EP2427255A2 - Récupération de dioxyde de carbone - Google Patents

Récupération de dioxyde de carbone

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Publication number
EP2427255A2
EP2427255A2 EP09730698A EP09730698A EP2427255A2 EP 2427255 A2 EP2427255 A2 EP 2427255A2 EP 09730698 A EP09730698 A EP 09730698A EP 09730698 A EP09730698 A EP 09730698A EP 2427255 A2 EP2427255 A2 EP 2427255A2
Authority
EP
European Patent Office
Prior art keywords
stream
adsorption
gas
swing adsorption
moisture
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.)
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Application number
EP09730698A
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German (de)
English (en)
Other versions
EP2427255A4 (fr
Inventor
Ravi Jain
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.)
InnoSepra LLC
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InnoSepra LLC
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Publication date
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Publication of EP2427255A2 publication Critical patent/EP2427255A2/fr
Publication of EP2427255A4 publication Critical patent/EP2427255A4/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • B01D53/047—Pressure swing adsorption
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    • 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
    • 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • 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
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • 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
    • 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
    • B01D2256/22—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
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • 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
    • B01D2257/60—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
    • 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
    • B01D2257/80—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
    • B01D2259/403—Further details for adsorption processes and devices using three beds
    • 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
    • B01D2259/406—Further details for adsorption processes and devices using more than four beds
    • B01D2259/4061—Further details for adsorption processes and devices using more than four beds using five beds
    • 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
    • B01D2259/4146—Contiguous multilayered adsorbents
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • 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
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/0465—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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/86—Carbon dioxide sequestration
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • the method and system disclosed herein relates to capturing carbon dioxide (CO 2 ) from combustion sources such as flue gas of a power plant and making the CO 2 available for sequestration or other uses.
  • CO 2 carbon dioxide
  • Emissions of greenhouse gases such as CO 2 may potentially affect climatic conditions. Conversion of fossil fuels such as coal and natural gas to energy is a source of greenhouse gas emissions. Emissions of the greenhouse gases can be reduced by various means such as increase in efficiency of the combustion process and use of renewable energy such as wind and solar but the reduction in the emission of the greenhouse gases required to stabilize the greenhouse gas levels cannot be achieved without capturing a substantial part of the greenhouse gases at the source of the greenhouse gas emissions during either the pre-combustion process or the post- combustion process.
  • Post-combustion capture of CO 2 from the flue gas of a power plant or other streams such as the flue gas from a refinery involves use of a solvent, typically an amine, which is regenerated using a part of the steam generated during the combustion process.
  • Pre-combustion capture of CO 2 involves chemical reaction of the fuel with air or oxygen and then with steam to produce a mixture of carbon dioxide and hydrogen. The carbon dioxide is removed from this stream through a CO 2 capture process and hydrogen may be used as a fuel for power generation. If oxygen is used for combustion, a flue gas containing mainly carbon dioxide is produced which can be easily separated for sequestration.
  • Net power output from the power plant is also decreased by 30% or more. Means to significantly decrease the power and capital penalty associated with the post-combustion CO 2 capture are sought.
  • the Department Of Energy (DOE) has a goal of less than 35% increase in power cost for 90% CO 2 capture.
  • the heats of adsorption of CO 2 on various zeolite and carbon based adsorbents range between 140-240 kcal/kg or 252-432 Btu/lb (Valenzuela, D. P. and A. L Myers, "Adsorption Equilibrium Data Handbook," Prentice Hall, Englewood Cliffs, NJ, 1989.) which is about a fifth of the heat of absorption for the amine-based systems.
  • Temperature swing adsorption systems have been used extensively for applications such as air drying, natural gas drying, and water and CO 2 removal prior to cryogenic distillation of air. These systems typically remove less than 2% of impurities and the regeneration outlet stream containing the impurities is not of high purity. Also the typical temperature swing adsorption processes have adsorption times of the order of A- 12 hours. For feed CO 2 concentrations between 10-12% in the flue gas, these adsorption times would require extremely large adsorption beds.
  • a plant processing 1000 tons/day of CO 2 in the feed would require about 8,000 m 3 (5.3 million kilograms) of the adsorbent, a size that makes the systems not practical for capturing carbon dioxide from combustion sources.
  • the method and system disclosed herein provides a solution for the efficient capture of CO 2 using a process based on a temperature and pressure swing adsorption cycles.
  • the method and system disclosed herein addresses the above stated need for separating carbon dioxide (CO 2 ) from a gas stream containing water vapor and additional impurities.
  • the method and system disclosed herein captures CO 2 using a process based on a temperature and pressure swing adsorption cycles.
  • the gas is a flue gas from a coal- fired power plant, a natural gas fired power plant, or a refinery.
  • High purity CO 2 i.e., CO 2 containing no more than about 10 percent by volume of impurities, is produced by subjecting a CO 2 gas stream to a temperature swing adsorption step.
  • the temperature swing adsorption step comprises an adsorption step for producing a substantially dry CO 2 -depleted stream, and an adsorbent regeneration step comprising heating the adsorbent bed to produce a substantially water vapor-free CO 2 stream.
