CA2759867A1 - Multi-stage process for purifying carbon dioxide and producing sulfuric acid and nitric acid - Google Patents

Multi-stage process for purifying carbon dioxide and producing sulfuric acid and nitric acid Download PDF

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Publication number
CA2759867A1
CA2759867A1 CA2759867A CA2759867A CA2759867A1 CA 2759867 A1 CA2759867 A1 CA 2759867A1 CA 2759867 A CA2759867 A CA 2759867A CA 2759867 A CA2759867 A CA 2759867A CA 2759867 A1 CA2759867 A1 CA 2759867A1
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Canada
Prior art keywords
nox
carbon dioxide
sulfuric acid
stream
rich
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Abandoned
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CA2759867A
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French (fr)
Inventor
Nick Joseph Degenstein
Minish Mahendra Shah
Ravi Kumar
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Praxair Technology Inc
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Praxair Technology Inc
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Publication of CA2759867A1 publication Critical patent/CA2759867A1/en
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/14—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 absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • F25J2210/70—Flue or combustion exhaust gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82—Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/32—Compression of the product stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/80—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/32—Direct CO2 mitigation
    • 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

Abstract

Carbon dioxide is purified by processes employing NOx-rich sulfuric acid that can be formed by removal of SO2 from the carbon dioxide. The NOx is stripped or desorbed from the NOx-rich sulfuric acid. Futhermore, nitric acid and sulfuric acid are formed in the process.

Description

MULTI-STAGE PROCESS FOR PURIFYING CARBON DIOXIDE
AND PRODUCING SULFURIC ACID AND NITRIC ACID

Field of the Invention [0001] The present invention relates to the treatment of gaseous streams such as flue gas containing carbon dioxide, to remove impurities from the gas and to produce valuable byproducts.

Background of the Invention [0002] It is often desirable to treat carbon dioxide streams, whether naturally occurring or produced by man-made processes, to remove other components and thereby purify the carbon dioxide. For instance, combustion processes, such as coal-fired boilers, produce flue gases that contain carbon dioxide which it may be desirable to capture and sequester, for instance in saline aquifers or in oil or gas wells where the carbon dioxide is used for enhancing the production of oil or gas from the well. However, flue gas often contains impurities such as SO2 and NOx which must be removed down to very low levels before the carbon dioxide can be used for enhanced oil recovery or sequestered. The present invention is a process for achieving such removal, in a way that also produces sulfuric acid and nitric acid of strengths, and in amounts, that are commercially valuable.

Brief Summary of the Invention [0003] One aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid with said gaseous feed stream and with NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;

- I -(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2; and (D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid.

(0004( A second aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid (preferably formed in step (E)) with said gaseous feed stream and NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and N02, (C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid; and (E) reacting water and oxygen with said NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide.
(00051 Another aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid (preferably formed in either or both of steps (C) and (D)) with said gaseous feed stream to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;

(C) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide; and (D) absorbing NOx from said S02-depleted NOx-containing gaseous carbon dioxide into one or both of NOx-reduced sulfuric acid and NOx-lean sulfuric acid (preferably formed in steps (B) or (C) respectively) to form NOx-rich sulfuric acid and NOx-lean S02-depleted gaseous carbon dioxide.
[00061 Yet another aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid (preferably formed in one or more of steps (E) and (F)) with said gaseous feed stream and NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;

(D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (C) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;

(E) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and S02-depleted NOx-containing carbon dioxide; and (F) absorbing NOx from said S02-depleted Nox-containing carbon dioxide into one or both of Nox-reduced sulfuric acid and Nox-lean sulfuric acid (preferably formed in step (B) or step(C) respectively) to form Nox-rich sulfuric acid and Nox-lean S02-depleted carbon dioxide.

[0007) A further aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;

(B) converting NO in NOx-rich sulfuric acid (preferably formed in one or both of steps (D) and (E)) to NO2, and desorbing NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(C) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;
(D) reacting water and oxygen with carbon dioxide in said feed stream and desorbed NO2 to form NOx-rich sulfuric acid and SO2-depleted NOx-containing carbon dioxide; and (E) absorbing NOx from said S02-depleted NOx-containing carbon dioxide into NOx-lean sulfuric acid (preferably formed in step (B)) to form NOx-rich sulfuric acid and NOx-lean S02-depleted carbon dioxide.
[00081 Other aspects of the invention comprise apparatus useful for treating gaseous carbon dioxide, such as:.

(I) Apparatus comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO
in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
and (C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO.

(II) Apparatus comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO
in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO; and (D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide.

(III) Apparatus comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO
in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;

(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO, (D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide; and (E) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean S02-depleted gaseous carbon dioxide.

(IV) Apparatus comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO
in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
= CA 02759867 2011-10-24 (C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide; and (E) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean S02-depleted gaseous carbon dioxide.

(V) Apparatus comprising (A) a converting unit to receive NOx-rich sulfuric acid which can catalytically convert NO in said NOx-rich sulfuric acid to NO2 and desorb NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;

(B) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;

(C) a reactor to receive NO2 desorbed in unit (A) and gaseous carbon dioxide that contains NOx and sulfur dioxide, and to react NOx and sulfur dioxide in said carbon dioxide with water and oxygen and said desorbed NO2 to form NOx-rich sulfuric acid and SO2-depeleted NOx-containing gaseous carbon dioxide; and (D) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said S02-depleted NOx-containing carbon dioxide into said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide.
[00091 Other aspects of the invention incorporate further processing of the carbon dioxide stream. For instance, another aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid (preferably formed in one or more of steps (E) and (F)) with said gaseous feed stream and NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (C) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;
(E) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and S02-depleted NOx-containing carbon dioxide;
(F) absorbing NOx from said S02-depleted NOx-containing carbon dioxide into one or both of NOx-reduced sulfuric acid and NOx-lean sulfuric acid (preferably formed in step (B) and/or step (C) respectively) to form NOx-rich sulfuric acid and NOx-lean S02-depleted carbon dioxide;
(G) subjecting the NOx-lean SO2-depleted carbon dioxide to a subambient-temperature recovery process, employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery process, and preferably employing only refrigeration provided by such expansion, to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream;

= CA 02759867 2011-10-24 (J) separating the vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption; and (K) recycling said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
[00101 Another aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;

(B) converting NO in NOx-rich sulfuric acid formed in one or both of steps (D) and (E) to NO2, and desorbing NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, (C) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;

(D) reacting water and oxygen with carbon dioxide in said feed stream and desorbed NO2 to form NOx-rich sulfuric acid and S02-depleted NOx-containing carbon dioxide; and (E) absorbing NOx from said S02-depleted NOx-containing carbon dioxide into NOx-lean sulfuric acid (preferably formed in step (B)) to form NOx-rich sulfuric acid and NOx-lean S02-depleted carbon dioxide;
(F) subjecting the NOx-lean SO2-depleted carbon dioxide to a subambient-temperature recovery process, employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery process, and preferably employing only refrigeration provided by such expansion, to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream;

(G) separating the vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption; and (H) recycling said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
[00111 Yet another aspect of the present invention is a process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid with said gaseous feed stream to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide;
(D) absorbing NOx from said S02-depleted NOx-containing gaseous carbon dioxide into one or both of NOx-reduced sulfuric acid and NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean S02-depleted gaseous carbon dioxide;
(E) subjecting the NOx-lean S02-depleted carbon dioxide to a subambient-temperature recovery process, employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery process, to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream;
(F) separating the vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption; and (G) recycling said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
[00121 Other aspects of the invention comprise apparatus useful for treating gaseous carbon dioxide, such as:
(1) Apparatus comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;

(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide;

(E) an absorber coupled to said reactor to receive S02-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said S02-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide;
(F) a subambient-temperature recovery unit coupled to said absorber to receive said NOx-lean S02-depleted carbon dioxide therefrom to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery unit;
(G) a vent stream separation unit coupled to said subambient-temperature recovery unit to receive said vent stream therefrom and separate said vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption;
and wherein said vent stream separation unit is coupled to said carbon dioxide-containing feed stream to feed said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.

(11) Apparatus comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide; and (E) an absorber coupled to said reactor to receive S02-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean S02-depleted gaseous carbon dioxide;
(F) a subambient-temperature recovery unit coupled to said absorber to receive said NOx-lean SO2-depleted carbon dioxide therefrom to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery unit;

(G) a vent stream separation unit coupled to said subambient-temperature recovery unit to receive said vent stream therefrom and separate said vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption;
and wherein said vent stream separation unit is coupled to said carbon dioxide-containing feed stream to feed said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.

(III) Apparatus comprising (A) a converting unit to receive NOx-rich sulfuric acid which can catalytically convert NO in said NOx-rich sulfuric acid to NO2 and desorb said NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;

(B) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;

(C) a reactor to receive NO2 desorbed in unit (A) and gaseous carbon dioxide that contains NOx and sulfur dioxide, and to react NOx and sulfur dioxide in said carbon dioxide with water and oxygen and said desorbed NO2 to form NOx-rich sulfuric acid and S02-depleted NOx-containing gaseous carbon dioxide;
and (D) an absorber coupled to said reactor to receive S02-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide;
(E) a subambient-temperature recovery unit coupled to said absorber to receive said NOx-lean S02-depleted carbon dioxide therefrom to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery unit;

(F) a vent stream separation unit coupled to said subambient-temperature recovery unit to receive said vent stream therefrom and separate said vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption;
and wherein said vent stream separation unit is coupled to said carbon dioxide-containing feed stream to feed said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
100131 Other aspects of the present invention include the embodiments described herein below.
10014] As used herein, "NOx" means a mixture of gaseous oxides of nitrogen that contains at least both NO and NO2.
100151 As used herein, "oxy-fuel combustion" means feeding fuel and feeding an oxidant stream having an oxygen content of at least 80 vol.% to a combustion process and combusting the fuel with oxygen, possibly with recycle to the combustion process of at least a portion of the gaseous products of the combustion. An oxyfuel combustion process generates a flue gas stream rich in carbon dioxide.
100161 As used herein, "pressure swing adsorption" means adsorbing a product, in this case carbon dioxide, from a gaseous feed stream onto a solid adsorbent at a first pressure, removing the feed stream depleted of the adsorbed product, and then desorbing the product at a second pressure different from the first pressure.
100171 As used herein, "vacuum pressure swing adsorption (VPSA)" means a pressure swing adsorption process in which the second pressure is subambient pressure.
100181 As used herein, "physical absorption" means absorbing a product, in this case carbon dioxide, from a gaseous feed stream by passing the feed stream into a liquid which preferentially dissolves the carbon dioxide from the feed stream, removing the feed stream depleted of the absorbed product, and then recovering the carbon dioxide from the liquid such as by lowering the pressure over the liquid or by stripping the carbon dioxide out of the liquid, wherein the absorption of the carbon dioxide into the liquid does not involve a chemical reaction of the carbon dioxide.
[00191 As used herein, "chemical absorption" means absorbing a product, in this case carbon dioxide, from a gaseous feed stream by passing the feed stream into a liquid which contains a component with which the carbon dioxide preferentially reacts, removing the feed stream depleted of the absorbed product, and then recovering the carbon dioxide from the liquid such as by lowering the pressure over the liquid or by stripping the carbon dioxide out of the liquid, wherein the absorption of the carbon dioxide into the liquid involves a chemical reaction of the carbon dioxide with a component in the liquid.

Brief Description of the Drawings [00201 Figure 1 is a block diagram of a process for treating flue gas, in which the present invention is useful.
[00211 Figure 2 is a block diagram of a preferred embodiment of a process according to the present invention. -100221 Figure 3 is a block diagram of an alternate embodiment of the process shown in Figure 2.

[00231 Figure 4 is a diagram of an embodiment of a subambient-temperature processing unit useful in the method of the present invention.

[00241 Figure 5 is a diagram of another embodiment of a subambient-temperature processing unit useful in the method of the present invention.
[00251 Figure 6 is a diagram of another embodiment of a subambient-temperature processing unit useful in the method of the present invention.

[00261 Figure 7 is a diagram of another embodiment of a subambient-temperature processing unit useful in the method of the present invention.

[00271 Figure 8 is a diagram of another embodiment of a subambient-temperature process useful in the method of the present invention.

[00281 Figure 9 is a diagram of another embodiment of a subambient-temperature process useful in the method of the present invention.
[00291 Figure 10 illustrates a cycle step chart for a carbon dioxide VPSA unit having six beds, three pressure equalization steps and flow through the evacuating bed, useful in the present invention.
[00301 Figure 11 shows a schematic drawing for a carbon dioxide VPSA unit of Figure 10.
[00311 Figure 12 shows the valve sequence for operation of the carbon dioxide VPSA unit shown in Figures 10 and 11.
[00321 Figure 13 illustrates an alternative cycle step chart for a carbon dioxide VPSA unit having five beds, two pressure equalization steps and flow through the evacuating bed, useful in the present invention.
[00331 Figure 14 illustrates another alternative cycle step chart for a carbon dioxide VPSA unit having seven beds, three pressure equalization steps and flow through the evacuating bed, useful in the present invention.

