WO2008038484A1 - procédé de séparation/de récupération de dioxyde de carbone - Google Patents

procédé de séparation/de récupération de dioxyde de carbone Download PDF

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Publication number
WO2008038484A1
WO2008038484A1 PCT/JP2007/066535 JP2007066535W WO2008038484A1 WO 2008038484 A1 WO2008038484 A1 WO 2008038484A1 JP 2007066535 W JP2007066535 W JP 2007066535W WO 2008038484 A1 WO2008038484 A1 WO 2008038484A1
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WO
WIPO (PCT)
Prior art keywords
carbon dioxide
gas
release
absorbent
carbon
Prior art date
Application number
PCT/JP2007/066535
Other languages
English (en)
Japanese (ja)
Inventor
Yoshinori Saito
Masaru Fujino
Original Assignee
Murata Manufacturing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co., Ltd. filed Critical Murata Manufacturing Co., Ltd.
Priority to JP2008536307A priority Critical patent/JPWO2008038484A1/ja
Publication of WO2008038484A1 publication Critical patent/WO2008038484A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/408—Alkaline earth metal or magnesium compounds of barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a method for separating and recovering carbon dioxide.
  • the present invention also relates to a method for separating and recovering carbon dioxide using a carbon dioxide absorbent capable of releasing carbon dioxide absorbed under predetermined conditions.
  • lithium silicate is used as an absorbent for carbon dioxide, and the gas containing carbon dioxide after steam reforming of the carbon-containing fuel is contacted with the absorbent at a temperature of 400 ° C to 700 ° C.
  • a method has been proposed in which carbon dioxide is absorbed by allowing the carbon dioxide and the absorbent material to react with each other, and then the absorbent material that has absorbed carbon dioxide is regenerated at a temperature of 700 to 900 ° C (Patent Document 2). reference).
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-054927
  • the present invention solves the above-mentioned problems of the prior art, and the absorbed diacid It is possible to provide a method for separating and recovering carbon dioxide capable of efficiently releasing carbonized carbon in a shorter time and converting carbon dioxide into carbon monoxide, which is more versatile. Objective.
  • the method for separating and recovering carbon dioxide according to the present invention comprises:
  • a carbon dioxide separation and recovery method comprising:
  • the carbon dioxide absorbing material that has absorbed carbon dioxide is heated while supplying hydrogen gas or hydrocarbon gas to release carbon dioxide.
  • the method for separating and recovering carbon dioxide according to claim 2 is characterized in that, in the configuration of the invention according to claim 1, the heating temperature in the releasing step (b) is 800 to 1000 ° C.
  • the method for separating and recovering carbon dioxide according to claim 3 is the structure of the invention according to claim 1 or 2, wherein the carbon dioxide absorbent mainly comprises an alkaline earth metal oxide, Alternatively, the main component is a composite oxide containing an alkaline earth metal oxide.
  • the carbon dioxide absorbent is any one of BaTiO3, SrTiO2, and BaCaTiO.
  • the carbon dioxide absorbent that absorbs carbon dioxide When carbon dioxide is released, the carbon dioxide absorbent that absorbs carbon dioxide is used. Since carbon dioxide is released by heating while supplying hydrogen gas or hydrocarbon gas, carbon dioxide is converted to carbon monoxide and recovered. The power S to do.
  • the mixed gas of carbon monoxide and hydrogen is called synthesis gas, and it contains methanol (CH OH), formaldehyde (HCHO) C
  • carbon dioxide can be recovered by being converted to carbon monoxide, which is more versatile than carbon dioxide, and the carbon dioxide absorbent can be efficiently regenerated (carbon dioxide Release of carbon dioxide and the energy required for the regeneration of the carbon dioxide absorbent can be suppressed as compared with the conventional method. , Very meaningful.
  • the heating temperature in the carbon dioxide releasing step is set to 800 to 1000 ° C. Carbon dioxide can be efficiently converted into carbon monoxide and hydrogen, and the present invention can be realized more effectively.
  • the temperature condition of the release step is
  • the temperature condition of the release process is less than 800 ° C, the carbon monoxide production rate tends to decrease, and the temperature condition of the release process When the temperature exceeds 1000 ° C, coking due to thermal decomposition of methane becomes severe and deterioration due to sintering of the carbon dioxide absorber is likely to occur.
  • the carbon dioxide absorbent is mainly composed of an alkaline earth metal oxide, or a composite oxide containing an alkaline earth metal oxide. Therefore, it is possible to improve the efficiency of the conversion of carbon dioxide to carbon monoxide and hydrogen, and to make the present invention more effective. .
  • alkaline earth metal oxide examples include CaO and SrO.
  • Examples of the main component of the composite oxide containing an alkaline earth metal oxide include Ba TiO, Sr TiO, and Ba Ca Ti O.
  • the main component is a composite oxide of Ba TiO, Sr TiO, and Ba Ca Ti O as a carbon dioxide absorbent.
  • Ba TiO is one of the most effective forces from the standpoint of the regeneration temperature and the reaction rate during regeneration.
  • CaO with a normal regeneration temperature of 800 ° C or less is also regenerated under pressure.
  • Example 1 A cylindrical stainless steel container having an inner diameter of 22 mm and a length of 300 mm equipped with an external electric heater was filled with 22 g (approximately 10 mU) of Ba TiO (carbon dioxide absorbent) having an average particle diameter of 2 mm.
  • carbon dioxide was circulated at a rate of 2 NL / h (carbon dioxide concentration was 10 mol%), and carbon dioxide absorption was started.