  • Temperature in the temperature swing adsorption step during the adsorbent regeneration step is increased to about 8O 0 C to 300 0 C. Duration of the temperature swing adsorption step is in a range of about 2 minutes to 60 minutes.
  • the adsorption is generally carried out in the gaseous phase at temperatures between 1O 0 C and 8O 0 C and at pressures in the range of about 1.07 to 40.0 bar absolute.
  • the CO 2 concentration is in a range of about 3% to 60% by volume.
  • the impurities that are preferably removed from the CO 2 containing gas stream are selected from the group comprising, for example, nitrogen, oxygen, hydrocarbons, nitrogen oxides, sulfur oxides, mercury, and argon.
  • the adsorption is conducted in a bed comprising an adsorbent material, which preferentially adsorbs or reacts with CO 2 in the gas stream.
  • the impurities comprising, for example, moisture, hydrocarbons, nitrogen oxides, sulfur oxides, and mercury are removed prior to CO 2 adsorption.
  • the moisture removal is performed using, for example, pressure swing adsorption, temperature swing adsorption, membrane separation, and absorption. Duration of the pressure swing adsorption process is in a range of about 4 minutes to about 60 minutes and duration of the temperature swing adsorption process is in a range of about 1 hour to 12.0 hours.
  • the moisture content in the moisture removal step is reduced to a dew point of -40 0 C or below.
  • Adsorbents for example, activated carbon, carbon molecular sieves, zeolites such as 4A, 5 A, 13X, NaY and CaX, metallorganic framework compounds, natural zeolites, modified natural and synthetic zeolites, modified activated carbon, pillared clays, etc. are used for CO 2 adsorption.
  • the CO 2 -depleted stream from the CO 2 adsorption section is used for the regeneration of the moisture adsorption system.
  • the feed containing moisture is sent directly to the CO 2 adsorption system wherein CO 2 from the feed is removed by activated carbon or by chemical reaction with sodium and potassium carbonates, amines or ionic liquids supported on a microporous support.
  • the material containing CO 2 is regenerated by direct or indirect heat transfer to produce a high purity CO 2 stream. Further CO 2 removal is performed by bed evacuation after heating.
  • the CO 2 produced is further purified by a membrane process, a distillation process, an adsorption process, or a getter process to remove impurities comprising, for example, nitrogen, oxygen, argon, nitrogen oxides, sulfur oxides, and moisture. Part of the purified CO 2 can be used as a rinse in the CO 2 separation system.
  • the method and system disclosed is effective for the removal of about 80% or higher amounts by volume of impurities from the CO 2 stream.
  • FIG. 1 illustrates an overall schematic of the carbon dioxide (CO 2) separation system for recovering high purity CO 2 from a feed stream containing CO 2 .
  • FIGS. 2A-2D exemplarily illustrate various configurations of the CO 2 separation system wherein moisture is optionally removed in a first separation unit followed by the capture of CO 2 by chemical reaction or adsorption in a second separation unit.
  • FIG. 3 exemplarily illustrates the configuration of a moisture adsorption system wherein the moisture and additional impurities, for example, hydrocarbons, sulfur oxides or nitrogen oxides, and mercury are removed by a combination of pressure and temperature swing adsorption.
  • the moisture and additional impurities for example, hydrocarbons, sulfur oxides or nitrogen oxides, and mercury are removed by a combination of pressure and temperature swing adsorption.
  • FIG. 4 exemplarily illustrates the configuration of the CO 2 separation system wherein CO 2 is removed from the feed stream by adsorption or chemical reaction and is recovered by heating directly or indirectly by steam, hot water or a dry stream recovered from the CO 2 separation system.
  • FIG. 1 illustrates an overall schematic of the carbon dioxide (CO 2) separation system 80 for recovering high purity CO 2 from a feed stream containing CO 2 .
  • the CO 2 is generated in a process 5 which could be a combustion process or another process that generates CO 2 .
  • process 5 is a combustion process
  • an oxygen-enriched stream 10 can be optionally used during the combustion to improve combustion efficiency and to increase the concentration of CO 2 resulting from combustion.
  • steam can be generated as stream 15.
  • a part of stream 15 can be taken as stream 20 and used in the CO 2 separation system 80 described later.
  • the remaining part of stream 15 is taken off as stream 25 and can be used for other purposes, for example, for power generation or for the production of synthesis gas in unit 30.
  • Stream 35 the low pressure stream or hot water in unit 30, can be used in the CO 2 separation system 80 or can be sent to unit 5 for generating steam.
  • a portion of electrical power generated in unit 30 can be sent to the CO 2 separation system 80 via line 45.
  • the remaining electrical power can be supplied to the end users such as the industrial and the residential customers through line 50.
  • the CO 2 containing stream such as the flue gas leaves process 5 as stream 55.
  • the stream 55 can be optionally sent to a feed conditioning unit 60 to remove impurities such as the oxides of nitrogen and sulfur, and mercury.
  • the pressure of stream 55 containing residual sulfur and nitrogen oxides, mercury, nitrogen, oxygen and argon as the main impurities can be raised, if needed, by a fan or a blower 65 after unit 60.
  • the CO 2 containing stream is from a chemical plant or a refinery or from a pre-combustion process, the CO 2 containing stream may contain additional impurities, for example, hydrogen, hydrocarbons, and carbon monoxide.
