[go: up one dir, main page]

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

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
carbon dioxide
adsorption
water
rich gas
carbon monoxide
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2005/009350
Other languages
German (de)
French (fr)
Inventor
Christian Benkmann
Hans-Jürgen GERHARDS
Matthias Grahl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
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 Linde GmbH filed Critical Linde GmbH
Priority to EP05781736A priority Critical patent/EP1848522A1/en
Publication of WO2006034765A1 publication Critical patent/WO2006034765A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • B01D53/02—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
    • 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
    • B01D53/0462—Temperature swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • 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
    • B01D2256/16—Hydrogen
    • 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
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • 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
    • 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
    • B01D2259/40088—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
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B2203/042—Purification by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)

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 Ceased WO2006034765A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05781736A EP1848522A1 (en) 2004-09-24 2005-08-30 Method for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004046343.3 2004-09-24
DE102004046343A DE102004046343A1 (en) 2004-09-24 2004-09-24 Process for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol

Publications (1)

Publication Number Publication Date
WO2006034765A1 true WO2006034765A1 (en) 2006-04-06

Family

ID=35063107

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/009350 Ceased WO2006034765A1 (en) 2004-09-24 2005-08-30 Method for the adsorptive separation of carbon dioxide and water or carbon dioxide and methanol

Country Status (4)

Country Link
EP (1) EP1848522A1 (en)
DE (1) DE102004046343A1 (en)
TW (1) TW200618853A (en)
WO (1) WO2006034765A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2909898A1 (en) * 2006-12-18 2008-06-20 Air Liquide PURIFICATION OF A H2 / CO MIXTURE WITH CONTROL OF THE HEATER SKIN TEMPERATURE
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
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
EP3603790A1 (en) 2018-08-02 2020-02-05 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Improved productivity of equilibrium-restricted reactions
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4233038A (en) * 1979-08-06 1980-11-11 Air Products And Chemicals, Inc. Reactivation system for water-carbon dioxide adsorbers
US5106396A (en) * 1989-12-28 1992-04-21 Mitariten Michael J Adsorption processes with intermediate product recovery using two adsorption zones
US5897686A (en) * 1997-10-22 1999-04-27 Air Products And Chemicals, Inc. Synthesis gas drying and CO2 removal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4233038A (en) * 1979-08-06 1980-11-11 Air Products And Chemicals, Inc. Reactivation system for water-carbon dioxide adsorbers
US5106396A (en) * 1989-12-28 1992-04-21 Mitariten Michael J Adsorption processes with intermediate product recovery using two adsorption zones
US5897686A (en) * 1997-10-22 1999-04-27 Air Products And Chemicals, Inc. Synthesis gas drying and CO2 removal

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 H2/CO mixtures by heater skin temperature control
US8221526B2 (en) 2006-12-18 2012-07-17 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Purification of an H2/CO mixture with heater skin temperature control
WO2008087312A2 (en) 2006-12-18 2008-07-24 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Purification of a h2/co mixture with heater-skin temperature control
FR2909898A1 (en) * 2006-12-18 2008-06-20 Air Liquide PURIFICATION OF A H2 / CO MIXTURE WITH CONTROL OF THE HEATER SKIN TEMPERATURE
WO2008087312A3 (en) * 2006-12-18 2008-12-11 Air Liquide Purification of a h2/co mixture with heater-skin temperature control
WO2008099108A1 (en) * 2007-01-17 2008-08-21 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Purification of a h2/co mixture with lead control of the regeneration heater
US8167977B2 (en) 2007-01-17 2012-05-01 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Purification of an H2/CO mixture with lead control of the regeneration heater
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 Purging of H2/CO mixtures by pre-control of regenerative heaters
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
EP3603790A1 (en) 2018-08-02 2020-02-05 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Improved productivity of equilibrium-restricted reactions
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
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
WO2020025810A1 (en) 2018-08-02 2020-02-06 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Improved productivity of equilibrium-restricted reactions
US11312635B2 (en) 2018-08-02 2022-04-26 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Productivity of equilibrium-restricted reactions

Also Published As

Publication number Publication date
EP1848522A1 (en) 2007-10-31
TW200618853A (en) 2006-06-16
DE102004046343A1 (en) 2006-03-30

Similar Documents

Publication Publication Date Title
DE69116781T2 (en) Integrated process for the production of carbon oxide
DE3886297T2 (en) Process for the production of high-purity oxygen gas from air.
DE3783478T2 (en) RECOVERY OF ARGON.
DE68922427T2 (en) Process for the recovery of oxygen-rich gas.
DE2443072C2 (en) Process for generating an oxygen-enriched gas
DE69514190T2 (en) Improved pressure swing adsorption process
DE69714890T2 (en) Vacuum pressure swing method
DE69618711T2 (en) Process for integrated air separation
DE3327091C2 (en)
DE69803143T2 (en) Method and device for producing a gaseous product
DE3851822T2 (en) Separation of hydrogen-containing gas mixtures.
EP0146124B1 (en) Pressure swing adsorption process
DE19513599C1 (en) Pressure swing adsorption process with recycle of void space gas
EP0083433B1 (en) Adsorption process for the separation of hydrocarbons
EP3390354B1 (en) Method for the provision of carbon dioxide for the synthesis of urea
WO2017020919A1 (en) Method for obtaining a helium-rich product fraction
DE3132572A1 (en) METHOD FOR THE ADSORPTIVE DISASSEMBLY OF A GAS MIXTURE
DE69406613T2 (en) Process for the recovery of ethylene from exhaust gases from ethylene oxide production
DE68918222T2 (en) Process for the production of carbon monoxide.
DE68912624T2 (en) Membrane process and system for the production of nitrogen.
EP2864242A1 (en) Method for producing co, h2 and methanol synthesis gas from a synthesis gas, in particular from acetylene off gas
EP0442254B1 (en) Process and arrangement for the production of ozonic gases and solutions
EP0595100A1 (en) Process for producing highly pure streams of hydrogen and carbon monoxide
DE102005025651A1 (en) Process and apparatus for recovering products from synthesis gas
DE3887986T2 (en) Pressure swing adsorption process.

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2005781736

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2005781736

Country of ref document: EP