  • the carbon dioxide absorbent that has absorbed carbon dioxide in this manner is heated using an electric heater equipped in the container, and the temperature of the carbon dioxide absorbent is controlled at 900 ° C, while the methane is removed. Carbon dioxide absorbed by the carbon dioxide absorbent was released at a rate of 10 NL / h.
  • Example 3 The ratio of carbon dioxide to carbon monoxide in the carbon dioxide releasing step was measured by the same method as in Example 1 except that the absorbent material temperature during carbon dioxide release was controlled to 1000 ° C. . The results are shown in Table 1.
  • a cylindrical stainless steel container having an inner diameter of 22 mm and a length of 300 mm equipped with an external electric heater was filled with 18 g (about 10 mL) of Sr TiO (carbon dioxide absorbent) having an average particle diameter of 2 mm.
  • carbon dioxide was circulated at a rate of 2 NL / h (carbon dioxide concentration was 10 mol%), and carbon dioxide absorption was started.
  • the carbon dioxide absorbent that has absorbed carbon dioxide is heated using an electric heater equipped in the container, and the temperature of the carbon dioxide absorbent is controlled at 900 ° C, while methane is reduced to 10 NL / h. The carbon dioxide absorbed in the carbon dioxide absorbent was released.
  • a cylindrical stainless steel container having an inner diameter of 22 mm and a length of 300 mm equipped with an external electric heater was charged with 14 g (about 10 mU) of CaO (carbon dioxide absorbent) having an average particle diameter of 2 mm.
  • Nitrogen gas was circulated through a stainless steel container at 18 NL / h, and the temperature of the nitrogen gas inlet was controlled at 600 ° C with a heat transfer heater.
  • carbon dioxide was circulated at a rate of 2 NL / h (carbon dioxide concentration was 10 mol%), and carbon dioxide absorption was started.
  • the carbon dioxide absorbing material that has absorbed carbon dioxide is heated using an electric heater equipped in the container, and the temperature of the carbon dioxide absorbing material is controlled at 900 ° C, while methane is reduced to 10 NL / h.
  • the carbon dioxide absorbed in the carbon dioxide absorbent was released.
  • Example 4 Further, as shown in Example 4, it was confirmed that carbon monoxide was produced at a high rate at a high rate even when hydrogen was circulated instead of methane.
  • reaction formula at this time is the same as the above-described reaction formula (2).
  • Example 5 when a composite oxide containing another alkaline earth metal oxide (Sr TiO in Example 5) is used as the carbon dioxide absorbent, Like, two
  • Example 7 in which CaO was used as the carbon dioxide absorbent and the temperature condition of the carbon dioxide release process was 700 ° C, the rate of carbon monoxide formation was not necessarily as high as 0.38. I understand that it is not. This result shows that the reaction between carbon dioxide and methane tends to proceed at high temperatures (above 800 ° C). However, also in Example 7, it was confirmed that carbon monoxide was reliably generated, and it was confirmed that the basic effect of the present invention was obtained.
  • the power described by taking as an example the case where methane is used as the hydrocarbon-based gas and the case where hydrogen is used as the sweep gas to be circulated in the release process it is possible to use a hydrocarbon-based gas other than methane, for example, propane, butane, etc., in a carbon dioxide releasing step. Also, depending on the purpose, a mixed gas in which a hydrocarbon-based gas and hydrogen are mixed. Furthermore, it is also possible to use a hydrocarbon-based gas or a mixed gas of hydrogen gas and other gas, for example, a mixed gas of hydrocarbon-based gas and water vapor or oxygen, or obtained by reforming it. It is also possible to use a mixed gas of carbon monoxide and hydrogen.
  • the carbon dioxide absorbing material is not limited to a granular form, and is in the form of a powder.
  • various forms such as forms, molded bodies formed into various shapes such as cubes, rectangular parallelepipeds, and spheres, sheet-like molded bodies, and structures having a combination of them. Is possible.
  • Ba TiO Sr TiO and CaO are used as the carbon dioxide absorbent.
  • absorbed carbon dioxide can be efficiently released in a shorter time, and carbon dioxide can be recovered by converting it to carbon monoxide, which is more versatile. It becomes possible.
  • the present invention can be widely applied to separation and recovery of carbon dioxide before combustion in the hydrogen production process and separation and recovery of carbon dioxide in combustion exhaust gas generated in a factory.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention permet de libérer de manière efficace du dioxyde carbone absorbé plus brièvement et de récupérer le dioxyde de carbone après sa conversion en monoxyde de carbone, recyclable dans une plus vaste gamme d'applications. Un absorbeur de dioxyde de carbone absorbe du dioxyde de carbone. Ensuite, on chauffe l'absorbeur de dioxyde de carbone contenant du dioxyde de carbone tout en y injectant du gaz hydrogène ou un gaz hydrocarbure pour libérer le dioxyde de carbone. Dans la phase de libération, l'absorbeur peut être porté à une température de 800-1 000 °C. L'absorbeur de dioxyde de carbone peut comprendre un oxyde de métal alcalino-terreux comme composant principal ou comprendre, comme composant principal, un oxyde composite englobant un oxyde de métal alcalino-terreux. L'absorbeur de dioxyde de carbone peut comprendre un oxyde composite sélectionné parmi Ba2TiO4, Sr2TiO4 et Ba3Ca2Ti2O9 comme composant principal.
PCT/JP2007/066535 2006-09-28 2007-08-27 procédé de séparation/de récupération de dioxyde de carbone WO2008038484A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008536307A JPWO2008038484A1 (ja) 2006-09-28 2007-08-27 二酸化炭素の分離回収方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006265982 2006-09-28
JP2006-265982 2006-09-28