100341 Figure 15 illustrates a further alternative cycle step for a carbon dioxide VPSA unit having six beds, three pressure equalization steps and direct mixing, useful in the present invention.
[00351 Figure 16 shows a schematic drawing for the carbon dioxide VPSA unit of Figure 15.
[00361 Figure 17 shows the valve sequence for operation of the carbon dioxide VPSA unit shown in Figures 15 and 16.
[00371 Figure 18 illustrates yet another cycle step chart for a carbon dioxide VPSA unit having five beds, two pressure equalization steps and direct mixing, useful in the present invention.
100381 Figure 19 illustrates yet another cycle step chart for a carbon dioxide VPSA unit having eight beds, two pressure equalization steps and direct mixing in which two beds are continuously on feed and at least two beds are continuously under evacuation, useful in the present invention.
[00391 Figure 20 illustrates a further cycle step chart for a carbon dioxide VPSA
unit having eleven beds, two pressure equalization steps and direct mixing in which three beds are continuously on feed and two beds are continuously under evacuation, useful in the present invention.
[00401 Figure 21 is a diagram of a process useful in employing absorption in the method of the present invention.

Detailed Description of the Invention [00411 The invention is useful in treatment of gaseous carbon dioxide streams which may be obtained in many ways. In particular, gaseous carbon dioxide streams with which the invention is useful include those produced by combustion, especially flue gas streams produced by combustion of hydrocarbonaceous fuels such as coal. The various aspects of the present invention are described below with particular reference to such flue gas streams, but without intending to be limited to such streams.

[00421 Figure 1 shows a schematic diagram of an overall flue gas treatment process which includes the aspects of the present invention. Carbon dioxide-rich flue gas is obtained from a combustion operation such as a coal-fired boiler, and preferably from an oxy-fuel combustion operation wherein coal or other fuel is combusted with gaseous oxidant having an oxygen content higher than that of air, i.e. higher that 20.9 vol.%, preferably higher than 50 vol.% and more preferably higher than 90 vol.% oxygen.

[00431 The flue gas is preferably treated, such as in an electrostatic precipitator (ESP in Figure 1) or in a cyclone or baghouse or other particulate removal device, to remove entrained particulate matter therefrom. Then the flue gas is cooled and any condensed water is removed.
[00441 The flue gas is then compressed to a pressure of at least 2 bar, preferably at least 20 bar, and typically 20 to 40 bar. Contaminants (SOx, NOx, and Hg) and moisture are removed and a cleaned-up stream containing carbon dioxide and atmospheric gases (02, N2 and Ar) is formed which is fed to a subambient-temperature processing stage which upgrades the purity of the carbon dioxide and produces a product stream having a desired high carbon dioxide level (95 to 99.9%). The vent stream from the subambient-temperature processing stage is fed to an adsorption or absorption stage such as a VPSA (vacuum pressure swing adsorption) unit to recover additional carbon dioxide. The recovered carbon dioxide from this stage, typically in a concentration on the order of 80 vol.%, is recycled and mixed with the feed stream of carbon dioxide-rich flue gas. The adsorption or absorption stage also produces a waste stream which is treated further or vented to the atmosphere.

[0045] Figure 1 illustrates one of many possible applications of the present invention. In Figure 1, air stream 51 is separated in an air separation unit 31 into an oxygen-rich stream 53 and a nitrogen-rich stream 52. The oxygen-rich stream 53 is fed to combustion unit 32 (e.g. furnace or boiler), preferably after being combined with recycled flue gas stream 55, along with fuel which is shown as stream 54. Combustion in unit 32 produces carbon dioxide-containing flue gas part of which may be recycled (as is preferably the case with combustion using oxidant having a high oxygen content) and part of which as stream 101 is fed to a particulate matter control device 1. The particulate matter control device 1 can also be located before the recycle stream 55 if necessary. The flue gas stream following particulate removal is fed to cooling and water removal devices 2 and 3, respectively. Stream 103 represents cooled flue gas proceeding from device 2 to device 3, though the cooling and water removal can instead be carried out in one device. Condensed water 104 is removed from the flue gas.
[0046] The flue gas stream 105 from the cooling and water removal is fed to compressor, 4, which could have multiple stages of compression, intercoolers and water knock-out drums. Preferably the flue gas 105 is compressed up to about bar in a staged compression train, although the process of this invention can operate at any pressure from about 2 bar to a pressure needed for carbon dioxide sequestration. Compressed stream 106 is heated in heat exchanger 5 to preferably at least about 160 C. If desired, the flue gas can be heated before it is compressed.
[0047] Typical characteristics of the hot, compressed flue gas stream 107 are shown in the following table:
= CA 02759867 2011-10-24 Characteristic Preferred range Temperature, C Up to 200 130-170 Pressure, bar 3-55 20 - 30 CO2 (vol.%) 50-98 70-90 Hg vapor, ppb 0.01 - 1000 10 - 50 NOx, ppm 20- 4000 300- 1000 S02 (vol.%) 0.1-3.0 1.0- 1.5 [00481 The carbon dioxide-containing feed gas may preferably be treated at some point to remove mercury. For instance, referring again to Figure 1, the compressed flue gas 107 is contacted in mercury removal stage 6 with sulfuric acid which is fed as stream 61. Stream 61 preferably comprises concentrated sulfuric acid which is produced in the process of the present invention (recovered as stream 115 or elsewhere in the process). The concentrated sulfuric acid oxidizes mercury vapor that is in the flue gas, and reacts with the mercury vapor, forming HgSO4 as a precipitate 62 which can be easily separated and removed from the flue gas stream producing feed stream 108 which in this case is mercury-depleted. Typically, mercury removal in stage 6 employs a vessel to which a small amount of concentrated (e.g. 93 wt.%) sulfuric acid is continually or intermittently fed to maintain an amount of sulfuric acid circulating within the vessel for contact with the flue gas. The temperatures of the flue gas streams entering and leaving stage 6 are preferably maintained approximately the same so that the moisture content of the flue gas remains approximately the same.
[00491 Feed stream 108 is fed to stage 40 where NOx and SO2 are removed from the flue gas, and sulfuric acid 115 and nitric acid 119 are formed, as described below. Stage 40 also produces NOx-lean S02-depleted flue gas stream 1 l 1 which is fed to subambient-temperature processing stage 60 where gases including oxygen, nitrogen and argon, and also including NOx and CO if present, are removed from the flue gas. Stage 60 produces stream 100 containing high-purity carbon dioxide, typically having a carbon dioxide content higher than 95 vol.%.
Stage 60 also produces a vent gas stream 68 comprising carbon dioxide as well as other gases removed from the flue gas in stage 60. Stream 68 is fed to stage where carbon dioxide is separated from the other gases by adsorption or chemical or physical absorption. Stage 70 produces waste gas stream 72 which can be further treated or vented to atmosphere, and carbon dioxide-containing product stream 19 which is recycled and combined with stream 105 (or, alternatively, with stream 106 or stream 107).

100501 Reference is now made to Figure 2, which illustrates embodiments of process stage 40.

[00511 Gaseous NOx-containing stream 117 and carbon dioxide-containing feed stream 108 are fed to NOx stripping unit 7. Streams 108 and 117 can be combined before being fed together to unit 7, or they can be fed to unit 7 in separate lines. Alternatively stream 117 can be combined with stream 109 before stream 109 enters reactor 8 or stream 117 can be fed independently into reactor 108. The main purpose of the NOx recycle afforded by stream 117 is to elevate the concentration of NOx in the reactor 8 such that the residence time of the flue gas in reactor 8 can be minimized. The idea behind administering stream 117 to the stripping unit 7 is to possibly increase the effective time that the flue gas is in an elevated NOx environment. In unit 7 the incoming feed gas stream at a temperature on the order of 150 C contacts NOx-rich sulfuric acid, fed as stream 120, to strip dissolved NOx from the acid. The stripped NOx joins the flue gas within unit 7 to form NOx-augmented gas stream 109 which exits unit 7. Stream 112 of NOx-reduced sulfuric acid also exits unit 7. The streams fed to unit 7 are contacted in any manner which provides effective gas-liquid contact, including the use of contact elements such as column packing elements or contact trays, or simply feeding the gas directly into the liquid within the unit.
[00521 Stream 120 contains sulfuric acid at a concentration of at least 50 wt.%
and preferably at least 70 wt.%. Contacting the feed gas stream with sulfuric acid, rather than water, is preferable as enables the production of concentrated product sulfuric acid, and provides enhanced ability to purify the carbon dioxide.
100531 The NOx-reduced sulfuric acid in stream 112 typically has a concentration of about 93 wt% sulfuric acid. More highly concentrated sulfuric acid (i.e. 98 wt.% or higher) may also be produced. The small amount of NOx which remains absorbed in this acid is removed in unit 10 by feeding stream 112 to unit 10 where NO in the NOx-reduced sulfuric acid is converted by a catalytically promoted reaction with oxygen (fed as stream 116) into NO2, and the NO2 is desorbed from the sulfuric acid. Effective catalytic material includes activated carbon.
Desorption can be effected by reducing the pressure over the acid, and/or by heating the acid. This reaction can be carried out to the extent that the total NOx remaining in the sulfuric acid is very low, even less than 5 ppm of NOx, so the resulting NO2-lean sulfuric acid has a concentration and purity that render it commercially salable. Product stream 115 of NOx-lean sulfuric acid is recovered from unit 10. Stream 113 of NOx-lean sulfuric acid is also recovered from unit for further processing as described herein. However, the NOx-lean sulfuric acid 113 can be the NOx-reduced sulfuric acid 112 without passing through unit 10, as is indicated by dashed line 112' in Figure 2. In this scenario at least some portion of stream 112 bypasses unit 10 and is fed into stream 113.

100541 As stated above, NO2 is fed to stripping unit 7. This NO2 is preferably obtained from gaseous stream 114 which contains NOx and which is produced by removal of NOx from the sulfuric acid in unit 10. Some NOx is removed from the system, preferably by treatment in nitric acid formation unit 11 to convert a portion of the NO2 that is in stream 114 to nitric acid by the addition of water 118.
The nitric acid, recovered as stream 119, is also a valuable product of the present invention. The formation of nitric acid proceeds according to the following equation:

3NO7 (g) + H, 0(l) -* 2HN03 (aq) + NO(g) The NOx entering unit 11 that is not converted to nitric acid constitutes stream 117 which is treated as described above.
100551 While as depicted in Figure 2 all of stream 114 can be fed to nitric acid formation unit 11, with only a portion of the NO2 being converted to nitric acid and the remaining NO2 being fed from unit 11 as stream 117, it will be recognized as an alternative that a main stream can lead directly from unit 10 to stripping unit 7, with a side stream branching off of this main stream to feed into unit 10 in which case all of the NO2 that is fed into unit 10 is converted to nitric acid.
[00561 The ability to remove nitrogen as nitric acid in stream 119 provides the ability to balance with the amount of nitrogen entering the process in feed gas stream 107. This is particularly useful when stripping unit 7 is part of an overall process for removing NOx from carbon dioxide such as flue gas. The operator can maintain control over this balance by controlling the proportion of NOx fed to unit 11 that is converted to nitric acid (for instance, by controlling how much water is fed to unit 11) or, in the alternative described above in which a main stream is fed from unit 10 to unit 11 and a side stream is fed to unit 11, by controlling how much of the main stream is diverted as the side stream.

[00571 The NOx circuit that is enabled by this control maintains a level of NOx high enough to promote formation of sulfuric acid in the next stages, while permitting formation in a reduced amount of time of nitric acid as the outlet for nitrogen entering the system.

100581 The N02-augmented gas stream 109 that exits unit 7 is fed to reactor 8 for conversion of SO2 that is in stream 109, preferably >99% of that SO2, into sulfuric acid. Water 125 is also fed to reactor 8. In reactor 8, NOx and SO2 autocatalytically react to oxidize SO2 in the feed gas to SO3, which then combines with water to form sulfuric acid. The chemistry is shown in the following Reactions 1, 2 and 3. As shown, SO2 reacts with NO2 forming SO3 which then reacts with water to form sulfuric acid. NO2 is consumed and NO2 is regenerated by oxidation of NO that forms with the SO3. Oxygen for this oxidation can be provided to reactor 8 as air, oxygen-enriched air, or commercially pure oxygen having an 02 content of 90 vol.% or higher. However typically no feed stream of oxidant will need to be added because the 02 level in the gas in stream 109 and in the ambient atmosphere is typically high enough to supply all of the oxidant needed for reaction 3. The cycle represented by Reactions 1, 2 and 3 continues until as much as desired, preferably as much as possible, of the SO2 has been converted to sulfuric acid. Conversion of more than 99% of the SO2, and even of more than 99.9% of the SO2, is obtained in this manner.