  • the pressure of the flue gas will typically be raised to about between 1.07 bara to 1.34 bara.
  • the pressure of the stream may be higher than 1.07-1.34 bara and may not have to be raised.
  • the pressure of the stream containing CO 2 may be several atmospheres and would not have to be raised.
  • the flue gas may be recycled to the combustion system to increase the concentration of CO 2 .
  • the CO 2 -containing stream is typically cooled to between near ambient temperature and 6O 0 C prior to CO 2 capture.
  • the flue gas cooling unit is not shown in FIG. 1. Many power plants have systems for the removal of particulates, nitrogen oxides, and sulfur oxides.
  • the systems may include selective catalytic reduction (SCR) for nitrogen oxides, electrostatic precipitators for the particulates, and wet scrubbers for sulfur oxides. Removal of particulates, nitrogen oxides, and sulfur oxides may not be necessary if stream 55 comes from a process such as partial oxidation or reforming.
  • SCR selective catalytic reduction
  • electrostatic precipitators for the particulates
  • wet scrubbers for sulfur oxides. Removal of particulates, nitrogen oxides, and sulfur oxides may not be necessary if stream 55 comes from a process such as partial oxidation or reforming.
  • the stream containing CO 2 leaves unit 65 as stream 70 and enters the CO 2 separation system 80.
  • the CO 2 separation system 80 contains at least one bed with a material that removes CO 2 from the feed stream by adsorption or chemical reaction.
  • the pressure of the bed ranges from about 1.07 bar absolute to about 40 bar absolute.
  • the CO 2 separation system 80 may contain additional units for the removal of other components in the feed stream such as moisture, residual sulfur oxides, nitrogen oxides, and mercury.
  • the moisture in the feed stream 70 may not have to be removed and the CO 2 -depleted stream 85 exiting the CO 2 separation system 80 would contain most of the moisture contained in stream 70. In this case, stream 85 can be vented. However, if a material such as a zeolite is used for CO 2 capture by adsorption, the moisture from the feed stream 70 would have to be removed prior to CO 2 adsorption and the CO 2 -depleted stream 85 would be relatively dry. In this case, a part or all of stream 85, stream 95, can be used for regenerating the moisture adsorption system 79.
  • the CO 2 captured in the CO 2 separation system 80 is recovered by desorbing the CO 2 .
  • the energy for CO 2 desorption can be provided by stream 20, stream 35 or electricity represented by stream 45.
  • Other external sources of heat and electricity can also be used for regenerating the material in the CO 2 separation system 80.
  • the adsorbent or reactant can be contacted directly by steam or condensate if the material is able to handle it.
  • the material in the CO 2 separation system 80 can also be regenerated by dry CO 2 depleted stream 85 which is heated with steam, hot water or electricity. If the adsorbent material is not water tolerant, the adsorbent bed would have to be heated indirectly by steam or hot water.
  • the regeneration of the moisture adsorption material and the CO 2 adsorption material in the CO 2 separation system 80 would be done in parallel to ensure that the CO 2 leaving the CO 2 separation system 80 is dry.
  • a vacuum pump may be used to remove CO 2 from the CO 2 separation system 80.
  • the stream used for regeneration is depicted as stream 90 in FIG. 1. More than 80% of the impurities are typically removed in the CO 2 separation section.
  • the desorbed CO 2 exits the CO 2 separation system 80 via line 105 and is sent to a CO 2 purification system 125.
  • An optional vacuum pump 110 may be used to facilitate the recovery of CO 2 from the CO 2 separation system 80.
  • Part of the CO 2 product enters the vacuum pump 110 as stream 100 and joins stream 105 after exiting the vacuum pump 110.
  • the stream 105 and the stream exiting the vacuum pump 110 are combined to form the CO 2 product stream which enters the CO 2 purification system 125 as stream 120.
  • the purity of the CO 2 product stream 120 produced during regeneration is dependent on the feed CO 2 concentration but would typically be higher than 90%.
  • This stream 120 can be optionally compressed to pressures between 1.1 bara and 200 bara prior to purification.
  • the CO 2 purification system 125 can be, for example, a distillation system, a membrane system, a pressure or temperature swing adsorption system or a getter system to remove small amounts of impurities such as nitrogen, oxygen, nitrogen oxides and sulfur oxides from CO 2 . Also, if the CO 2 stream exiting the CO 2 separation system 80 is wet, the moisture is also removed. Purified CO 2 leaves as stream 130 from the CO 2 purification system 125. Stream 135, which is a small part of stream 120, stream 115, or stream 130, may be used to purge the inerts in the CO 2 separation system 80. This stream 135 enters the CO 2 separation system 80 as stream 145.
  • the purified CO 2 product exits the CO 2 purification system 125 as stream 140 and is available for food or beverage applications, industrial applications, enhanced oil or gas recovery, and sequestration.
  • the CO 2 product stream 140 may have to be compressed, liquefied or both prior to some of these applications.
  • FIGS. 2A-2D exemplarily illustrate various configurations of the CO 2 separation system 80 wherein moisture is optionally removed in a first separation unit followed by the capture of CO 2 by chemical reaction or adsorption in a second separation unit.