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WO2008038484A1 true WO2008038484A1 (fr) 2008-04-03

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WO (1) WO2008038484A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023037652A1 (fr) 2021-09-08 2023-03-16 国立研究開発法人産業技術総合研究所 Méthode de production de monoxyde de carbone et dispositif utilisé à cet effet

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292525A (ja) * 2003-03-26 2004-10-21 Jfe Engineering Kk 二酸化炭素分離燃料化の装置及び方法、並びに二酸化炭素分離回収の装置及び方法
WO2006013695A1 (fr) * 2004-08-03 2006-02-09 Murata Manufacturing Co., Ltd. Matériau absorbant de dioxyde de carbone, et procede et appareil de séparation de dioxyde de carbone à l’aide dudit matériau

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292525A (ja) * 2003-03-26 2004-10-21 Jfe Engineering Kk 二酸化炭素分離燃料化の装置及び方法、並びに二酸化炭素分離回収の装置及び方法
WO2006013695A1 (fr) * 2004-08-03 2006-02-09 Murata Manufacturing Co., Ltd. Matériau absorbant de dioxyde de carbone, et procede et appareil de séparation de dioxyde de carbone à l’aide dudit matériau

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023037652A1 (fr) 2021-09-08 2023-03-16 国立研究開発法人産業技術総合研究所 Méthode de production de monoxyde de carbone et dispositif utilisé à cet effet

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