SO, + NO2 - SO3 + NO Reaction I
S03(g)+H_0(1)->H,S04(l) Reaction 2 NO + 0.5 O, (g) - NO, Reaction 3 [00591 S02-depleted gas stream 110 is obtained from reactor 8. It still contains SO2, typically much less than 0.1 vol.% SO2. Stream 110 also contains NOx.
NOx-rich sulfuric acid stream 121 also exits from reactor 8. A side stream 122 is taken from stream 121, cooled in heat exchanger 13, and returned to reactor 8 as needed in order to maintain temperature control within reactor 8. The remaining NOx-rich sulfuric acid stream 123 can be recycled, with heating as needed in heater 12, to unit 7.
[00601 Stream 1 10, which still contains high levels of NOx, is fed to absorber 9 as is stream 113 of NOx-lean sulfuric acid, after cooling as needed (typically to about 30 C) in heat exchanger 14. The NOx-lean sulfuric acid used in this step has a sulfuric acid content of at least 50 wt.% and preferably at least 70 wt.%.
Using sulfuric acid instead of water affords many advantages, especially in enabling the production of a highly concentrated sulfuric acid product. The NOx-lean sulfuric acid is preferably obtained from unit 10 (or unit 7). The cooled NOx-lean sulfuric acid 113 is contacted with S02-depleted gas from stream 110 in absorber 9 to absorb NOx from the gas. Contact is preferably provided in any manner which provides effective gas-liquid contact, including the use of contact elements such as column packing elements or contact trays, or simply feeding the gas directly into the liquid within the unit. Product NOx-lean S02-depleted gas stream 111 leaves absorber 9. Stream 111 contains SO2, in amounts typically of 1-10 ppm or higher. The NOx content of stream 111 is typically about 50ppm or less. This corresponds to 0.02 lb NOx/MMbtu of power generation in combustion unit 32 which is about one-seventh of the strictest emission requirements now applicable to carbon-dioxide-emitting combustion units.
100611 NOx-rich sulfuric acid stream 124 is also recovered from absorber 9.
This stream can be heated as needed and can be recycled to unit 7, for instance by combining streams 124 and 123 as shown in Figure 2.

[00621 The production and usage of concentrated sulfuric acid in the manner of the process of the present invention has many added benefits, one of which is the drying of the carbon dioxide-containing gas prior to any further treatment thereof.
This eliminates the need for any subsequent drying before the gas stream proceeds on to the subambient-temperature processing stage for separation of inert gases from the carbon dioxide. The gas leaving absorber 9 has typically been dehydrated to a dewpoint of less than -70 C such that this stream can be directly fed to the subambient-temperature processing stage.

100631 The pressure in all stages should be at least 2 bar, and preferably in the range of 20 to 40 bar.
[00641 Characteristics of the process streams in this invention are set forth in the following tables:

Into unit 7: Preferred range Stream 108 Temperature, C Up to 200 130-170 Pressure, bar 3-55 20-30 CO2 (vol.%) 50 - 98 70-90 Hg vapor, (ppb) .001 - 100 0.001-2 NOx (vol.%) .0002 - 4 0.5-2 SOx (vol.%) 0.1 -3.0 1.0-1.5 Into unit 7: Preferred range Stream 120 Temperature, C 20- 150 40-80 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5 - 5 1-3 NOx (wt.%) 0.1 - 20 1-5 H2SO4 (wt.%) 70 - 100 90-98 Out of unit 7/ Preferred range Into unit 8:
Stream 109 Temperature, C 50- 150 60-120 Pressure, bar 3-50 20-30 CO2 (vol.%) 50 - 98 70-90 NOx (vol.%) .0002 - 4 0.5-2 SOx (vol.%) 0.1 -3.0 1.0-1.5 Out of unit 7/ Preferred range Into unit 10:

Stream 112 Temperature, C 80 - 200 140-180 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5 - 10 1-5 NOx (wt.%) 5ppm- 1% 0.01-0.3 H2S04 (wt.%) 70 - >100 93-98 Out of unit 8/ Preferred range Into unit 9:
Stream 110 Temperature, C 40- 150 60-100 Pressure, bar 3-50 20-30 CO2 (vol.%) 50 - 98 70-90 NOx (vol.%) 0.1 - 3.0 0.5-2 SOx (vol.%) 1 ppm - 0.5 0.01-0.1 Out of unit 8: Preferred range Stream 121 Temperature, C 40 - 180 60-150 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5- 10 1-5 NOx (wt.%) .0002 - 4 0.1-2 H2SO4 (wt.%) 70 - >100 93-98 Into unit 9: Preferred range Stream 113 Temperature, C 60- 200 80-180 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5 - 10 1-5 NOx (wt.%) 5ppm- 1% 0.01-0.3 H2SO4 (wt.%) 70 - >100 93-98 Out of unit 9: Preferred range Stream 111 .Temperature, C 20 - 100 30-50 Pressure, bar 3-50 20-30 CO2 (vol.%) 50 - 98 70-90 NOx (ppm) 0.1- 1-50ppm 300ppm SOx (ppm) 10- 10-300ppm 1500ppm Out of unit 9: Preferred range Stream 124 Temperature, C 20 - 100 40-70 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5 - 15 1-5 NOx (wt.%) .0002 - 4 0.1-3 H2SO4 (wt.%) 70 - >100 80-98 Out of unit 10: Preferred range Stream 113 Temperature, C 60 -200 80-180 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5 - 10 1-5 NOx (wt.%) 5ppm- 1% 0.01-0.3 H2SO4 (wt.%) 70 - >100 93-98 Out of unit 10/ Preferred range Into unit 11:
Stream 114 Temperature, C 60 -200 80-180 Pressure, bar 3-50 20-30 CO2 (vol.%) 0.5 - 10 1-5 NOx (vol.%) 0.lppm- lppm-I000ppm 1%
SOx (vol.%) 70 - >100 93-98 Out of unit 10: Preferred range Stream 115 Temperature, C 60 - 200 80-180 Pressure, bar 3-50 20-30 CO2 (wt.%) 0.5 - 10 1-5 NOx (wt.%) 0.lppm - lppm-I000ppm 1%
H2SO4 (wt.%) 70 - >100 93-98 Out of unit 11: Preferred range Stream l l7 Temperature, C 60- 200 80-180 Pressure, bar 3-50 20-30 CO2 (vol.%) 0.5 - 90 1-60 NOx (vol.%) 1 - 100 20-60 SOx (vol.%) 1 ppm - 10-10000ppm 10%
Out of unit 11: Preferred range Stream 119 Temperature, C 60- 200 80-180 Pressure, bar 3-50 20-30 CO2 (wt.%) 1 ppm - 0.1-2 10%
HNO3 (wt.%) 20 - 100 40-60 SOx (wt.%) lppm - 10ppm-10% 1000ppm [00651 The various aspects of the present invention have numerous distinguishing features and provide numerous advantages.
[00661 The process preferably operates at higher temperatures than conventional practice, specifically in stripping unit 7 where NOx is stripped out of sulfuric acid. The higher temperature used in stripping unit 7 enables the production of higher sulfuric acid concentrations. Prior practice of units such as unit 7 may only be able to produce sulfuric acid at or below 76 wt%. The factor limiting this concentration is the ability of the process to strip NOx out of the acid solution.
As the acid becomes more concentrated, NOx is absorbed more strongly and is thus more difficult to remove by stripping.
[00671 The process of the present invention is able to overcome this limitation and produce concentrated acid, because of at least the following two features.
Higher temperatures in unit 7 allow NOx to be more easily stripped, and the high temperature catalytic NOx removal reaction in unit 10 helps to remove any residual NOx in the product acid.
[00681 The concentrated sulfuric acid, typically exhibiting a concentration higher than 93 wt% acid, which is produced with the process of the present invention has other advantages, such as:
1) Mercury in the flue gas stream can be oxidized using high temperature, >130 C, concentrated acid, >85 wt%, which can be the product sulfuric acid formed and recovered in unit 10. This occurs upstream of the rest of the process to make sure mercury does not contaminate the product acid.

2) The concentrated acid that is fed to absorber 9 (operating at low temperature, on the order of 40 C) and the high process pressure help to reduce NOx amounts in the gas stream leaving the process to uniquely low levels, i.e.
<50ppm.

3) The concentrated acid that is fed to the absorber 9 effectively reduces the moisture content of the gas stream leaving the process to very low levels. A dew point of less than -70 C can be expected if 93 wt% or greater sulfuric acid is used in the absorber 9 (for a process operating at -25 bar).
If the flue gas is to be further processed for inert removal as the case may be for carbon dioxide sequestration, this will eliminate the need to use any subsequent drying adsorbents before the flue gas is subjected to cooling in a subambient-temperature processing stage.
[00691 Other advantages of the present invention include that SO2, NOx and Hg can be recovered separately. Also, sulfuric acid and nitric acid are produced which are of high enough quality that they may be sold for an additional revenue stream. In addition, the process of the present invention operates at elevated pressure which serves to speed the rate of the homogeneous reactions involved in the process and to reduce the size of the equipment which is needed for the flue gas processing.

[00701 The recycling NOx circuit comprised of the NOx in the acid streams and the gas streams shown in Figure 2, is a preferred feature of this invention.
It concentrates the NOx in the system which serves to significantly reduce the necessary residence time of the process. The smaller equipment sizes of the process allowed by the elevated pressure operation and short residence times, allowed by the NOx recycle circuit, serves to reduce the capital cost and footprint of this SOx and NOx removal strategy.
[0071] The process of the present invention also permits any subsequent contaminant control devices, such as a selective catalytic reduction unit, mercury adsorbent bed, or water adsorbent bed to be eliminated. This serves to greatly reduce the cost associated with the flue gas processing operation.
[0072] Operating costs associated with the process of the present invention will also be reduced over a comparable wet-limestone based desulfurization process because this process will yield separate streams of concentrated saleable sulfuric and nitric acid. If the SOx and NOx is captured as acid and sold, the costs associated with purchase, transportation and disposal of limestone will be eliminated while additional income will be realized.
[0073] Additional embodiments of the present invention in addition to those described above may also be practiced. In case the purity of the acid streams produced is not high enough (with respect to residual NOx) for sale on the acid market, additional purification steps may be employed. If further NOx removal from sulfuric acid is necessary, it is evident to one of ordinary skill in the art that there are many processes of NOx removal from sulfuric acid that may also be employed. These processes may include the use of hydrazine, H202, sulfamic acid, and the like.
[0074] Although the embodiments shown in the Figures show only one unit at each stage of the process, each operating at one given pressure, it is within the scope of this invention to have multiple units at any stage or at each stage operating at a single or multiple pressures. Having multiple absorbers and/or reactors may allow for better control of the NO:NO2 ratio and for more complete NOx and/or SOx containment. Also, the catalytic stripping and/or recycle of NOx may be staged at different locations within a single absorber/reactor or may be staged in multiple absorber and/or reactors.
[0075] In another embodiment of this invention, shown in Figure 3, stripping unit 7 is not employed. This embodiment is useful if the amount of NOx in stream 120 is too low to provide significant amounts of stripped NOx into the flue gas stream 108. In such a case, stream 120 (which may be referred to in this embodiment as a NOx-enriched sulfuric acid stream) is sent directly to unit 10, and stream 117 from unit 11 as well as stream 108 are fed to reactor 8 whether or not streams 117 and 108 are joined before entering reactor 8.
[00761 In another embodiment of Figure 3, the operation of stripping unit 7 can be physically integrated with reactor 8 such that the features of both stripping unit 7 and reactor 8 are combined in a single vessel. In such a case, stream 120 is sent directly to unit 10, and stream 117 from unit 11 as well as stream 108 are fed to reactor 8 whether or not streams 117 and 108 are joined before entering reactor 8.
100771 Direct contact intercoolers and aftercoolers may also be used in this system for cooling of the flue gas. Direct contact intercooling is advantageous due to the large volume of gas which would otherwise need to be indirectly cooled. Water or any other solution including sulfuric and/or nitric acid may be used in these direct contact heat exchange stages.
[00781 In cases in which oxy-fuel combustion produces flue gas that contains only extremely low amounts of NOx, it may be necessary to add NOx in the form of NO, NO2, nitric acid, or ammonia to the process (for instance, into unit 7) to maintain efficient SO2 removal from the flue gas. Addition of NOx, nitric acid or ammonia may also be necessary during process startups to quickly build up the amount of NOx absorbed in the NOx-rich sulfuric acid to a level which is appropriate for efficient SO2 removal.
[00791 As stated above, the NOx-lean S02-depleted flue gas stream 1 I 1 can be used in another industrial or commercial process, combined with other additives, or further purified. Exemplary further purification is described in the following.
SUBAMBIENT-TEMPERATURE PROCESSING
[00801 The NOx-lean SO2-depleted flue gas stream 111 is fed to stage 60 for separation of 02, N2 and argon, as well as NOx and CO if present, from the carbon dioxide. Preferably the process used in this stage employs subambient-temperature processing, such as: partial condensation followed by distillation;
partial condensation followed by phase separation; first partial condensation followed by phase separation followed by further partial condensation of the gas stream from the first partial condensation followed by further phase separation.
[0081] Examples of preferred subambient-temperature processes are illustrated in Figures 4-9. Referring first to Figures 4-7, feed stream 111 from stage 60 and specifically from absorber 9 is introduced into a main heat exchanger 224 in .which it is partly cooled and then introduced into a reboiler 226 that serves to produce boil up or initiate an ascending vapor phase within distillation column 228. Feed stream Ill is then again introduced into main heat exchanger 224 in which it is fully cooled to at least partially liquefy carbon dioxide in stream 111.
The stream 111 is then introduced through an expansion valve 230 into column 228 to initiate a descending liquid phase within such column.

