WO2006034765A1 - Method for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol - Google Patents

Method for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol Download PDF

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Publication number
WO2006034765A1
WO2006034765A1 PCT/EP2005/009350 EP2005009350W WO2006034765A1 WO 2006034765 A1 WO2006034765 A1 WO 2006034765A1 EP 2005009350 W EP2005009350 W EP 2005009350W WO 2006034765 A1 WO2006034765 A1 WO 2006034765A1
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carbon dioxide
adsorption
water
rich gas
carbon monoxide
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PCT/EP2005/009350
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German (de)
French (fr)
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Christian Benkmann
Hans-Jürgen GERHARDS
Matthias Grahl
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Linde Aktiengesellschaft
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Priority to EP05781736A priority Critical patent/EP1848522A1/en
Publication of WO2006034765A1 publication Critical patent/WO2006034765A1/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
    • B01D53/02—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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
    • B01D53/0462—Temperature swing adsorption
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01D—SEPARATION
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    • B01D2256/20—Carbon monoxide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/702—Hydrocarbons
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    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • 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
    • B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4145—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged in series
    • 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
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • 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
    • 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
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a method for adsorptive separation of carbon dioxide and water from a carbon dioxide and water-containing carbon monoxide and hydrogen-rich gas mixture.
  • Such gas mixtures are also referred to as synthesis gas mixtures and as a rule further processed or treated in low-temperature decomposition.
  • the invention relates to a method for adsorptive separation of carbon dioxide and methanol from a carbon dioxide and methanol-containing carbon monoxide and hydrogen-rich gas mixture.
  • Object of the present invention is to provide generic method for adsorptive separation of carbon dioxide and water or carbon dioxide and methanol, which avoid the aforementioned disadvantages.
  • a method for the adsorptive separation of carbon dioxide and water is proposed, which is characterized in that the carbon monoxide and hydrogen-rich gas mixture in a first, containing a silica gel adsorption of water and in a second, a molecular sieve-containing adsorption of Carbon dioxide is purified and the
  • the inventive method for adsorptive separation of carbon dioxide and methanol is characterized in that the carbon monoxide and hydrogen-rich gas mixture is purified in a first, containing a silica gel adsorption of methanol and in a second molecular sieve containing an adsorption of carbon dioxide and the regeneration the two adsorption layers by means of a carbon monoxide-rich gas (mixture) it takes place, wherein the temperature of 70 to 150 0 C, preferably 90 to 110 0 C.
  • the desired carbon dioxide purities can be achieved by means of the procedures according to the invention.
  • the formation of the undesirable formic acid is considerably reduced, so that little or no damage to the molecular sieve used takes place; This has the consequence that the life of the molecular sieve used significantly extended.
  • the inventive method allows energy savings, since the gas stream used for the regeneration now only at 70 to 150 or 90 to 110 0 C must be heated while it was heated in the known procedures to at least 150 0 C.
  • the quantitative ratio between silica gel and molecular sieve will in practice be based on the operating temperature, the water content and the carbon dioxide content to be removed.
  • the molecular sieve used in the second adsorption step is preferably a 4 A, 5 A or 13 X type, with the latter type having been found to be most suitable.
  • the silica gel used in the first adsorption layer is - according to a further advantageous embodiment of the method according to the invention - a small-pored silica gel.
  • the silica gel used in the first adsorption layer may be preceded by a splash-proof silica gel or a splash-proof activated clay as spray-water protection.
  • the two adsorption layers or the adsorption materials used therefor are preferably arranged within an adsorber or adsorption container. It is also conceivable to realize both adsorption layers in two or more Adsorbem or Adsorptions alternem.

