsorptive separation of the at least one pollutant from liquid carbon dioxide to remove the pollutants thereof from at least one fixed-bed adsorber (1) is present, and
- die Betriebstemperatur der Vorrichtung im Bereich von - 70 0C bis -30 0C liegt. - The operating temperature of the device in the range of - 70 0 C to -30 0 C.
7. Vorrichtung nach Anspruch 6, 7. Apparatus according to claim 6,
dadurch gekennzeichnet, dass der mindestens eine Festbett- Adsorber (1) zur adsorptiven Abtrennung zumindest ein Adsor- bens aus der Gruppe Aktivkohle, Zeolith, Tonerde oder mindestens ein Polymer mit großer Oberfläche aufweist. characterized in that the at least one fixed bed adsorber (1) for adsorptive separation at least one adsorbent from the group consisting of activated carbon, zeolite, alumina or at least one polymer having a high surface area.
8. Vorrichtung nach einem der Ansprüche 6 oder 7, 8. Device according to one of claims 6 or 7,
dadurch gekennzeichnet, dass der mindestens eine Festbett- Adsorber (1) mehrfach vorhanden ist und in Gruppen parallel verschaltbar ist, so dass Adsorber oder Gruppen von Adsorbern zur Regenerierung der Adsorbentien umschaltbar sind. characterized in that the at least one fixed-bed adsorber (1) is present several times and can be connected in parallel in groups, so that adsorbers or groups of adsorbers for regeneration of the adsorbents can be switched over.
PCT/EP2010/060335 2009-07-30 2010-07-16 Process for removing harmful substances from liquid carbon dioxide and apparatus for performance thereof WO2011012470A1 (en)

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CN201080032593.XA CN102470287B (en) 2009-07-30 2010-07-16 The method of harmful substance and the device for implementing the method is removed from liquid carbon dioxide
CA2769495A CA2769495C (en) 2009-07-30 2010-07-16 Process for removing harmful substances from carbon dioxide and apparatus for the performance thereof
RU2012107387/05A RU2551510C2 (en) 2009-07-30 2010-07-16 Method of removing harmful substances from carbon dioxide and device for its realisation
AU2010277760A AU2010277760B2 (en) 2009-07-30 2010-07-16 Process for removing harmful substances from liquid carbon dioxide and apparatus for performance thereof
BR112012001719A BR112012001719A2 (en) 2009-07-30 2010-07-16 process to remove harmful carbon dioxide substances and apparatus for carbon dioxide performance
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