[0082] In a manner well known in this art, column 228 preferably has structured packing to contact the ascending vapor phase flowing up through the packing with a descending liquid flow of the liquid phase. Other vapor-liquid contacting elements known in the art could be used such as sieve trays. As a result of the contact, the descending liquid phase becomes evermore rich in carbon dioxide, the less volatile component and the ascending vapor phase becomes evermore rich in impurities that have a higher volatility than the carbon dioxide. Column 228 produces a carbon dioxide-lean column overhead stream 231 and a carbon dioxide-rich, liquid column bottom stream 244.

[0083] Column overhead stream 231 from column 228 is then passed through an auxiliary heat exchanger 232 so that the carbon dioxide in overhead stream 231 is at least partially liquefied. The carbon dioxide overhead stream 231 is then passed through a phase separator 234 to produce a carbon dioxide-depleted vapor stream 68 and a carbon dioxide-rich liquid stream 238. Carbon dioxide-rich liquid stream 238 is expanded through an expansion valve 240. Expansion through valve 240 provides refrigeration for the partial liquefaction of carbon dioxide overhead stream 231. Expanded stream 238 and stream 68 are passed through auxiliary heat exchanger 232 and through main heat exchanger 224.
[0084] Stream 68 is passed to stage 70 which is described herein.
[0085] Stream 238 after having passed through main heat exchanger 224 can be combined with stream 68 and fed to stage 70, or stream 238 can be recycled (not shown) to the inlet of an appropriate stage of a compressor 30.
100861 A carbon dioxide product stream 244 as a liquid can be extracted from column 228 and is composed of carbon dioxide-rich liquid column bottoms. The carbon dioxide product stream 244 can then be expanded in an expansion valve 246 to generate refrigeration for the process and can thereafter be vaporized within main heat exchanger 224 and compressed in a product compressor 95 to produce a compressed carbon dioxide stream 100 as the carbon dioxide product.
The product compressor 95 could be a multi-stage compressor with interstage cooling.

[00871 In the embodiment depicted in Figure 5, carbon dioxide product stream 244 is not expanded all at the same pressure but is split into subsidiary streams 252 and 254 and at least the subsidiary stream 252 is expanded by the use of expansion valve 256 to a pressure lower than the pressure to which stream 254 is expanded. Streams 252 and 254 are expanded to their respective expanded pressures by the use of expansion valves 256 and 258, respectively, which have different orifices for such purposes. Both subsidiary streams 252 and 254 are then vaporized in main heat exchanger 224. The resultant lower pressure subsidiary stream 262 is introduced into the inlet of product compressor 95. The higher pressure subsidiary stream 264 is introduced into an intermediate stage of product compressor 95. The compressed product stream 100 is recovered from compressor 95.
[00881 In the embodiment depicted in Figure 6, column overhead stream 231 can simply be passed into main heat exchanger 224. This recovers refrigeration from column overhead stream 231.
[00891 In the embodiment depicted in Figure 7, feed stream 111 after expansion through valve 230 is introduced into a phase separator 260 to produce a vapor phase stream 2262 and a liquid phase stream 2264. Liquid phase stream 2264 is introduced into column 228 to produce the carbon dioxide containing column bottoms 244 and vapor phase stream 231 which can be combined with stream 2262 and passed through auxiliary heat exchanger 232 as described in connection with the embodiment of the invention described with respect to Figure 4. Phase separator 260 could be used in any embodiment of the present invention.
100901 Figure 8 shows an alternative configuration of subambient-temperature processing based on partial condensation followed by one stage of phase separation. Feed stream 111 is cooled in a heat exchanger 224 against cold streams being warmed. Feed stream 111 is cooled to 0 F to -70 F to partially condense it and is then fed to a phase separator 129. A carbon dioxide product stream with > 90% purity (by volume), preferably > 95% purity, is withdrawn as a liquid stream 145. A carbon dioxide-lean stream from the phase separator 129 is recovered as a gaseous stream 161. The liquid stream 145 is expanded through at least one expansion valve 256. It will be advantageous to split stream 145 into two separate streams 252 and 254 and expand them through two expansion valves 256 and 258 to two different pressures. The pressure to which the carbon dioxide liquid product is expanded is usually 50 to 300 psia lower than the pressure of feed 111 to the subambient-temperature processing unit. The resultant expanded carbon dioxide product streams 262 and 264 and gaseous stream 161 are warmed through heat exchanger 224. The carbon dioxide-lean stream 68 is then fed to adsorption based or absorption based separation in unit 70. The carbon dioxide product streams 262 and 264 can be compressed and recovered as described herein.

[00911 Figure 9 shows another embodiment of subambient-temperature processing where partial condensation is followed by two stages of phase separation. The feed stream 111 is first cooled in heat exchanger 224 to 0 F
to -40 F to cause partial condensation, and is then fed to a phase separator 129.
The first carbon dioxide product is recovered as liquid stream 153 and expanded through expansion valve 256. The vapor stream 161 from phase separator 129 is further cooled in another heat exchanger 2264 to -20 F to -70 F to partially condense it. The partially condensed stream 161 is then fed to another phase separator 139. A second product carbon dioxide stream is recovered as liquid stream 155 which is expanded through expansion valve 258. Further carbon dioxide-depleted vapor stream 163 is recovered from the phase separator 139.
The expanded second carbon dioxide product stream 155 and vapor stream 163 are warmed through heat exchangers 2264 and 224 and the expanded first carbon dioxide product stream 153 is warmed through heat exchanger 224. The carbon dioxide-lean stream 68 and the two carbon dioxide product streams 262 and 264 are further processed as described herein.

[00921 Purified carbon dioxide is obtained from the subambient-temperature processing in one stream or in two streams such as streams 262 and 264 which may be at the same pressure or at two different pressures. The purified carbon dioxide stream or streams can if desired be compressed in e.g. a multistage compressor 95 to a pressure of 500 to 3000 psia, preferably to 1500 to 2500 psia.
Such compression is desirable for pipeline transport or other disposition of the stream. The purity of carbon dioxide is generally greater than 95%. Using the subambient-temperature process, 60 - 93 percent of carbon dioxide contained in stream 11 1 is recovered as product carbon dioxide in stream 100. The extent of recovery depends on the concentration of carbon dioxide in stream 111. The remaining carbon dioxide is contained in vent stream 68, which is usually at pressure close to the pressure of feed stream 111. The concentration of carbon dioxide in vent stream 68 is usually in the 25 - 40% range.

[00931 As illustrated in Figure 1, stream 68 is then fed to unit 70 where it undergoes further separation, by adsorption, by physical absorption or by chemical absorption. Unit 70 produces a carbon dioxide-rich stream 19 at 15 -psia and carbon dioxide depleted stream 72 at essentially the pressure of stream 68 that was fed to unit 70. The carbon dioxide-rich stream 19 is recycled and mixed with flue gas stream 105, 106, 107 or 108. By recovering additional carbon dioxide from vent stream 68 by processing in unit 70 and recycling it, the overall carbon dioxide recovery can be increased to the range of 96 - 99%.
Thus, the product stream 100 contains 96% to 99% of the carbon dioxide contained in flue gas stream 101.
ADSORPTION
100941 In this embodiment, vent stream 68 is passed on to a vacuum pressure swing adsorption (VPSA) unit 70. The VPSA unit contains multiple beds containing adsorbent that selectively adsorbs carbon dioxide. The VPSA unit produces a carbon dioxide-rich stream 19 at 15 - 20 psia and the carbon dioxide depleted stream 72 at essentially the pressure of stream 68 that was fed to the VPSA.

[00951 After the carbon dioxide concentration is increased by multiple depressurizations in unit 70 it can be used to produce the carbon dioxide product by further pressure reduction. For some adsorbents, depressurization from high to low pressure increases carbon dioxide concentration in the adsorbent bed. This step in the process can be used to eliminate several process steps as described in the prior art. Consequently, several pieces of rotating machinery (e.g., rinse compressor, purge compressor, recycle compressor) and associated power requirements can be eliminated, thus providing a process and system that enhances operation and improves efficiency.
[00961 In one embodiment of VPSA stage 70, the processes provide for flow through the evacuating bed (see for example, Figures 10-14). The flow through embodiments can be accomplished using a varying number of beds and pressure equalization steps. For example, flow through the evacuating bed can be accomplished with six beds and three pressure equalization steps (Figures 10-14).
Alternatively, flow through the evacuating bed can be accomplished with five beds and two pressure equalization steps (Figure 13) or seven beds and three pressure equalization steps (Figure 14). At any time during any of these processes, the beds will be in one of the following categories of steps: feed, depressurizations, evacuation, pressure equalizations, and repressurization.
In addition, a purge step can be included in the cycle for the embodiment shown in Figure 14.

[00971 In other alternative embodiments, the carbon dioxide product produced during the final depressurization step (DPf) is not passed through another bed under evacuation. Rather, this stream is mixed directly with the stream from the evacuating bed. In one preferred and exemplary embodiment, this can be accomplished with a carbon dioxide VPSA unit having six beds and three pressure equalization steps (Figures 15-17). In other embodiments, this can be accomplished by using a carbon dioxide VPSA unit having five beds and two pressure equalization steps (Figure 18). At any time during any of these processes, the beds will be in one of the following categories of steps: feed, depressurizations, evacuation, pressure equalizations, and repressurization.

[00981 Combinations of flow through and direct mixing can also be used. In such embodiments, a portion of the stream produced during the depressurization step (DPf) flows through the bed under evacuation and the remainder is directly mixed with the stream exiting the bed under evacuation.

[00991 In embodiments where increased plant capacity is desirable, the embodiments shown in Figures 19 and 20 can be utilized. More specifically, Figure 19 shows a cycle step chart for an embodiment of the present invention in which two pressure equalizations and eight beds are used with direct mixing.
In this embodiment, two beds are continuously on feed and at least two beds are continuously under evacuation. This arrangement is expected to allow for an increase in the capacity of the plant. Figure 20 illustrates a cycle step chart for an embodiment of the present invention in which two pressure equalizations and eleven beds are used with direct mixing. In this embodiment, three beds are continuously on feed and two beds are continuously under evacuation. This arrangement is also expected to allow for an increase in the capacity of the plant.
At any time during any of these processes, the beds will be in one of the following categories of steps: feed, depressurizations, evacuation, pressure equalizations, and repressurization.
[01001 In any of the embodiments, each bed is preferably packed with at least two layers of adsorbents. The type and sizing of the adsorbent layer toward the feed end (i.e. a water-selective adsorbent layer) in the bed is selected to remove moisture in the feed stream such that any residual moisture does not deteriorate the performance of the main (i.e., carbon dioxide-selective) adsorbent layer.
The water-selective adsorbent layer is also preferably capable of removing impurities (e.g., trace amounts of sulfur or heavy hydrocarbon compounds) from the feed stream, to the extent such impurities are present. The main, second adsorbent layer (i.e., the carbon dioxide-selective adsorbent layer) is used for selectively adsorbing carbon dioxide from the feed stream after sufficient moisture has been removed.
[01011 For the first adsorbent layer (i.e. the water-selective adsorbent layer, adsorbents such as activated alumina, silica gel or zeolite molecular sieve are preferred. These adsorbents are intended to be illustrative and other adsorbents capable of removing sufficient moisture are also suitable for use in accordance with the present invention. Preferred characteristics for such adsorbent(s) include: high crush strength capabilities, high attrition resistance, large bulk density, low inter-particle void, high heat capacity, large thermal conductivity, low-pressure drop and stable in liquid water.
[01021 The main layer of adsorbent (i.e., the carbon dioxide-selective adsorbent layer) following the water-selective adsorbent layer preferably has the following characteristics: high selectivity, high working capacity, fast kinetics and low heat of adsorption. Typical examples of such adsorbents include, but are not limited to: are NaY, HY, NaX, silica gel, and activated carbon. Other desired physical properties of the main layer adsorbent (i.e. the carbon dioxide-selective layer) include: high crush strength, high attrition resistance, large bulk density, low inter-particle void, high heat capacity, large thermal conductivity and low-pressure drop during the feed and evacuation steps.