Abstract

The invention relates to a method for the adsorptive separation of carbon dioxide and water from a carbon monoxide and hydrogen-rich gas mixture that contains carbon dioxide and water. According to the invention, the carbon monoxide and hydrogen-rich gas mixture is purified from water in a first, silica gel-containing adsorption layer and from carbon dioxide in a second adsorption layer which contains a molecular sieve. The two adsorption layers are regenerated by means of a carbon monoxide-rich gas (mixture) whose temperature ranges from 70 to 150 °C. The invention also relates to an analogous method for the adsorptive separation of carbon dioxide and methanol.

Description

Beschreibung description
Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Wasser oderMethod for the adsorptive separation of carbon dioxide and water or
Kohlendioxid und MethanolCarbon dioxide and methanol
Die Erfindung betrifft ein Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Wasser aus einem Kohlendioxid und Wasser enthaltenden Kohlenmonoxid- und Wasserstoff-reichen Gasgemisch.The invention relates to a method for adsorptive separation of carbon dioxide and water from a carbon dioxide and water-containing carbon monoxide and hydrogen-rich gas mixture.
Derartige Gasgemische werden auch als Synthesegasgemische bezeichnet und im Regelfall in Tieftemperaturzerlegungen weiterverarbeitet bzw. -behandelt.Such gas mixtures are also referred to as synthesis gas mixtures and as a rule further processed or treated in low-temperature decomposition.
Des Weiteren betrifft die Erfindung ein Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Methanol aus einem Kohlendioxid und Methanol enthaltenden Kohlenmonoxid- und Wasserstoff-reichen Gasgemisch.Furthermore, the invention relates to a method for adsorptive separation of carbon dioxide and methanol from a carbon dioxide and methanol-containing carbon monoxide and hydrogen-rich gas mixture.
Gattungsgemäße Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Wasser bzw. Kohlendioxid und Methanol werden bisher mittels Molekularsieben realisiert. Die Regenerierung des beladenen Molekularsiebes erfolgt anschließend mittels eines unter Druck stehenden Kohlenmonoxid-reichen Gasgemisches, wobei dieses eine Temperatur von ca. 150 bis 250 °C aufweist. Der Kohlenmonoxid-Partialdruck des Gasgemisches beträgt hierbei ca. 0.5 bis 20 bar.Generic processes for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol have hitherto been realized by means of molecular sieves. The regeneration of the loaded molecular sieve is then carried out by means of a pressurized carbon monoxide-rich gas mixture, this having a temperature of about 150 to 250 ° C. The carbon monoxide partial pressure of the gas mixture in this case is about 0.5 to 20 bar.
Es hat sich gezeigt, dass bei dieser Art der Regenerierung die gewünschten Kohlendioxid-Reinheiten in dem aus der adsorptiven Abtrennung abgezogenen Gasgemisch nach einer gewissen Betriebszeit nicht mehr erreicht werden. Die Lebensdauer des verwendeten Molekularsiebes wird drastisch verkürzt, da es bei den vorgenannten Bedingungen zu einer Bildung von Ameisensäure, die die verwendeten Molekularsiebe schädigt, kommt. Dies führt dazu, dass häufiger als eigentlich erforderlich, ein Austausch der verwendeten Molekularsiebe erforderlich wird.It has been found that in this type of regeneration, the desired carbon dioxide purities in the gas mixture withdrawn from the adsorptive separation after a certain period of operation are no longer achieved. The life of the molecular sieve used is drastically shortened, since it comes under the aforementioned conditions to formic acid which damages the molecular sieves used. As a result, replacement of the molecular sieves used is required more frequently than actually required.
Aufgabe der vorliegenden Erfindung ist es, gattungsgemäße Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Wasser bzw. Kohlendioxid und Methanol anzugeben, die die vorgenannten Nachteile vermeiden. Zur Lösung dieser Aufgabe wird ein Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Wasser vorgeschlagen, das dadurch gekennzeichnet ist, dass das Kohlenmonoxid- und Wasserstoff-reiche Gasgemisch in einer ersten, ein Silikagel enthaltenden Adsorptionsschicht von Wasser und in einer zweiten, ein Molekularsieb enthaltenden Adsorptionsschicht von Kohlendioxid gereinigt wird und dieObject of the present invention is to provide generic method for adsorptive separation of carbon dioxide and water or carbon dioxide and methanol, which avoid the aforementioned disadvantages. To solve this problem, a method for the adsorptive separation of carbon dioxide and water is proposed, which is characterized in that the carbon monoxide and hydrogen-rich gas mixture in a first, containing a silica gel adsorption of water and in a second, a molecular sieve-containing adsorption of Carbon dioxide is purified and the