  • a wet CO 2 stream 70 is passed through a bed of material that adsorbs or reacts with CO 2 in the presence of moisture.
  • the adsorption or chemical reaction system contains at least two beds at least one of which is removing CO 2 from the feed stream while at least one of which is undergoing regeneration at any given time. As disclosed later in relation to FIG. 4, additional beds may be used for other steps such as cooling, pressurization, rinse, and evacuation.
  • the rinse step can be performed using a relatively pure CO 2 stream 145.
  • the CO 2 product stream exits the CO 2 separation system 80 as stream 105 and as an additional optional stream 100.
  • wet CO 2 stream 70 is passed through a membrane dryer 71 where the moisture from the feed stream is removed.
  • the dry feed stream 72 is sent to the adsorption or reaction bed 81 wherein the CO 2 from the feed is removed and a dry CO 2 - depleted stream 85 exits the CO 2 separation system 80. While CO 2 is being adsorbed at least one other bed 81 is undergoing regeneration using stream 90. As in the case of FIG. 2A, additional beds may be used for other steps such as cooling, pressurization, rinse, and evacuation. Part or all of stream 85 is taken as stream 95 and is used to purge the permeated moisture in the membrane dryer 71. The moisture laden stream exits the membrane dryer 71 as stream 73. An optional vacuum pump 74 may be used to increase the driving force across the membrane and to facilitate the moisture removal, and the moisture-laden stream exits the vacuum pump 74 as stream 75.
  • wet CO 2 stream 70 is passed through an absorption system 76 wherein the moisture from the feed stream is removed by an absorbent such as ethylene glycol.
  • the beds used for moisture removal would normally contain dumped or structured packing for mass transfer between the feed and the absorbent phases and streams would typically flow in the countercurrent direction.
  • the dry feed stream 72 exiting the absorption system 76 is sent to CO 2 adsorption beds 81 wherein the CO 2 from feed is removed and a dry CO 2 -depleted stream 85 exits the CO 2 separation system 80. While CO 2 is being adsorbed at least one other bed 81 is undergoing regeneration using stream 90. Additional beds may be used for other steps such as cooling, pressurization, rinse and evacuation.
  • stream 85 Part or all of CO 2 -depleted stream, stream 85, is taken as stream 95, heated in a heat exchanger or heater 96, and passed through the absorption system 76 as stream 97 to regenerate the moisture loaded solvent stream 77.
  • the solvent loaded with moisture can also be regenerated by countercurrent heat exchange in a heat exchanger (not shown) with steam.
  • the regenerated solvent stream 78 is sent to the absorption system 76 for moisture removal.
  • the stream 95 can be heated by heat exchange with steam or condensate, or the stream 95 may be heated directly using the electrical energy.
  • the moisture loaded stream exits the absorption system 76 as stream 75. In FIG.
  • 2D wet CO 2 stream 70 is passed through a moisture adsorption system 79 where the moisture from the feed stream is removed by an adsorbent such as activated alumina, silica gel or a molecular sieve.
  • the dry feed stream 72 exiting the moisture adsorption system 79 is sent to the CO 2 adsorption beds 81 where the CO 2 from feed is removed and a dry CO 2 -depleted stream 85 exits the CO 2 separation system 80.
  • CO 2 While CO 2 is being removed in one or more CO 2 adsorption beds 81, at least one other CO 2 adsorption bed 81 is undergoing regeneration using stream 90. Additional beds may be used for other steps such as cooling, pressurization, rinse, and evacuation.
  • stream 95 Part or all of stream 85 is taken as stream 95, optionally heated in a heat exchanger or heater 96, and is used to regenerate the moisture adsorption beds in the moisture adsorption system 79. If stream 95 is heated prior to regeneration of the moisture adsorption beds, the stream 95 can be heated by heat exchange with steam or hot water. The stream 95 can also be heated directly using electrical energy.
  • the moisture loaded stream exits the moisture adsorption system 79 as stream 73.
  • An optional vacuum pump 74 can be used to provide additional driving force for the moisture removal and the water loaded stream then exits the vacuum pump 74 as stream 75.
  • the moisture adsorption system 79 would typically contain multiple moisture adsorption beds for the removal of moisture as well as other impurities such as the heavy hydrocarbons that can hinder the adsorption of CO 2 in the CO 2 adsorption beds 81.
  • Moisture adsorption beds in the moisture adsorption system 79 can also be designed to remove some of the sulfur oxides, nitrogen oxides and mercury impurities in the feed.
  • the moisture adsorption beds in the moisture adsorption system 79 would normally be operated in a pressure swing, temperature swing, or a vacuum swing mode.
  • pressure or vacuum swing adsorption the heat of water adsorption would be retained during adsorption and stream 95 at reduced pressure would desorb the moisture. While it is possible to remove moisture by pressure swing adsorption alone, it may be necessary to use the temperature swing adsorption for desorption of other impurities such as the heavy hydrocarbons, sulfur oxides, nitrogen oxides and mercury.
  • FIG. 3 exemplarily illustrates the configuration of the moisture adsorption system 79 wherein the moisture and additional impurities, for example, hydrocarbons, sulfur oxides or nitrogen oxides, and mercury are removed by a combination of pressure and temperature swing adsorption.