[01031 Those skilled in the art will appreciate that a composite mixed layer containing both adsorbents could be used in the present invention so long as the characteristics of the adsorbents are satisfied.

[01041 Referring now to Figures 10-12, a first embodiment of the present invention having six beds (A1-A6) and using ten steps with flow through the evacuating bed to produce enriched carbon dioxide is illustrated. The process steps include:

1. Feed Step. Feed stream 68 containing carbon dioxide at a high pressure between about 100-500 psia (for example, about 375 psia) is fed to the carbon dioxide VPSA unit. After a predetermined time or after carbon dioxide breakthrough from the bed on the feed 68, the feed step is terminated.
2. Co-Current (CoC) Depressurization 1 (DPI). The carbon dioxide VPSA
bed, which has finished the feed step is now at high feed pressure (e.g., 100-psia), is depressurized to a medium pressure (e.g., 80-400 psia) in a direction the same (shown in Figure 10) or opposite (not shown in Figure 10) as the feed flow.

3. Co-Current (CoC) Depressurization 2 (DP2). The carbon dioxide VPSA
bed, which is now at some medium pressure (e.g., 80-400 psia), is further depressurized to a lower pressure (e.g., 60-300 psia) in a direction the same as (shown in Figure 10) or opposite (not shown in Figure 10) as the feed flow.
4. Co-Current (CoC) Depressurization 3 (DP3). The carbon dioxide VPSA
bed, which is now at some medium pressure (e.g., 60-300 psia), is further depressurized to a lower pressure (e.g., 50-200 psia) in a direction the same as (shown in Figure 10) or opposite (not shown in Figure 10) as the feed flow.
5. Final Depressurization (DPf). The carbon dioxide VPSA bed, which is now at a pressure lower than at the start of step 4 (about 50-200 psia) is further depressurized to a pressure close to ambient (about 20 psia) in a direction the same as (shown in Figure 10) and/or the opposite (not shown in Figure 10) the feed flow.
As shown by the arrows in Figure 10 (i.e. arrows from DPf to bed under evacuation), the stream from this step (DPf) flows through the bed under evacuation (e.g. in Figure 10: bed 1 to bed 6, bed 2 to bed 1, bed 3 to bed 2, bed 4 to bed 3, bed 5 to bed 4 or bed 6 to bed 5 on the respective cycle steps).
6. Evacuation. The carbon dioxide VPSA bed, which is now close to ambient pressure (about 20 psia), is evacuated to a predetermined low pressure, a subambient pressure (about 1-12 psia) in a direction the same as (not shown in Figure 10) or opposite (shown in Figure 10) to the feed flow. As shown in Figure and outlined in the description of step 5 (DPf) above, this bed is receiving gas from another bed in the DPf step. The gas from the bed under evacuation constitutes the carbon dioxide product stream.
7. Countercurrent (CcC) Pressure Equalization 3 (PE3). The evacuated bed is now pressure equalized to a pressure range of the gas produced in step 4 (DP3) (i.e., to about 50-200 psia) in a direction the same as (not shown in Figure 10) or opposite (shown in Figure 10) to the feed flow. This step increases carbon dioxide recovery by keeping the carbon dioxide from step 4 within the VPSA
system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

8. Countercurrent (CcC) Pressure Equalization 2 (PE2). The bed pressure equalized in step 7 is now pressure equalized to a pressure range of the gas produced in step 3 (DP2) (i.e., to about 60-300 psia) in a direction the same as (not shown in Figure 10) or opposite (shown in Figure 10) to the feed flow.
This step increases carbon dioxide recovery by keeping the carbon dioxide from step within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

9. Countercurrent Pressure (CcC) Equalization 1 (PEI). The bed pressure equalized in step 8 is further pressure equalized to a pressure range of the gas produced in step 2 (DP I) (i.e., to about 80-400 psia) in a direction the same as (not shown in Figure 10) or opposite (shown in Figure 10) to the feed flow.
This step further increases carbon dioxide recovery by keeping the carbon dioxide from step 2 within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

10. Rcpressurization (FcRP). The pressure-equalized bed is repressurized to a feed pressure (100-500 psia) either by the feed gas or by part of the effluent generated from another bed in step 1 (i.e. feed effluent). Following repressurization to feed pressure, this bed is now ready to go back to step 1.
10105J The ten-step process described is for one cycle for one bed in the carbon dioxide VPSA unit. The above ten steps for this flow through the evacuating bed embodiment are carried out in a cyclic manner with the other beds in the unit such that feed-into and feed-effluent from step 1 are continuous. In addition, the evacuation step (number 6) is designed to be continuous. This ensures that the vacuum pump operates continuously, and that there is no break in feed-into the carbon dioxide VPSA unit. Six adsorption beds are utilized in the embodiment described above to maintain the continuity of the key process steps.

[0106] Exemplary corresponding hardware and a flow schematic of the carbon dioxide VPSA process corresponding to the cycle shown in Figure 10 is depicted in Figure 11. The various valves in Figure 11 can be operated in the manner illustrated in Figure 12 to carry out the ten steps in the six-bed process as described hereinabove. It should be appreciated that pressures and step durations shown are only for illustrative purposes. Those skilled in the art will appreciate that other combinations of pressures and step durations may be used.

[01071 As can be appreciated from the above description, the present invention thus relies upon depressurizations of at least one carbon dioxide-selective adsorbent from high pressure to low pressure to increase carbon dioxide concentration in the bed. After carbon dioxide concentration is increased, it produces the carbon dioxide product by further pressure reduction. This became possible based on the recognition that for some adsorbents, pressure reduction from high to low pressure increases carbon dioxide concentration on the adsorbent.

[0108] In the embodiment shown in Figures 10-12 and as described, the gas produced during the final depressurization (step number 5, DPf) flows through the bed under evacuation as shown by the arrows in the cycle step chart in Figure 10.
[01091 Alternative and additional exemplary embodiments that utilize the final depressurization gas stream (DPf) flow through the evacuating bed are illustrated in Figures 13 and 14.

[01101 Referring now to Figure 13, a cycle step chart for an eight-step process that utilizes five beds and two pressure equalization steps is shown. These cycle steps are carried out in a similar to those steps described above with reference to Figure 10, except that steps DP3 and PE3 have been eliminated. More specifically, the cycle steps for Figure 13 include the following:
1. Feed Step. Feed stream 68 containing carbon dioxide at a high pressure between about 100-500 psia (for example, about 375 psia) is fed to carbon dioxide VPSA unit 70. After a predetermined time or after carbon dioxide breakthrough from the bed on the feed 68, the feed step is terminated.

2. Co-Current (CoC) Depressurization 1 (DPI). The carbon dioxide VPSA bed, which has finished the feed step is now at high feed pressure (e.g., 100-500 psia), is depressurized to a medium pressure (e.g., 80-400 psia) in a direction the same (shown in Figure 13) or opposite (not shown in Figure 13) as the feed flow.
3. Co-Current (CoC) Depressurization 2 (DP2). The carbon dioxide VPSA bed, which is now at some medium pressure (e.g., 80-400 psia), is further depressurized to a lower pressure (e.g., 60-300 psia) in a direction the same as (shown in Figure 13) or opposite (not shown in Figure 13) as the feed flow.
4. Final Depressurization (DPf). The carbon dioxide VPSA bed, which is now at a pressure lower than at the start of step 4 (about 50-200 psia) is further depressurized to a pressure close to ambient (about 20 psia) in a direction the same as (shown in Figure 13) and/or the opposite (not shown in Figure 13) the feed flow.
As shown by the arrows in Figure 13 (i.e. arrows from DPf to bed under evacuation), the stream from this step (DPf) flows through the bed under evacuation (e.g. as shown in Figure 13: bed 1 to bed 5, bed 2 to bed 1, bed 3 to bed 2, bed 4 to bed 3 or bed 5 to bed 4 on the respective cycle steps).
5. Evacuation. The carbon dioxide VPSA bed, which is now close to ambient pressure (about 20 psia), is evacuated to a predetermined low pressure, a subambient pressure (about 1-12 psia) in a direction the same as (not shown in Figure 13) or opposite (shown in Figure 13 to the feed flow. As shown in Figure 13 and as outlined in the description of step 4 (DPf) above, this bed is receiving gas from another bed in the DPf step for the duration of the DPf step. The gas from the bed under evacuation constitutes the carbon dioxide product stream.
6. Countercurrent (CcC) Pressure Equalization 2 (PE2). The evacuated bed is now pressure equalized to a pressure range of the gas produced in step (DP2) (i.e., to about 60-300 psia) in a direction the same as (not shown in Figure 13) or opposite (shown in Figure 13) to the feed flow. This step increases carbon dioxide recovery by keeping the carbon dioxide from step 3 within the VPSA
system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

7. Countercurrent Pressure (CcC) Equalization I (PEI). The bed pressure equalized in step 6 is further pressure equalized to a pressure range of the gas produced in step 1 (DPI) (i.e., to about 80-400 psia) in a direction the same as (not shown in Figure 13) or opposite (shown in Figure 13) to the feed flow.
This step further increases carbon dioxide recovery by keeping the carbon dioxide from step 2 within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

8. Repressurization (FeRP). The pressure-equalized bed is repressurized to a feed pressure (100-500 psia) either by the feed gas or by part of the effluent generated from another bed in step I (i.e. feed effluent). Following repressurization to feed pressure, this bed is now ready to go back to step 1.
[01111 The eight-step process described is for one cycle for one bed in the carbon dioxide VPSA unit. The above eight steps for this flow through the evacuating bed embodiment are carried out in a cyclic manner with the other beds in the unit such that feed-into and feed-effluent from step I are continuous. In addition, the evacuation step (number 5) is designed to be continuous. This ensures that the vacuum pump operates continuously, and that there is no break in feed-into the carbon dioxide VPSA unit. Five adsorption beds are utilized in the embodiment described above to maintain the continuity of the key process steps.
[01121 Referring now to Figure 14, a cycle step chart for an eleven-step process that utilizes seven beds and three pressure equalization steps is shown. These cycle steps are carried out in a similar manner to those steps described above with reference to Figure 10, except that an additional step (Rf) is included between the final depressurization step (DPf) and the evacuation step. More specifically, the cycle steps for Figure 14 include the following:
1. Feed Step. Feed stream 68 containing carbon dioxide at a high pressure between about 100-500 psia (for example, about 375 psia) is fed to carbon dioxide VPSA unit 70. After a predetermined time or after carbon dioxide breakthrough from the bed on the feed 68, the feed step is terminated.

2. Co-Current (CoC) Depressurization 1 (DPI). The carbon dioxide VPSA bed, which has finished the feed step is now at high feed pressure (e.g., 100-500 psia), is depressurized to a medium pressure (e.g., 80-400 psia) in a direction the same (shown in Figure 14) or opposite (not shown in Figure 14) as the feed flow.

3. Co-Current (CoC) Depressurization 2 (DP2). The carbon dioxide VPSA bed, which is now at some medium pressure (e.g., 80-400 psia), is further depressurized to a lower pressure (e.g., 60-300 psia) in a direction the same as (shown in Figure 14) or opposite (not shown in Figure 14) as the feed flow.
4. Co-Current (CoC) Depressurization 3 (DP3). The carbon dioxide VPSA bed, which is now at some medium pressure (e.g., 60-300 psia), is further depressurized to a lower pressure (e.g., 50-200 psia) in a direction the same as (shown in Figure 14) or opposite (not shown in Figure 14) as the feed flow.
5. Final Depressurization (DPf). The carbon dioxide VPSA bed, which is now at a pressure lower than at the start of step 4 (about 50-200 psia) is further depressurized to a pressure close to ambient (about 20 psia) in a direction the same as (shown in Figure 14) and/or the opposite (not shown in Figure 14) the feed flow.

6. Receive Purge (Rf). The stream produced by DPf (e.g., bed I in Figure 14) is fed to another bed having completed DPf, but not yet under evacuation (e.g., bed 7 in Figure 14). During this time (duration of the Rf step), the effluent (e.g., bed 7 in Figure 14) flows to tank 442 as carbon dioxide product.
During the remaining time period of DPf of bed 1, the gas flows through the bed under evacuation (e.g., bed 7 in Figure 14).