Regenerierung der beiden Adsorptionsschichten mittels eines Kohlenmonoxid-reichen Gas(gemisch)es erfolgt, wobei dessen Temperatur 70 bis 150 0C, vorzugsweise 90 bis 110 0C beträgt.Regeneration of the two adsorption layers by means of a carbon monoxide-rich gas (mixture) it takes place, wherein the temperature of 70 to 150 0 C, preferably 90 to 110 0 C.
Das erfindungsgemäße Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Methanol zeichnet sich dadurch aus, dass das Kohlenmonoxid- und Wasserstoff-reiche Gasgemisch in einer ersten, ein Silikagel enthaltenden Adsorptionsschicht von Methanol und in einer zweiten, ein Molekularsieb enthaltenden Adsorptionsschicht von Kohlendioxid gereinigt wird und die Regenerierung der beiden Adsorptionsschichten mittels eines Kohlenmonoxid-reichen Gas(gemisch)es erfolgt, wobei dessen Temperatur 70 bis 150 0C, vorzugsweise 90 bis 110 0C beträgt.The inventive method for adsorptive separation of carbon dioxide and methanol is characterized in that the carbon monoxide and hydrogen-rich gas mixture is purified in a first, containing a silica gel adsorption of methanol and in a second molecular sieve containing an adsorption of carbon dioxide and the regeneration the two adsorption layers by means of a carbon monoxide-rich gas (mixture) it takes place, wherein the temperature of 70 to 150 0 C, preferably 90 to 110 0 C.
Es hat sich gezeigt, dass mittels der erfindungsgemäßen Verfahrensweisen die gewünschten Kohlendioxid-Reinheiten erreicht werden können. Darüber hinaus wird die Bildung der unerwünschten Ameisensäure erheblich reduziert, so dass keine oder eine nur geringe Schädigung des verwendeten Molekularsiebes erfolgt; dies hat zur Folge, dass sich die Lebensdauer des verwendeten Molekularsiebes deutlich verlängert. Des Weiteren ermöglichen die erfindungsgemäßen Verfahren eine Energieeinsparung, da der für die Regenerierung verwendete Gasstrom nunmehr lediglich auf 70 bis 150 bzw. 90 bis 110 0C erhitzt werden muss, während er bei den bekannten Verfahrensweisen auf wenigstens 150 0C erhitzt wurde.It has been found that the desired carbon dioxide purities can be achieved by means of the procedures according to the invention. In addition, the formation of the undesirable formic acid is considerably reduced, so that little or no damage to the molecular sieve used takes place; This has the consequence that the life of the molecular sieve used significantly extended. Furthermore, the inventive method allows energy savings, since the gas stream used for the regeneration now only at 70 to 150 or 90 to 110 0 C must be heated while it was heated in the known procedures to at least 150 0 C.
Das Mengenverhältnis zwischen Silikagel und Molekularsieb wird sich in der Praxis an der Betriebstemperatur, dem Wassergehalt sowie dem zu entfernenden Kohlendioxid- Gehalt orientieren.The quantitative ratio between silica gel and molecular sieve will in practice be based on the operating temperature, the water content and the carbon dioxide content to be removed.
Das in der zweiten Adsorptionsstufe verwendete Molekularsieb ist vorzugsweise ein 4 A-, 5 A- oder 13 X-Typ, wobei sich der letztgenannte Typ als am geeignetsten erwiesen hat. Das in der ersten Adsorptionsschicht verwendete Silikagel ist - gemäß einer weiteren vorteilhaften Ausgestaltung der erfindungsgemäßen Verfahren - ein engporiges Silikagel.The molecular sieve used in the second adsorption step is preferably a 4 A, 5 A or 13 X type, with the latter type having been found to be most suitable. The silica gel used in the first adsorption layer is - according to a further advantageous embodiment of the method according to the invention - a small-pored silica gel.
Des Weiteren kann es von Vorteil sein, wenn dem in der ersten Adsorptionsschicht verwendeten Silikagel als Spritzwasserschutz ein spritzwasserfestes Silikagel oder eine spritzwasserfeste aktivierte Tonerde vorgeschaltet ist.Furthermore, it may be advantageous for the silica gel used in the first adsorption layer to be preceded by a splash-proof silica gel or a splash-proof activated clay as spray-water protection.
Die beiden Adsorptionsschichten bzw. die dafür verwendeten Adsorptionsmaterialien werden vorzugsweise innerhalb eines Adsorbers bzw. Adsorptionsbehälters angeordnet. Es ist auch denkbar, beide Adsorptionsschichten in zwei oder mehreren Adsorbem bzw. Adsorptionsbehältem zu realisieren. The two adsorption layers or the adsorption materials used therefor are preferably arranged within an adsorber or adsorption container. It is also conceivable to realize both adsorption layers in two or more Adsorbem or Adsorptionsbehältem.