  • a three-bed pressure and temperature swing adsorption system for the removal of moisture and other impurities is illustrated in FIG. 3; however, the moisture and trace-impurities removal process is not limited to a three-bed system.
  • PSA pressure swing adsorption
  • VSA vacuum swing adsorption
  • TSA temperature swing adsorption
  • VSA operation and more than one bed can be used for the TSA operation.
  • the number of moisture adsorption beds in the moisture adsorption system 79 is not critical to the operation of this process.
  • the wet feed enters the moisture adsorption system 79 as stream 70 through valves 200, 210 and 220, respectively.
  • These valves 200, 210 and 220 control flow of feed gas into vessels 230, 235 and 240 respectively.
  • Vessels 230, 235 and 240 each have first adsorbent layers 230a, 235a and 240a respectively which comprise adsorbents such as activated alumina, silica gel or a molecular sieve such as 3 A, 4A, 5 A and 13X zeolites for moisture removal.
  • adsorbent(s) selective for hydrocarbons, nitrogen and sulfur oxides, and mercury are optional layers 230b, 235b and 240b, respectively, which comprise adsorbent(s) selective for hydrocarbons, nitrogen and sulfur oxides, and mercury.
  • Adsorbents such as activated carbon, zeolites such as 13X, and impregnated aluminas can be used for adsorbing these impurities. Modified activated carbons and silicates can be used for the removal of mercury impurities.
  • the adsorbents in vessels 230, 235 and 240 are chosen to minimize the adsorption of CO 2 so as to maximize the recovery of CO 2 in the CO 2 adsorption beds 81.
  • the preferred adsorbents for moisture removal are 3A and 4A zeolites, activated alumina, silica gel, and mixtures of activated alumina and zeolites 3A and 4A.
  • the outlet ends of vessels 230, 235, and 240 are connected to discharge lines with valves 245, 260, and 275, respectively.
  • dry CO 2 -containing stream exits the moisture adsorption system 79 through one of these valves 245 as stream 72 and is sent to the CO 2 separation system 80.
  • the purge stream 95 from the CO 2 separation system 80 is used to regenerate the moisture adsorption beds.
  • the purge gas 95 enters through valve 290 and then one of the valves 250, 265, and 280 and exits the moisture adsorption system 79 via corresponding valves 205, 215, and 225 as stream 73.
  • the purge gas 95 exits the moisture adsorption system 79 as stream 75.
  • the purge gas 95 is heated in the heater or heat exchanger 96 and enters the vessels 230, 235 and 240 through one of the open valves 255, 270, and 285 and exits the moisture adsorption system 79 via corresponding valves 205, 215, and 225. If a vacuum pump 74 is not used the purge gas 95 exits the moisture adsorption system 79 as stream 73. If a vacuum pump 74 is used the purge gas 95 exits the moisture adsorption system 79 as stream 75. In normal operation, regeneration of one of the vessels by PSA or VSA and another vessel by TSA is contemplated.
  • the various layers are preferably contained in single vessels, as shown in the drawing, although each layer may be contained in separate vessels, if desired.
  • the duration of each complete cycle of the PSA stage is, at most, several minutes (mins) typically 4-60 minutes, while the duration of the thermal regeneration is generally about 1-12 hours; accordingly, during any single phase of the process, the two vessels in the PSA or VSA mode will undergo many PSA or VSA cycles while the third vessel undergoes a single thermal regeneration step.
  • the PSA or VSA process is carried out with pressurization to super atmospheric pressure during the adsorption step and reduction of pressure to atmospheric pressure or below during the bed regeneration step.
  • the pressure in the vessel undergoing thermal regeneration is at or near atmospheric pressure.
  • the process described below comprises three phases; a first phase, in which vessels 230 and 235 are initially operating in an alternating PSA or VSA cycle and the adsorbent in vessel 240 is undergoing thermal regeneration; a second phase, in which vessels 235 and 240 are operating in an alternating PSA or VSA cycle while the adsorbent in vessel 230 undergoes thermal regeneration; and a third phase, in which vessels 230 and 240 are operating in an alternating PSA or VSA cycle, while the adsorbent in vessel 235 undergoes thermal regeneration.
  • one of the vessels 230 or 235 for example vessel 230 is in the adsorption mode and the other vessel is in the regeneration mode.
  • wet feed 70 enters the bed through open valve 200 and exits the bed through open valve 245.
  • vessel 230 Prior to start of adsorption, vessel 230 is pressurized to the adsorption pressure through valve 200.
  • the dew point of the gas stream exiting the moisture adsorption system 79 would normally be below -4O 0 C and more preferably below -60 0 C.
  • part of the purge gas 95 enters through open valves 290 and 265 and picks up moisture from the adsorbent bed 235 and exits through valve 215.
  • the purge gas may be heated prior to its use in the PSA or VSA process.
  • the remainder of the purge gas entering the moisture adsorption system 79 is heated in heater or heat exchanger 96 and then flows through the layers 240a and 240b in vessel 240.
  • the purge gas desorbs the residual moisture, hydrocarbons, nitrogen and sulfur oxides, and mercury from different layers that have gradually built up in this vessel 240 over the previous PSA or VSA stages carried out in this vessel.