7. Evacuation. The carbon dioxide VPSA bed, which is now close to ambient pressure (about 20 psia), is evacuated to a predetermined low pressure, a subambient pressure (about 1-12 psia) in a direction the same as (not shown in Figure 14) or opposite (shown in Figure 14) to the feed flow. As shown in Figure 14, this bed (bed 1) is receiving gas from another bed in the DPf step (bed 2). The gas from the bed under evacuation constitutes at least part of the carbon dioxide product stream.
8. Countercurrent (CcC) Pressure Equalization 3 (PE3). The evacuated bed is now pressure equalized to a pressure range of the gas produced in step (DP3) (i.e., to about 50-200 psia) in a direction the same as (not shown in Figure 14) or opposite (shown in Figure 14) to the feed flow. This step increases carbon dioxide recovery by keeping the carbon dioxide from step 4 within the VPSA
system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

9. Countercurrent (CcC) Pressure Equalization 2 (PE2). The bed pressure equalized in step 7 is now pressure equalized to a pressure range of the gas produced in step 3 (DP2) (i.e., to about 60-300 psia) in a direction the same as (not shown in Figure 14) or opposite (shown in Figure 14) to the feed flow.
This step increases carbon dioxide recovery by keeping the carbon dioxide from step within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

10. Countercurrent Pressure (CcC) Equalization I (PEI). The bed pressure equalized in step 9 is further pressure equalized to a pressure range of the gas produced in step 2 (DP 1) (i.e., to about 80-400 psia) in a direction the same as (not shown in Figure 14) or opposite (shown in Figure 14) to the feed flow.
This step further increases carbon dioxide recovery by keeping the carbon dioxide from step 2 within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.
11. Repressurization (FeRP). The pressure-equalized bed is repressurized to a feed pressure (100-500 psia) either by the feed gas or by part of the effluent generated from another bed in step 1 (i.e. feed effluent).
Following repressurization to feed pressure, this bed is now ready to go back to step 1.
[01131 The eleven-step process described is for one cycle for one bed in the carbon dioxide VPSA unit. The above eleven steps for this flow through the evacuating bed embodiment are carried out in a cyclic manner with the other beds in the unit such that feed-into and feed-effluent from step 1 are continuous.
In addition, the evacuation step (number 7) is designed to be continuous. This ensures that the vacuum pump operates continuously, and that there is no break in feed-into the carbon dioxide VPSA unit. Seven adsorption beds are utilized in the embodiment described above to maintain the continuity of the key process steps.
[01141 Referring now to Figures 15-17, an embodiment of the present invention having six beds (A1-A6) and using ten steps with direct mixing of carbon dioxide gas from the DPf step and the evacuation step to produce a final carbon dioxide-enriched gas is illustrated. The process steps include:
1. Feed Step. Feed stream 68 containing carbon dioxide at a high pressure (for example, about 375 psia) is fed to carbon dioxide VPSA unit 70.
After a predetermined time or after carbon dioxide breakthrough from the bed on the feed 68, the feed step is terminated.

2. Co-Current (CoC) Depressurization 1 (DPI). The carbon dioxide VPSA bed, which has finished the feed step is now at high feed pressure (e.g., 100-500 psia), is depressurized to a medium pressure (e.g., 80-400 psia) in a direction the same (shown in Figure 15) or opposite (not shown in Figure 15) as the feed flow.
3. Co-Current (CoC) Depressurization 2 (DP2). The carbon dioxide VPSA bed, which is now at some medium pressure (e.g., 80-400 psia), is further depressurized to a lower pressure (e.g., 60-300 psia) in a direction the same as (shown in Figure 15) or opposite (not shown in Figure 15) as the feed flow.
4. Co-Current (CoC) Depressurization 3 (DP3). The carbon dioxide VPSA bed, which is now at some medium pressure (e.g., 60-300 psia), is further depressurized to a lower pressure (e.g., 50-200 psia) in a direction the same as (shown in Figure 15) or opposite (not shown in Figure 15) as the feed flow.

5. Final Depressurization (DPf). The carbon dioxide VPSA bed, which is now at a pressure lower than at the start of step 4 (about 50-200 psia) is further depressurized to a pressure close to ambient (about 20 psia) in a direction the same as (not shown in Figure 15) and/or the opposite (shown in Figure 15) the feed flow to produce carbon dioxide product 438 shown in Figure 16. This stream may constitute part of the carbon dioxide product (stream 19).
6. Evacuation. The carbon dioxide VPSA bed, which is now close to ambient pressure (about 20 psia), is evacuated to a predetermined low pressure, a subambient pressure (about 1-12 psia) in a direction the same as (not shown in Figure 15) or opposite (shown in Figure 15) to the feed flow. The gas from the bed under evacuation (stream 436 in Figure 16) constitutes part of the carbon dioxide product stream (stream 19). Optionally, stream 436 can be further compressed using a blower (not shown) prior to passing to tank 442.
7. Countercurrent (CcC) Pressure Equalization 3 (PE3). The evacuated bed is now pressure equalised to a pressure range of the gas produced in step (DP3) (i.e., to about 50-200 psia) in a direction the same as (not shown in Figure 15) or opposite (shown in Figure 15) to the feed flow. This step increases carbon dioxide recovery by keeping the carbon dioxide from step 4 within the VPSA
system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.
8. Countercurrent (CcC) Pressure Equalization 2 (PE2). The bed pressure equalized in step 7 is now pressure equalized to a pressure range of the gas produced in step 3 (DP2) (i.e., to about 60-300 psia) in a direction the same as (not shown in Figure 15) or opposite (shown in Figure 15) to the feed flow.
This step increases carbon dioxide recovery by keeping the carbon dioxide from step within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.
9. Countercurrent Pressure (CcC) Equalization 1 (PEI). The bed pressure equalized in step 8 is further pressure equalized to a pressure range of the gas produced in step 2 (DPI) (i.e., to about 80-400 psia) in a direction the same as (not shown in Figure 15) or opposite (shown in Figure 15) to the feed flow.
This step further increases carbon dioxide recovery by keeping the carbon dioxide from step 2 within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.
10. Repressurization (FeRP). The pressure-equalized bed is repressurized to a feed pressure (100-500 psia) either by the feed gas or by part of the effluent generated from another bed in step I (i.e. feed effluent). Following repressurization to feed pressure, this bed is now ready to go back to step 1.
[01151 As further shown in Figure 15, carbon dioxide product 19 is formed of carbon dioxide from streams 438 (step 6) and 436 (step 7) fed to product tank 442. Product 19 is expected to have a carbon dioxide purity level of approximately 80 mole percent or greater.
101161 The ten-step process described is for one cycle for one bed in the carbon dioxide VPSA unit. The above ten steps for this direct mixing embodiment are carried out in a cyclic manner with the other beds in the unit such that feed-into and feed-effluent from step 1 are continuous. In addition, the evacuation step (number 6) is designed to be continuous. This ensures that the vacuum pump operates continuously, and that there is no break in feed-into the carbon dioxide VPSA unit. Six adsorption beds are utilized in the embodiment described above to maintain the continuity of the key process steps.

101171 Exemplary corresponding hardware and a flow schematic of the carbon dioxide VPSA process corresponding to the cycle shown Figure 15 is depicted in Figure 16. The various valves in Figure 16 can be operated in the manner illustrated in Figure 17 to carry out the ten steps in the six-bed process as described hereinabove. It should be appreciated that pressures and step durations shown are only for illustrative purposes. Those skilled in the art will appreciate that other combinations of pressures and steps may be used.

101181 In the embodiment shown in Figures 15-17 and as described herein, the gas produced during the final depressurization step (DPf) is mixed with the evacuated gas from step number 6.
[01191 Another exemplary embodiment that utilizes direct mixing of the final depressurization gas stream (DPf) with the gas produced by evacuation bed is illustrated in Figure 18.

101201 Referring now to Figure 18, a cycle step chart for an eight-step process that utilizes five beds and two pressure equalization steps is shown. These cycle steps are carried out in a similar manner to those steps described above with reference to Figure 15, except that steps DP3 and PE3 have been eliminated.
More specifically, the cycle steps for Figure 18 include the following:
1. Feed Step. Feed stream 68 containing carbon dioxide at a high pressure between about 100-500 psia (for example, about 375 psia) is fed to carbon dioxide VPSA unit 70. After a predetermined time or after carbon dioxide breakthrough from the bed on the feed 68, the feed step is terminated.
2. Co-Current (CoC) Depressurization 1 (DPI). The carbon dioxide VPSA
bed, which has finished the feed step is now at high feed pressure (e.g., 100-psia), is depressurized to a medium pressure (e.g., 80-400 psia) in a direction the same (shown in Figure 18) or opposite (not shown in Figure 18) as the feed flow.
3. Co-Current (CoC) Depressurization 2 (DP2). The carbon dioxide VPSA
bed, which is now at some medium pressure (e.g., 80-400 psia), is further depressurized to a lower pressure (e.g., 60-300 psia) in a direction the same as (shown in Figure 18) or opposite (not shown in Figure 18) as the feed flow.
4. Final Depressurization (DPf). The carbon dioxide VPSA bed, which is now at a pressure lower than at the start of step 4 (about 50-200 psia) is further depressurized to a pressure close to ambient (about 20 psia) in a direction the same as (not shown in Figure 18) and/or the opposite (shown in Figure 18) the feed flow to produce carbon dioxide product 438. This stream may constitute part of the carbon dioxide product (stream 19).
5. Evacuation. The carbon dioxide VPSA bed, which is now close to ambient pressure (about 20 psia), is evacuated to a predetermined low pressure, a subambicnt pressure (about 1-12 psia) in a direction the same as (not shown in Figure 18) or opposite (shown in Figure 18) to the feed flow. The gas from the bed under evacuation (stream 36a in Figure 16) constitutes part of the carbon dioxide product stream (stream 19). Optionally, stream 436 can be further compressed using a blower (not shown) prior to passing to tank 442.
6. Countercurrent (CcC) Pressure Equalization 2 (PE2). The evacuated bed is now pressure equalized to a pressure range of the gas produced in step 3 (DP2) (i.e., to about 60-300 psia) in a direction the same as (not shown in Figure 18) or opposite (shown in Figure 18) to the feed flow. This step increases carbon dioxide recovery by keeping the carbon dioxide from step 3 within the VPSA
system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.

7. Countercurrent Pressure (CcC) Equalization I (PEI). The bed pressure equalized in step 6 is further pressure equalized to a pressure range of the gas produced in step 2 (DPI) (i.e., to about 80-400 psia) in a direction the same as (not shown in Figure 18) or opposite (shown in Figure 18) to the feed flow.
This step further increases carbon dioxide recovery by keeping the carbon dioxide from step 2 within the VPSA system. This minimizes carbon dioxide loss by eliminating the need to send the carbon dioxide to a waste stream.
8. Repressurization (FeRP). The pressure-equalized bed is repressurized to a feed pressure (100-500 psia) either by the feed gas or by part of the effluent generated from another bed in step I (i.e. feed effluent). Following repressurization to feed pressure, this bed is now ready to go back to step 1.
[0121] The carbon dioxide product stream 19 is formed of carbon dioxide from streams 438 (step 4) and 436 (step 5) in product tank 442.
[0122] The eight-step process described is for one cycle for one bed in the carbon dioxide VPSA unit. The above eight steps for this direct mixing embodiment are carried out in a cyclic manner with the other beds in the unit such that feed-into and feed-effluent from step 1 are continuous. In addition, the evacuation step (number 5) is designed to be continuous. This ensures that the vacuum pump operates continuously, and that there is no break in feed-into the carbon dioxide VPSA unit. Five adsorption beds are utilized in the embodiment described above to maintain the continuity of the key process steps.

[0123] It is also expected that the present invention can be modified to produce higher amounts of carbon dioxide and thus high plant capacity. For example, one may need or desire to process higher feed flow rates than may be handled by a single vacuum train or single vessel (due to fluidization or transportation limitations). In such situations, the process steps may be arranged such that at least two beds are on feed and at least two beds are under evacuation all the time.
Such exemplary cycle step charts and arrangement are shown in Figures 19 and 20. Alternatively or in addition, multiple trains can be used.

ABSORPTION
[01241 When stage 70 uses physical absorption with solvents such as selexol and rectisol, it can be placed just downstream of subambient-temperature processing stage 60. The carbon dioxide -depleted stream from such a physical absorption unit will be generally free of moisture. Physical absorption units process vent stream 68 from stage 60 and produce carbon dioxide -rich stream 19 and carbon dioxide -lean stream 72.
[01251 When stage 70 uses chemical absorption with reactant streams such as an aqueous solution of alkyl-substituted amine, ammonia or potassium carbonate, stream 68 is passed to the chemical absorption system 70 where it is treated by any known method in which the gaseous stream 68 is contacted with an aqueous solution of alkylamine, ammonia or potassium carbonate to absorb carbon dioxide from the gaseous stream into the aqueous stream, and the carbon dioxide is subsequently stripped from the resulting carbon dioxide-enriched aqueous stream.
101261 Figure 21 shows a flowsheet applicable to physical absorption and chemical absorption based carbon dioxide separation systems. The carbon dioxide -containing stream 68 is introduced into absorber 501 from the bottom.
Stream 505 of solvent (as that term is used respectively with respect to physical absorption and chemical absorption processes) is fed to absorber 501 from the top.
The solvent absorbs carbon dioxide from the feed stream. The resulting carbon dioxide-laden stream 510 is heated in heat exchanger 512 by recovering heat from carbon dioxide -lean solvent 520. The heated carbon dioxide -laden stream 513 is fed to the stripper 503. Optionally, the stripper is heated from the bottom by supplying heat via reboiler 530. A carbon dioxide-rich stream 19 is recovered from the top of stripper 503. The carbon dioxide -lean solvent 520 is cooled in heat exchanger 512 and then in cooler 523 and recycled to absorber 501 as stream 505.