Claims

Patentansprüche claims
1. Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Wasser aus einem Kohlendioxid und Wasser enthaltenden Kohlenmonoxid- und Wasserstoff-reichen Gasgemisch, dadurch gekennzeichnet, dass das Kohlenmonoxid- und Wasserstoff-reiche Gasgemisch in einer ersten, ein Silikagel enthaltenden1. A method for adsorptive separation of carbon dioxide and water from a carbon dioxide and water-containing carbon monoxide and hydrogen-rich gas mixture, characterized in that the carbon monoxide and hydrogen-rich gas mixture in a first, a silica gel-containing
Adsorptionsschicht von Wasser und in einer zweiten, ein Molekularsieb enthaltenden Adsorptionsschicht von Kohlendioxid gereinigt wird und die Regenerierung der beiden Adsorptionsschichten mittels eines Kohlenmonoxid- reichen Gas(gemisch)es erfolgt, wobei dessen Temperatur 70 bis 150° C beträgt.Adsorption of water and in a second, a molecular sieve-containing adsorption of carbon dioxide is purified and the regeneration of the two adsorption by means of a carbon monoxide rich gas (mixture) it takes place, wherein the temperature is 70 to 150 ° C.
2. Verfahren zur adsorptiven Abtrennung von Kohlendioxid und Methanol aus einem Kohlendioxid und Methanol enthaltenden Kohlenmonoxid- und Wasserstoff¬ reichen Gasgemisch, dadurch gekennzeichnet, dass das Kohlenmonoxid- und Wasserstoff-reiche Gasgemisch in einer ersten, ein Silikagel enthaltenden2. A method for the adsorptive separation of carbon dioxide and methanol from a carbon dioxide and methanol-containing carbon monoxide and hydrogen rich gas mixture, characterized in that the carbon monoxide and hydrogen-rich gas mixture in a first, containing a silica gel
Adsorptionsschicht von Methanol und in einer zweiten, ein Molekularsieb enthaltenden Adsorptionsschicht von Kohlendioxid gereinigt wird und die Regenerierung der beiden Adsorptionsschichten mittels eines Kohlenmonoxid- reichen Gas(gemisch)es erfolgt, wobei dessen Temperatur 70 bis 150 0C beträgt.Adsorption of methanol and in a second, a molecular sieve-containing adsorption of carbon dioxide is purified and the regeneration of the two adsorption by means of a carbon monoxide rich gas (mixture) it takes place, wherein the temperature is 70 to 150 0 C.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Regenerierung der Adsorptionsschichten mittels eines Kohlenmonoxid-reichen Gas(gemisch)es erfolgt, wobei dessen Temperatur 90 bis 110 °C beträgt.3. The method according to claim 1 or 2, characterized in that the regeneration of the adsorption by means of a carbon monoxide-rich gas (mixture) it takes place, wherein the temperature is 90 to 110 ° C.
4. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 3, dadurch gekennzeichnet, dass beide Adsorptionsschichten innerhalb eines Adsorbers bzw. Adsorptionsbehälters realisiert werden.4. The method according to any one of the preceding claims 1 to 3, characterized in that both adsorption layers are realized within an adsorber or adsorption vessel.
5. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, dass beide Adsorptionsschichten getrennt in mehreren Adsorbern bzw. Adsorptionsbehältern realisiert werden 5. The method according to any one of the preceding claims 1 to 4, characterized in that both adsorption layers are realized separately in a plurality of adsorbers or adsorption containers
6. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das in der zweiten Adsorptionsschicht verwendete Molekularsieb ein 4 A-, 5 A- oder 13 X-Typ ist.6. The method according to any one of the preceding claims 1 to 5, characterized in that the molecular sieve used in the second adsorption layer is a 4 A, 5 A or 13 X type.
7. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das in der ersten Adsorptionsschicht verwendete Silikagel ein engporiges Silikagel ist.7. The method according to any one of the preceding claims 1 to 6, characterized in that the silica gel used in the first adsorption layer is a small-pored silica gel.
8. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 7, dadurch gekennzeichnet, dass dem in der ersten Adsorptionsschicht verwendeten Silikagel als Spritzwasserschutz ein spritzwasserfestes Silikagel oder eine spritzwasserfeste aktivierte Tonerde vorgeschaltet ist. 8. The method according to any one of the preceding claims 1 to 7, characterized in that the water-silica gel used in the first adsorption layer or a splash-proof activated alumina is connected in front of the silica gel used as spray water protection.
PCT/EP2005/009350 2004-09-24 2005-08-30 Method for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol WO2006034765A1 (en)