  • the regeneration gas, together with the desorbed impurities leaves vessel 240 through open valve 225.
  • vessel 230 starts undergoing regeneration while vessel 235 starts removing moisture and other impurities.
  • Vessels 230 and 235 continue under PSA or VSA operation for a period of several hours or days, typically 8 to 96 hours, while vessel 240 is thermally regenerated during part of this time.
  • the temperatures for thermal regeneration typically range between 100 0 C and 300 0 C but can be higher or lower depending on the material.
  • the impurities such as nitrogen and sulfur oxides removed during the thermal regeneration may be sent to the existing nitrogen and sulfur removal systems for further reduction of these impurities.
  • one of the vessels 235 or 240 for example vessel 235 is in the adsorption mode and the other vessel is in the regeneration mode.
  • wet feed 70 enters the bed through open valve 210 and exits the bed through open valve 260 and is purified in the process.
  • vessel 235 Prior to start of adsorption, vessel 235 is pressurized to the adsorption pressure through valve 210.
  • part of the purge gas 95 enters through open valves 290, and 280, picks up moisture from the adsorbent bed 240 and exits through open valve 225.
  • the remainder of the purge gas entering the moisture adsorption system 79 is heated in a heater or heat exchanger 96 and then flows through the layers 230a and 230b in vessel 230 and desorbs the residual moisture, hydrocarbons, nitrogen and sulfur oxides and mercury from different layers that have gradually built up in this vessel 230 over the previous PSA or VSA stages carried out in this vessel 230.
  • the regeneration gas, together with the desorbed impurities leaves vessel 230 through open valve 205.
  • vessel 235 starts undergoing regeneration while vessel 240 starts removing moisture and other impurities.
  • Vessels 235 and 240 continue under alternating PSA or VSA operation for a period of several hours or days while vessel 230 is thermally regenerated during part of this time.
  • vessels 230 and 240 are in PSA or VSA service and the adsorbent in vessel 235 undergoes thermal regeneration. Operation of the third phase is similar to the operation of the first and the second phases. After all the three phases are completed the process starts again with phase one and all three phases are repeated in a cyclic manner.
  • the CO 2 adsorption or reaction beds (beds A to E in FIG. 4) also undergo a cyclic process to provide continuous operation and also to maximize CO 2 recovery.
  • These beds contain one or more materials that have a significant selectivity for CO 2 over other major components of the flue gas, namely oxygen, nitrogen and argon.
  • Some of the materials that can be used to capture CO 2 from the flue gas comprise, for example, activated carbon, carbon molecular sieves, zeolites such as 4A, 5 A, 13X, NaY and CaX, metallorganic framework compounds, natural zeolites, modified natural and synthetic zeolites, modified activated carbon, pillared clays and reactive sorbents such as sodium and potassium carbonates, amines or ionic liquids supported on a microporous support.
  • FIG. 4 exemplarily illustrates the configuration of the CO 2 separation system 80 wherein CO 2 is removed from the feed stream by adsorption or chemical reaction and is recovered by heating directly or indirectly by steam, hot water or a dry stream recovered from the CO 2 separation system 80.
  • a five-bed CO 2 capture process is illustrated schematically in FIG. 4. The CO 2 feed step and the CO 2 production steps are continuous in this cycle. While the CO 2 capture is illustrated using a five-bed process the CO 2 capture process is not limited to five beds. The process can use less than five beds or more than five beds though a minimum of two beds are required to carry out CO 2 capture and production at the same time. As illustrated in FIG.
  • one bed is removing CO 2 from feed using adsorption or reaction, another bed is undergoing equalization and pressurization steps, a third bed is producing CO 2 while being heated, a fourth bed is producing CO 2 during heating and evacuation steps and the fifth bed is undergoing the steps of CO 2 rinse and equalization.
  • Other cycles similar to this can be used omitting the steps such as the CO 2 rinse and adding steps such as bed cooling after the heating steps.
  • the equalization can be done from the bottom, from the top or from both top and the bottom. Pressurization can also be done from the bottom using the feed or from the top using the CO 2 -depleted stream.
  • Each individual step of the CO 2 capture process is likely to be of the order of 2-60 minutes to maximize the productivity of the process.
  • a typical cycle using the five-bed configuration of FIG. 4 is given in Table I.
  • the feed to adsorbers A to E is typically at a temperature between about 10 and 8O 0 C and at pressures between about 1.07 bara and 40 bara, and at a temperature in the range of about 2O 0 C and 6O 0 C.
  • the pressures will be in the range of about 1.07 and 1.34 bara.
  • the regeneration temperatures are in the range of about 8O 0 C and 300 0 C and more typically in the range of about 80°C-150°C.
  • the concentration of CO 2 in the feed gas is about 3% for a natural gas fired power plant, about 12% for a coal-fired power plant and up to 60% of CO 2 for various chemical processes.
  • the beds in adsorbers A to E may be heated to temperatures higher than 300 0 C to remove any residual moisture contained therein. High temperature regeneration may also be performed to remove impurities built up during normal operation.
  • steps 1 and 2 of Table I The operation of various valves is illustrated using steps 1 and 2 of Table I.