Claims (53)

1. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid with said gaseous feed stream and with NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2; and (D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid.
2. A process according to claim 1 wherein said NOx-rich sulfuric acid is formed by absorbing NOx into said NOx-lean sulfuric acid.
3. A process according to claim 1 wherein said NOx-rich sulfuric acid is formed by absorbing NOx into said NOx-reduced sulfuric acid.
4. A process according to claim 1 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
5. A process according to claim 1-wherein said gascous feed stream of carbon dioxide is formed by combustion.
6. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;

(B) contacting NOx-rich sulfuric acid with said gaseous feed stream and NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid; and (E) reacting water and oxygen with said NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide.
7. A process according to claim 6 wherein NOx-rich sulfuric acid formed in step (E) is contacted in step (B) with said gaseous feed stream.
8. A process according to claim 6 wherein said NOx-rich sulfuric acid is formed by absorbing NOx into said NOx-lean sulfuric acid.
9. A process according to claim 6 wherein said NOx-rich sulfuric acid is formed by absorbing NOx into said NOx-reduced sulfuric acid.
10. A process according to claim 6 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
11. A process according to claim 6 wherein said gaseous feed stream of carbon dioxide is formed by combustion.
12. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid with said gaseous feed stream to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide; and (D) absorbing NOx from said SO2-depleted NOx-containing gaseous carbon dioxide into one or both of NOx-reduced sulfuric acid and NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide.
13. A process according to claim 12 wherein NOx-rich sulfuric acid formed in one or both of steps (C) and (D) is contacted in step (B) with said gaseous feed stream.
14. A process according to claim 12 wherein NOx-rich sulfuric acid formed in both of steps (C) and (D) is contacted in step (B) with said gaseous feed stream.
15. A process according to claim 12 wherein NOx is absorbed in step (D) into NOx-reduced sulfuric acid formed in step (B).
16. A process according to claim 12 wherein NOx is absorbed in step (D) into NOx-lean sulfuric acid formed in step (C).
17. A process according to claim 12 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
18. A process according to claim 12 wherein said gaseous feed stream of carbon dioxide is formed by combustion.
19. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) contacting NOx-rich sulfuric acid with said gaseous feed stream and with NO2 desorbed in step (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;
(E) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and SO2-depleted NOx-containing carbon dioxide; and (F) absorbing NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted carbon dioxide.
20. A process according to claim 19 wherein NOx-rich sulfuric acid formed in one or both of steps (E) and (F) is contacted in step (B) with said gaseous feed stream.
21. A process according to claim 19 wherein NOx-rich sulfuric acid formed in both of steps (E) and (F) is contacted in step (B) with said gaseous feed stream.
22. A process according to claim 19 wherein NOx is absorbed in step (D) into NOx-reduced sulfuric acid formed in step (B).
23. A process according to claim 19 wherein NOx is absorbed in step (D) into NOx-lean sulfuric acid formed in step (C).
24. A process according to claim 19 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
25. A process according to claim 19 wherein said gaseous feed stream of carbon dioxide is formed by combustion.
26. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) converting NO in NOx-rich sulfuric acid to NO2, and desorbing NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(C) controlling the amount of desorbed NO2 fed to step (D) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;
(D) reacting water and oxygen with NOx and sulfur dioxide in said feed stream and desorbed NO2 to form NOx-rich sulfuric acid and SO2-depleted NOx-containing carbon dioxide; and (E) absorbing NOx from said SO2-depleted NOx-containing carbon dioxide into said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted carbon dioxide.
27. A process according to claim 26 wherein NOx-rich sulfuric acid formed in one or both of steps (D) and (E) is contacted in step (B) with said gaseous feed stream.
28. A process according to claim 26 wherein NOx-rich sulfuric acid formed in both of steps (D) and (E) is contacted in step (B) with said gaseous feed stream.
29. A process according to claim 26 wherein NOx is absorbed in step (E) into NOx-lean sulfuric acid formed in step (B).
30. A process according to claim 26 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
31. A process according to claim 26 wherein said gaseous feed stream of carbon dioxide is formed by combustion.
32. Apparatus for treating gaseous carbon dioxide, comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO

in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
and (C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO.
33. Apparatus for treating gaseous carbon dioxide, comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;

(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO

in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO; and (D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide.
34. Apparatus for treating gaseous carbon dioxide, comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;

(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO

in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;

(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide; and (E) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide.
35. Apparatus for treating gaseous carbon dioxide, comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO

in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide; and (E) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide.
36. Apparatus for treating gaseous carbon dioxide, comprising (A) a converting unit to receive NOx-rich sulfuric acid which can catalytically convert NO in said NOx-rich sulfuric acid to NO2 and desorb NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(B) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(C) a reactor to receive NO2 desorbed in unit (A) and gaseous carbon dioxide that contains NOx and sulfur dioxide, and to react NOx and sulfur dioxide in said carbon dioxide with water and oxygen and said desorbed NO2 to form NOx-rich sulfuric acid and SO2-depeleted NOx-containing gaseous carbon dioxide; and (D) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide.
37. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;

(B) contacting NOx-rich sulfuric acid with said gaseous feed stream and NO2 desorbed in step (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;

(C) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;
(E) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and SO2-depleted NOx-containing carbon dioxide;
(F) absorbing NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted carbon dioxide;
(G) subjecting the NOx-lean SO2-depleted carbon dioxide to a subambient-temperature recovery process, employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery process, to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream;
(H) separating the vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption; and (I) recycling said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
38. A process according to claim 37 wherein in step (G) said refrigeration is provided only by expansion of said at least one liquid carbon dioxide product stream formed by said subambient-temperature recovery process.
39. A process according to claim 37 wherein NOx-rich sulfuric acid formed in one or both of steps (E) and (F) is contacted in step (B) with said gaseous feed stream.
40. A process according to claim 37 wherein NOx-rich sulfuric acid formed in both of steps (E) and (F) is contacted in step (B) with said gaseous feed stream.
41. A process according to claim 37 wherein NOx is absorbed in step (D) into NOx-reduced sulfuric acid formed in step (B).
42. A process according to claim 37 wherein NOx is absorbed in step (D) into NOx-lean sulfuric acid formed in step (C).
43. A process according to claim 37 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
44. A process according to claim 37 wherein said gaseous feed stream of carbon dioxide is formed by combustion.
45. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;
(B) converting NO in NOx-rich sulfuric acid formed in one or both of steps (D) and (E) to NO2, and desorbing NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(C) controlling the amount of desorbed NO2 fed to step (D) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid;

(D) reacting water and oxygen with NOx and sulfur dioxide in said feed stream and desorbed NO2 to form NOx-rich sulfuric acid and SO2-depleted NOx-containing carbon dioxide;

(E) absorbing NOx from said SO2-depleted NOx-containing carbon dioxide into said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted carbon dioxide;
(F) subjecting the NOx-lean SO2-depleted carbon dioxide to a subambient-temperature recovery process, employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery process, to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream;
(G) separating the vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption; and (H) recycling said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
46. A process according to claim 45 wherein in step (F) said refrigeration is provided only by expansion of said at least one liquid carbon dioxide product stream formed by said subambient-temperature recovery process.
47. A process according to claim 45 wherein NOx is absorbed in step (E) into NOx-lean sulfuric acid formed in step (B).
48. A process according to claim 45 further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid.
49. A process according to claim 45 wherein said gaseous feed stream of carbon dioxide is formed by combustion.
50. A process for treating gaseous carbon dioxide, comprising (A) providing a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar;

(B) contacting NOx-rich sulfuric acid with said gaseous feed stream to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(C) reacting water and oxygen with the NOx-augmented gaseous carbon dioxide to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide;

(D) absorbing NOx from said SO2-depleted NOx-containing gaseous carbon dioxide into one or both of NOx-reduced sulfuric acid and NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide;
(E) subjecting the NOx-lean SO2-depleted carbon dioxide to a subambient-temperature recovery process, employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery process, to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream;

(F) separating the vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption; and (G) recycling said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
51. Apparatus for treating gaseous carbon dioxide, comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;

(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO

in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;

(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide;
(E) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide;
(F) a subambient-temperature recovery unit coupled to said absorber to receive said NOx-lean SO2-depleted carbon dioxide therefrom to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery unit;
(G) a vent stream separation unit coupled to said subambient-temperature recovery unit to receive said vent stream therefrom and separate said vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption;
and wherein said vent stream separation unit is coupled to said carbon dioxide-containing feed stream to feed said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
52. Apparatus for treating gaseous carbon dioxide, comprising (A) a stripping unit in which NOx-rich sulfuric acid can be contacted with a gaseous feed stream of carbon dioxide that also comprises NOx and sulfur dioxide, and that is at a pressure of at least 2 bar and with NO2 desorbed in the converting unit (B) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that comprises SO2 and NO2;
(B) a converting unit which is coupled to said stripping unit to receive NOx-reduced sulfuric acid therefrom which can catalytically convert NO

in said NOx-reduced sulfuric acid to NO2 and desorb said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2, and which is coupled to said stripping unit to feed desorbed NO2 to said stripping unit;
(C) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(D) a reactor coupled to said stripping unit to receive said NOx-augmented gaseous carbon dioxide therefrom and react it with water and oxygen to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide; and (E) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one or both of said NOx-reduced sulfuric acid and said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-lean SO2-depleted gaseous carbon dioxide.
(F) a subambient-temperature recovery unit coupled to said absorber to receive said NOx-lean SO2-depleted carbon dioxide therefrom to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery unit;

(G) a vent stream separation unit coupled to said subambient-temperature recovery unit to receive said vent stream therefrom and separate said vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption;
and wherein said vent stream separation unit is coupled to said carbon dioxide-containing feed stream to feed said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
53. Apparatus for treating gaseous carbon dioxide, comprising (A) a converting unit to receive NOx-rich sulfuric acid which can catalytically convert NO in said NOx-rich sulfuric acid to NO2 and desorb said NO2 from said NOx-rich sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2;
(B) a nitric acid formation unit coupled to said converting unit to receive desorbed NO2 therefrom and to convert said received desorbed NO2 to nitric acid and NO;
(C) a reactor to receive NO2 desorbed in unit (A) and gaseous carbon dioxide that contains NOx and sulfur dioxide, and to react NOx and sulfur dioxide in said carbon dioxide with water and oxygen and said desorbed NOx to form NOx-rich sulfuric acid and SO2-depleted NOx-containing gaseous carbon dioxide; and (D) an absorber coupled to said reactor to receive SO2-depleted NOx-containing gaseous carbon dioxide therefrom and absorb NOx from said SO2-depleted NOx-containing carbon dioxide into one said NOx-lean sulfuric acid to form NOx-rich sulfuric acid and NOx-1can SO2-depleted gaseous carbon dioxide;
(E) a subambient-temperature recovery unit coupled to said absorber to receive said NOx-lean SO2-depleted carbon dioxide therefrom to produce at least one gaseous carbon dioxide product stream and at least one gaseous carbon dioxide-containing vent stream employing refrigeration provided by expansion of at least one liquid carbon dioxide product stream formed by said recovery unit;

(F) a vent stream separation unit coupled to said subambient-temperature recovery unit to receive said vent stream therefrom and separate said vent stream into a carbon dioxide-rich stream and a carbon dioxide-depleted stream, by pressure swing adsorption or by physical or chemical absorption;
and wherein said vent stream separation unit is coupled to said carbon dioxide-containing feed stream to feed said carbon dioxide-rich stream to said carbon dioxide-containing feed stream.
CA2759867A 2008-09-26 2009-09-24 Multi-stage process for purifying carbon dioxide and producing sulfuric acid and nitric acid Abandoned CA2759867A1 (en)

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US10041108P 2008-09-26 2008-09-26
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US12/564,500 2009-09-22
US12/564,206 US7927572B2 (en) 2008-09-26 2009-09-22 Purifying carbon dioxide and producing acid
US12/564,500 US7927573B2 (en) 2008-09-26 2009-09-22 Multi-stage process for purifying carbon dioxide and producing acid
PCT/US2009/058125 WO2010036748A1 (en) 2008-09-26 2009-09-24 Multi-stage process for purifying carbon dioxide and producing sulfuric acid and nitric acid