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CN101563145B (en) * 2006-12-18 2012-02-29 乔治洛德方法研究和开发液化空气有限公司 Purification of a h2/co mixture with heater-skin temperature control
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FR2909898A1 (en) * 2006-12-18 2008-06-20 Air Liquide Purification or separation of flow of supply gas with impurities e.g. carbon dioxide and mixture of water and methanol, comprises contacting the supply gas with a first and a second adsorbent, and recuperating the purified or separated gas
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FR2911289A1 (en) * 2007-01-17 2008-07-18 Air Liquide Supply gas flow purifying method for e.g. petrochemical plant, involves stopping circulation of regeneration gas by reducing skin temperature of heater until temperature is less than specific degree Celsius and performing purging of heater
CN101594923B (en) * 2007-01-17 2013-01-16 乔治洛德方法研究和开发液化空气有限公司 Purification of a h2/co mixture with lead control of the regeneration heater
FR2952833A1 (en) * 2009-11-20 2011-05-27 Air Liquide Integration of a unit for the production of cast iron, a drying and adsorption unit and a cryogenic separation unit, comprises a first compressor unit, a pipe to pass compressed feed gas to first compressor, and a second compressor unit
EP3604210A1 (en) 2018-08-02 2020-02-05 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Production of carbon dioxide and ammonia from residual gases in the steel and metal industries
EP3603790A1 (en) 2018-08-02 2020-02-05 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Improved productivity of equilibrium-restricted reactions
WO2020025810A1 (en) 2018-08-02 2020-02-06 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Improved productivity of equilibrium-restricted reactions
WO2020025815A1 (en) 2018-08-02 2020-02-06 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Production of carbon dioxide and ammonia from residual gases in the steel and metal industries
US11312635B2 (en) 2018-08-02 2022-04-26 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Productivity of equilibrium-restricted reactions

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