  • feed gas 72 enters the bed through open valve 302
  • CO 2 is captured in the bed and the CO 2 -depleted stream exits the bed as stream 85 through the open valve 312.
  • beds B and E undergo pressure equalization through open valves 340 and 430.
  • bed B is pressurized using bed A through open valves 320 and 350.
  • bed C is regenerated by heating under vacuum and valves 366 is open.
  • the high purity CO 2 product leaves as stream 100 prior to entering the vacuum pump 110.
  • bed D is regenerated by heating, valves 398 and 408 are open and product CO 2 leaves as stream 105.
  • step 2 bed E is rinsed with product CO 2 stream 145 which enters the bed through open valve 424 and exits through open valve 434. Operation of various valves during steps 3 to 10 is similar to operation during steps 1 and 2. Once all the steps are completed, the cycle is repeated continuously starting at step 1.
  • One such configuration is the shell and tube configuration wherein the adsorbents or reactants are contained in small diameter tubes and the heating medium flows on the shell side during the regeneration part of the cycle. Regeneration temperatures of about 8O 0 C -300 0 C can be obtained using steam or hot water as the heating medium. A heated liquid or vapor stream utilizing the electricity generated in the power plant can also be used for regeneration.
  • An alternative configuration includes the adsorbent material on the shell side and the heating or the cooling fluid on the tube side.
  • Another configuration that allows indirect heating is a plate and frame configuration wherein adsorbents are contained in alternate parallel passages and the heated fluid flows in alternate parallel passages. Steam or a heated fluid may be used as the heating medium.
  • cold fluid can be used during the CO 2 removal step to remove the heat of adsorption or chemical reaction.
  • Cold fluid can also be used for the bed cooling steps.
  • both the horizontal and the radial beds can be used for carrying out the cycle.
  • either the shell and tube configuration or the plate and frame configuration can be used for heat exchange with horizontal or the radial beds.
  • the CO 2 generated during the heating and the evacuation parts of the cycle would typically have a purity of higher than 90%.
  • This stream is compressed and sent to a CO 2 purification plant as discussed earlier. If a membrane is used for CO 2 purification, a small portion of the CO 2 stream is allowed to permeate the membrane to produce a higher purity CO 2 stream which is used as the rinse stream in the CO 2 separation system 80. The rest of the stream may be further compressed and used for enhanced oil recovery, industrial applications or for CO 2 sequestration. If a getter process is used for CO 2 purification impurities such as oxygen and sulfur dioxide are removed by reaction with the getter and the purified CO 2 stream may be further compressed and used in various applications.
  • CO 2 is produced as the bottoms product and the non-condensibles are removed as the overheads of the distillation column.
  • Part of the CO 2 produced by distillation may be used to provide the purge in the CO 2 capture section; the rest is pumped to a higher pressure and used for various applications such as enhanced oil recovery or sequestration.
  • the non- condensibles stream may be further purified by a membrane or an adsorption process to recover additional amounts of CO 2 .
  • 5A zeolite of 8x12 mesh size (about 1.5 mm) was obtained from Aldrich Corporation and loaded in two 18 mm diameter adsorbent beds. The total weight of adsorbent was about 500 grams (gms). A feed stream containing about 12.5% CO 2 with the balance being nitrogen, to simulate flue gas from a coal-fired power plant, was passed through these beds at a flow rate of 11 standard liters/min and at a pressure of 1.34 bara. The standard conditions refer to 21.1 0 C and 1 bara. The adsorbing bed was cooled with a jacket containing a water/glycol mixture at 3O 0 C. The regenerating bed was heated with a jacket containing water / glycol mixture at 100 0 C.
  • the concentrations in the CO 2 -depleted stream and in the CO 2 product were analyzed using an infrared CO 2 analyzer.
  • the cycle for this process is shown in Table II. After heating, the beds were evacuated to a pressure of about 0.25 bara during the evacuation steps. For these process conditions, an average CO 2 purity of 99.8% and an average CO 2 recovery of 85.8% were obtained.
  • Example 1 The process of Example 1 was run at different adsorption temperatures. Other process conditions, namely the feed pressure, feed CO 2 concentration, and the adsorbent material were the same as in Example 1. Again, the concentrations in the CO 2 -depleted stream and in the CO 2 product stream were analyzed using an infrared CO 2 analyzer. The process cycle of Table II was used. For a feed temperature of 20 0 C, an average CO 2 purity of 99.0% and an average CO 2 recovery of 88% were obtained. For a feed temperature of 4O 0 C, an average CO 2 purity of 99.2% and an average CO 2 recovery of 84% were obtained.
  • Example 1 The process of Example 1 was run with a commercially available 13X zeolite of
  • Example 4 8x12 mesh size (1.5 mm) obtained from the Aldrich Corporation.
  • the feed pressure, and the feed CO 2 concentration were the same as in Example 1 and the process cycle of Table II was used. Again, the concentrations in the CO 2 -depleted stream and in the CO 2 product stream were analyzed using an infrared CO 2 analyzer. For a feed temperature of 2O 0 C, an average CO 2 purity of 98.5% and an average CO 2 recovery of 87% were obtained. For a feed temperature of 30 0 C, an average CO 2 purity of 98.5% and an average CO 2 recovery of 78% were obtained.