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Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130122432A1 (en) * 2010-05-03 2013-05-16 Massachusetts Institute Of Technology Carbon dioxide purification
CN101837233B (en) * 2010-05-11 2012-07-18 华北电力大学（保定） System for recycling SO2 and NO from oxygen-enriched combustion boiler fume CO2 collection
US9381461B2 (en) 2010-05-31 2016-07-05 Mitsubishi Heavy Industries, Ltd. Air pollution control system and method
CA2800994C (en) * 2010-05-31 2015-12-08 Mitsubishi Heavy Industries, Ltd. Air pollution control system and method
CA2801008C (en) 2010-05-31 2015-12-08 Mitsubishi Heavy Industries, Ltd. Air pollution control system and method
US8282901B2 (en) * 2010-07-08 2012-10-09 Air Products And Chemicals, Inc. Integration of catalytic CO2 oxidation and oxyfuel sour compression
US8025860B1 (en) * 2010-07-08 2011-09-27 Air Products And Chemicals, Inc. Removal of acid mists
GB2489197B (en) * 2011-02-25 2018-09-05 Costain Oil Gas & Process Ltd Process and apparatus for purification of carbon dioxide
DE102011014007A1 (en) * 2011-03-15 2012-09-20 Linde Aktiengesellschaft Process and plant for flue gas denitrification
ES2582829T3 (en) * 2011-07-11 2016-09-15 General Electric Technology Gmbh Thermal integration for cryogenic CO2 separation
US20130111948A1 (en) * 2011-11-04 2013-05-09 Air Products And Chemicals, Inc. Purification of Carbon Dioxide
EP2724766A1 (en) 2012-10-26 2014-04-30 Alstom Technology Ltd A method of treating a carbon dioxide rich flue gas and a flue gas treatment system
EP2724770A1 (en) * 2012-10-26 2014-04-30 Alstom Technology Ltd Absorption unit for drying flue gas
CA2896836C (en) * 2012-12-31 2021-12-28 Inventys Thermal Technologies Inc. System and method for integrated carbon dioxide gas separation from combustion gases
CN107208964B (en) * 2015-02-27 2020-06-19 埃克森美孚上游研究公司 Reducing refrigeration and dehydration duty of feed streams to cryogenic distillation processes
WO2017165977A1 (en) 2016-03-31 2017-10-05 Inventys Thermal Technologies Inc. Adsorptive gas separation employing steam for regeneration
RU2764773C2 (en) * 2017-06-27 2022-01-21 Касале Са Method for producing argon and nitrogen
EP3533512A1 (en) * 2018-03-01 2019-09-04 Casale Sa Process for reducing the content of nox and n2o from a tail gas of a nitric acid process
CN108905488A (en) * 2018-07-11 2018-11-30 华电电力科学研究院有限公司 A kind of low-carbon clean and effective type distributed energy resource system and its operation method
CN110743313A (en) * 2019-10-29 2020-02-04 中国华能集团有限公司 Low-temperature flue gas adsorption denitration method
WO2023064977A1 (en) * 2021-10-18 2023-04-27 Dimer Technologies Pty. Ltd. A process and plant of vacuum pressure swing adsorption for producing pure carbon dioxide from industrial off-gas containing co2
US20230356139A1 (en) * 2022-05-04 2023-11-09 International Business Machines Corporation Two-system gas stream separation

Family Cites Families (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2184707A (en) * 1935-11-22 1939-12-26 Berl Ernst Pressure synthesis of sulphuric acid
GB498223A (en) 1936-05-04 1939-01-04 Us Fire Prot Corp Removal of nitrogen oxides from gaseous combustion products
US2247625A (en) * 1940-01-05 1941-07-01 Charles L Coughlin Production of inert gas
DE1095866B (en) 1959-09-30 1960-12-29 Linde S Eismaschinen Ag Zweign Process and device for the separation of carbon dioxide from compressed gases
US3511027A (en) 1968-03-26 1970-05-12 Treadwell Corp Sulfur dioxide recovery process
US3531664A (en) * 1968-11-07 1970-09-29 Avco Corp Means for and method of removing pollutants from products of combustion
US3649188A (en) * 1970-03-24 1972-03-14 Us Health Education & Welfare Method of converting sulfur dioxide to sulfuric acid
US4148868A (en) * 1975-03-10 1979-04-10 Ciba-Geigy Corporation Process for separating SO2 from a current of gas containing the same
DE2604305A1 (en) 1976-02-04 1977-08-11 Linde Ag PROCEDURE FOR SEPARATING GAS MIXTURES
DE2654582A1 (en) 1976-12-02 1978-06-08 Texaco Development Corp Nitrogen oxides and sulphur dioxide removal from waste gas - with by prodn. of sulphur and sulphuric acid
US4152129A (en) 1977-02-04 1979-05-01 Trentham Corporation Method for separating carbon dioxide from methane
US4171206A (en) 1978-08-21 1979-10-16 Air Products And Chemicals, Inc. Separation of multicomponent gas mixtures
JPS5677673A (en) 1979-11-28 1981-06-26 Nippon Oxygen Co Ltd Lowwtemperature liquefying separating method for carbonic acid gas
US4417449A (en) 1982-01-15 1983-11-29 Air Products And Chemicals, Inc. Process for separating carbon dioxide and acid gases from a carbonaceous off-gas
US4441900A (en) 1982-05-25 1984-04-10 Union Carbide Corporation Method of treating carbon-dioxide-containing natural gas
JPS60191002A (en) 1984-03-07 1985-09-28 Osaka Oxgen Ind Ltd Method for concentrating hydrogen in mixed gas containing at least hydrogen by using adsorption method
US4595404A (en) 1985-01-14 1986-06-17 Brian J. Ozero CO2 methane separation by low temperature distillation
FR2584307B1 (en) 1985-07-08 1989-10-20 Air Liquide PROCESS FOR TREATING A GASEOUS MIXTURE BY ADSORPTION
US4711645A (en) 1986-02-10 1987-12-08 Air Products And Chemicals, Inc. Removal of water and carbon dioxide from atmospheric air
US4770676A (en) 1986-05-16 1988-09-13 Air Products And Chemicals, Inc. Recovery of methane from land fill gas
US5051115A (en) 1986-05-21 1991-09-24 Linde Aktiengesellschaft Pressure swing adsorption process
US4753666A (en) 1986-07-24 1988-06-28 Chevron Research Company Distillative processing of CO2 and hydrocarbons for enhanced oil recovery
DE3639779A1 (en) 1986-11-21 1988-06-01 Linde Ag Process for extracting CO2 from a CO2-rich natural gas
US4762543A (en) 1987-03-19 1988-08-09 Amoco Corporation Carbon dioxide recovery
US4869894A (en) 1987-04-15 1989-09-26 Air Products And Chemicals, Inc. Hydrogen generation and recovery
US4813980A (en) 1987-10-16 1989-03-21 Air Products And Chemicals, Inc. Recovery of nitrogen, hydrogen and carbon dioxide from hydrocarbon reformate
US4846851A (en) 1987-10-27 1989-07-11 Air Products And Chemicals, Inc. Purification of ammonia syngas
US4790858A (en) 1988-01-29 1988-12-13 Air Products And Chemicals, Inc. Fractionation of multicomponent gas mixtures by pressure swing adsorption
US4963339A (en) 1988-05-04 1990-10-16 The Boc Group, Inc. Hydrogen and carbon dioxide coproduction
US5000925A (en) 1988-05-04 1991-03-19 The Boc Group, Inc. Hydrogen and carbon dioxide coproduction apparatus
US4857083A (en) 1988-10-25 1989-08-15 Air Products And Chemicals, Inc. Vacuum swing adsorption process with vacuum aided internal rinse
US4914218A (en) 1989-02-17 1990-04-03 Ravi Kumar Adsorptive process for separating multicomponent gas mixtures
US4913709A (en) 1989-02-17 1990-04-03 Ravi Kumar Adsorption process for recovering two high purity gas products from multicomponent gas mixtures
US4915711A (en) 1989-05-18 1990-04-10 Air Products And Chemicals, Inc. Adsorptive process for producing two gas streams from a gas mixture
US4952223A (en) 1989-08-21 1990-08-28 The Boc Group, Inc. Method and apparatus of producing carbon dioxide in high yields from low concentration carbon dioxide feeds
US5017204A (en) 1990-01-25 1991-05-21 Air Products And Chemicals, Inc. Dephlegmator process for the recovery of helium
US5203888A (en) 1990-11-23 1993-04-20 Uop Pressure swing adsorption process with multiple desorption steps
US5321946A (en) 1991-01-25 1994-06-21 Abdelmalek Fawzy T Method and system for a condensing boiler and flue gas cleaning by cooling and liquefaction
SE9202155L (en) 1992-07-13 1993-08-16 Bal Ab COMBINED COMBUSTION COMBUSTION AND EXHAUST WAS
US5248322A (en) 1992-10-01 1993-09-28 Air Products And Chemicals, Inc. Depressurization effluent repressurized adsorption process
US5354346A (en) 1992-10-01 1994-10-11 Air Products And Chemicals, Inc. Purge effluent repressurized adsorption process
US5294247A (en) 1993-02-26 1994-03-15 Air Products And Chemicals, Inc. Adsorption process to recover hydrogen from low pressure feeds
US5792239A (en) 1994-10-21 1998-08-11 Nitrotec Corporation Separation of gases by pressure swing adsorption
JP3233802B2 (en) * 1994-12-15 2001-12-04 関西電力株式会社 Method for removing carbon dioxide and nitrogen oxides from flue gas
US6090312A (en) 1996-01-31 2000-07-18 Ziaka; Zoe D. Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions
WO1999035455A1 (en) 1998-01-08 1999-07-15 Satish Reddy Autorefrigeration separation of carbon dioxide
US5974829A (en) 1998-06-08 1999-11-02 Praxair Technology, Inc. Method for carbon dioxide recovery from a feed stream
CA2350574C (en) 1998-11-10 2004-08-17 Fluor Corporation Recovery of co2 and h2 from psa offgas in an h2 plant
US6070431A (en) 1999-02-02 2000-06-06 Praxair Technology, Inc. Distillation system for producing carbon dioxide
US6210467B1 (en) 1999-05-07 2001-04-03 Praxair Technology, Inc. Carbon dioxide cleaning system with improved recovery
US6245127B1 (en) 1999-05-27 2001-06-12 Praxair Technology, Inc. Pressure swing adsorption process and apparatus
US6340382B1 (en) 1999-08-13 2002-01-22 Mohamed Safdar Allie Baksh Pressure swing adsorption process for the production of hydrogen
US6224843B1 (en) 1999-09-13 2001-05-01 Saudi Basic Industries Corporation Carbon dioxide purification in ethylene glycol plants
US20010004838A1 (en) 1999-10-29 2001-06-28 Wong Kenneth Kai Integrated heat exchanger system for producing carbon dioxide
WO2001087464A1 (en) 2000-05-12 2001-11-22 Powerspan Corp. Process for scrubbing flue gas using acids
US6500241B2 (en) 2000-12-19 2002-12-31 Fluor Corporation Hydrogen and carbon dioxide coproduction
US6497852B2 (en) 2000-12-22 2002-12-24 Shrikar Chakravarti Carbon dioxide recovery at high pressure
CN1283344C (en) 2001-07-31 2006-11-08 成都天立化工科技有限公司 Two-sectional variable pressure adsorption and decarbonizing process of recovering hydrogen and nitrogen gas for urea production
US6898936B1 (en) 2002-12-04 2005-05-31 The United States Of America As Represented By The United States Department Of Energy Compression stripping of flue gas with energy recovery
US7124605B2 (en) 2003-10-30 2006-10-24 National Tank Company Membrane/distillation method and system for extracting CO2 from hydrocarbon gas
US7828877B2 (en) 2004-11-05 2010-11-09 Xebec Adsorption, Inc. Separation of carbon dioxide from other gases
FR2877939B1 (en) 2004-11-16 2007-02-02 Air Liquide PROCESS AND PLANT FOR THE COMBINED PRODUCTION OF HYDROGEN AND CARBON DIOXIDE
FR2872890A1 (en) 2005-08-08 2006-01-13 Air Liquide Integrated process for adsorption and cryogenic separation for the production of carbon dioxide from sources containing low percentages of carbon dioxide
US7416716B2 (en) 2005-11-28 2008-08-26 Air Products And Chemicals, Inc. Purification of carbon dioxide
US7871457B2 (en) 2006-04-03 2011-01-18 Praxair Technology, Inc. Carbon dioxide production method
US7550030B2 (en) 2006-04-03 2009-06-23 Praxair Technology, Inc. Process and apparatus to recover high purity carbon dioxide
US7618478B2 (en) 2006-04-03 2009-11-17 Praxair Technology, Inc. Process and apparatus to recover medium purity carbon dioxide
US7666251B2 (en) 2006-04-03 2010-02-23 Praxair Technology, Inc. Carbon dioxide purification method

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ZA201102253B (en) 2012-08-29
JP2012503593A (en) 2012-02-09
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US7927572B2 (en) 2011-04-19
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US20100080745A1 (en) 2010-04-01
WO2010036748A1 (en) 2010-04-01

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