  • Example 4 Example 4:
  • the beds containing 5A as in Example 1 were used ( total weight of about 500 gms) with a feed stream containing about 3.4% CO 2 with the balance being nitrogen, to simulate the flue gas from a natural gas fired power plant.
  • the feed was passed through these beds at a total flow rate of 17 standard liters/min.
  • the adsorbing bed was cooled with a jacket containing a water/glycol mixture at 20 0 C.
  • the process cycle in Table II was used.
  • the regenerating bed was heated with a jacket containing water/glycol mixture at 100 0 C.
  • the concentrations in the CO 2 -depleted stream and in the CO 2 product were analyzed using an infrared CO 2 analyzer.
  • the 5A zeolite of Example 1 was used to obtain the results for a vacuum swing adsorption process without any thermal regeneration.
  • the feed comprised 12.8% CO 2 at 1.34 bara and 30 0 C.
  • the beds were evacuated to a pressure of 0.25 bara during the regeneration step. Both the adsorption and the regeneration steps were carried out at 30 0 C.
  • the process cycle comprised adsorption, equalization, rinse with pure CO 2 , evacuation, equalization and pressurization steps.
  • Example 1 Commercially available F-200 activated alumina from Alcoa (1.5 mm size) was loaded in the beds of Example 1.
  • the total weight of the adsorbent was about 300 gms.
  • a feed stream saturated with water at 25 0 C and containing about 12.5% CO 2 with the balance being nitrogen was passed through these beds at a total flow rate of 10 standard liters/min and at a pressure of 1.34 bara.
  • the cycle comprised an adsorption time of 5 minutes, a purge time of 4.5 minutes, and a pressurization and depressurization time of 0.25 minutes each and was designed to retain most of the heat of water adsorption in the beds.
  • the dry product exiting the adsorbing bed was used for purge after reducing the pressure to about atmospheric.
  • the dew point of the product stream exiting the beds was monitored continuously and the product moisture concentration remained below 1 parts per million (ppm) during a period of five days.
  • This example illustrates that under certain conditions the feed stream to the CO 2 separation can be dried to very low moisture levels to improve the CO 2 recovery in the CO 2 separation section.
  • the purge gas in a process wherein the moisture is removed prior to CO 2 adsorption would be the CO 2 -depleted stream from the CO 2 adsorption section.
  • the method and system disclosed herein for the capture of CO 2 offers a number of advantages.
  • the process can be used both for retrofit applications as well as for the new plants. Modifications required to the power plant for retrofit applications are significantly smaller than those needed for amine-based CO 2 capture.
  • the process is applicable to both coal-fired and natural-gas fired power plants.
  • the process is also applicable to other streams such as the refinery and chemical process streams containing carbon dioxide. Unlike absorption processes where nitrogen and sulfur oxides (N0 ⁇ and S0 ⁇ ) in the feed can react with the solvent irreversibly and require removal to below about 10 ppm levels, the N0 ⁇ and SO ⁇ in the feed do not affect the adsorbent adversely.
  • Oxygen in the feed has no effect on the adsorbents unlike absorption-based processes where oxygen degrades the amine solvent.
  • the process provides dry CO 2 product eliminating the drying step prior to CO 2 compression and liquefaction, and the power and capital costs associated with it.
  • the feed gas containing CO 2 can come from other processes such as a natural gas fired power plant or from a coal gasification plant.

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Abstract

L'invention porte sur un procédé et un système pour séparer du dioxyde de carbone (CO2) à partir d'un courant de gaz contenant du CO2 et contenant de la vapeur d'eau et des impuretés additionnelles, par exemple, de l'azote, de l'oxygène, des oxydes de soufre, des oxydes d'azote et du mercure. On capture le CO2 en soumettant le courant d'alimentation de gaz contenant du CO2 à une étape d'adsorption modulée en température. L'étape d'adsorption modulée en température comprend une étape d'adsorption pour produire un courant appauvri en dioxyde de carbone, sensiblement sec, et une étape de régénération d'adsorbant, comprenant un chauffage du lit d'adsorbant pour produire un courant de dioxyde de carbone sensiblement exempt de vapeur d'eau. L'humidité provenant du courant de gaz contenant CO2 est facultativement éliminée par adsorption modulée en pression, adsorption modulée en température, séparation sur membrane ou absorption avant la capture de CO2.
EP09730698A 2008-04-06 2009-04-07 Récupération de dioxyde de carbone Withdrawn EP2427255A4 (fr)

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JP2012522627A (ja) 2012-09-27
CN102083512A (zh) 2011-06-01
WO2009126607A3 (fr) 2010-01-21
KR101312914B1 (ko) 2013-09-30
BRPI0911793A2 (pt) 2017-05-02
CA2726383A1 (fr) 2009-10-15
MX2010011017A (es) 2011-01-21
WO2009126607A2 (fr) 2009-10-15
CA2726383C (fr) 2015-08-25
WO2009126607A4 (fr) 2010-03-11
AU2009233890B2 (en) 2014-10-30
ZA201007593B (en) 2013-09-25

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