JP2008080211A - Carbon dioxide absorber, carbon dioxide separating method using the same, and carbon dioxide separation apparatus - Google Patents

Carbon dioxide absorber, carbon dioxide separating method using the same, and carbon dioxide separation apparatus Download PDF

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JP2008080211A
JP2008080211A JP2006261369A JP2006261369A JP2008080211A JP 2008080211 A JP2008080211 A JP 2008080211A JP 2006261369 A JP2006261369 A JP 2006261369A JP 2006261369 A JP2006261369 A JP 2006261369A JP 2008080211 A JP2008080211 A JP 2008080211A
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carbon dioxide
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Hiroshi Marusawa
博 丸澤
Yoshinori Saito
芳則 斉藤
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Murata Manufacturing Co Ltd
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    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon dioxide absorber which enables an absorption of a carbon dioxide at a high temperature, has a small attenuation rate by the CO<SB>2</SB>absorption in a maximum weight variation even if a cycle of an absorption/discharge of CO<SB>2</SB>is repeated many times, and can correspond to a cycle operation repeating the absorption/discharge of CO<SB>2</SB>stably, a carbon dioxide separating method using the carbon dioxide absorber, and a carbon dioxide separation apparatus. <P>SOLUTION: Ni is contained at a rate of 0.2 wt.% or more when considered in terms of metals, in the carbon dioxide absorber containing mainly a composite oxide containing a component material X being at least one kind of Sr and Ba, and Ti at a rate of a molar ratio (X/Ti):1.8-2.2. Further, Ni is contained at a rate of 0.4-6.0 wt.% when considered in terms of metals. Using the carbon dioxide absorber, the absorption of the carbon dioxide is carried out under the following conditions: pressure:1.0×10<SP>4</SP>-1.0×10<SP>6</SP>Pa and temperature:500-900°C, and the discharge of the carbon dioxide is carried out under the following conditions: pressure:1,000 Pa or less and temperature:750°C or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本願発明は、高温条件下で炭酸ガスを吸収し、所定の条件下で吸収した炭酸ガスを放出させて再生することにより、繰り返して使用することが可能な炭酸ガス吸収材、それを用いた炭酸ガス分離方法、および炭酸ガス分離装置に関する。   The present invention relates to a carbon dioxide absorbent that can be used repeatedly by absorbing carbon dioxide under a high temperature condition, releasing the carbon dioxide absorbed under a predetermined condition, and regenerating the carbon dioxide. The present invention relates to a gas separation method and a carbon dioxide separation device.

５００℃を超える温度域で炭酸ガスを吸収する材料としては、例えば、一般式：ＬｉxＳｉyＯzで表されるリチウムシリケートからなる群より選ばれる少なくとも１種以上を含有する炭酸ガス吸収材が知られている。 Examples of the material that absorbs carbon dioxide in a temperature range exceeding 500 ° C. include a carbon dioxide absorbent containing at least one selected from the group consisting of lithium silicate represented by the general formula: Li x Si y O z It has been known.

しかしながら、リチウムシリケートを用いた場合、燃焼排ガスなどの７００℃を超えるような高温のガスから炭酸ガスを効率よく吸収することは困難であるのが実情である。   However, when lithium silicate is used, it is difficult to efficiently absorb carbon dioxide gas from a high-temperature gas exceeding 700 ° C. such as combustion exhaust gas.

そこで、本願の出願人は、高温のガスから炭酸ガスを効率よく吸収することが可能な炭酸ガス吸収材として、ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物（例えば、Ｂａ2ＴｉＯ4（オルソチタン酸バリウム）や、（Ｓｒ，Ｂａ）ｘＴｉＯ4（ｘ＝１．８〜２．２））を主成分とする炭酸ガス吸収材を提案している（特許文献１参照）。 Therefore, the applicant of the present application, as a carbon dioxide absorbing material capable of efficiently absorbing carbon dioxide from a high-temperature gas, contains a component substance X, which is at least one of Sr and Ba, and Ti in a molar ratio ( X / Ti): a composite oxide containing a ratio of 1.8 to 2.2 (for example, Ba 2 TiO 4 (barium orthotitanate) or (Sr, Ba) x TiO 4 (x = 1.8 to 2. 2)) has been proposed as a main component (see Patent Document 1).

この特許文献１の炭酸ガス吸収材（例えば、Ｂａ2ＴｉＯ4）は、下記の式(１)の反応によりＣＯ2を吸収してＢａＴｉＯ3になり、常圧付近で５００〜９００℃というような高温下で炭酸ガスを吸収する能力を備えている。
Ｂａ2ＴｉＯ4＋ＣＯ2 → ＢａＴｉＯ3＋ＢａＣＯ3 ……（１） The carbon dioxide gas absorbing material (for example, Ba 2 TiO 4 ) of Patent Document 1 absorbs CO 2 by the reaction of the following formula (1) to become BaTiO 3 , such as 500 to 900 ° C. near normal pressure. It has the ability to absorb carbon dioxide at high temperatures.
Ba 2 TiO 4 + CO 2 → BaTiO 3 + BaCO 3 (1)

また、特許文献１の炭酸ガス吸収材は、例えば、積層コンデンサの廃棄シートを原料として製造することが可能であり、その際には、Ｃａ、Ｚｒ、Ｍｇ、Ｓｉ、Ｍｎ、Ｎａ、Ｎｉなどが微量混入してもよいとされている。   In addition, the carbon dioxide absorbent of Patent Document 1 can be manufactured using, for example, a waste sheet of a multilayer capacitor as a raw material, and in that case, Ca, Zr, Mg, Si, Mn, Na, Ni, etc. It is said that a trace amount may be mixed.

しかしながら、この特許文献１の炭酸ガス吸収材は、ＣＯ2吸収・放出（ＣＯ2 ２０％、Ｎ2 ８０％条件）のサイクル数が多くなると、ＣＯ2吸収率が低下する傾向がある。そのため、さらに安定的にＣＯ2の吸収・放出を繰り返して行うことが可能な炭酸ガス吸収材が求められている。
国際公開第２００６／０１３６９５号パンフレット However, the carbon dioxide absorbent of Patent Document 1 has a tendency that the CO 2 absorption rate decreases when the number of cycles of CO 2 absorption / release (CO 2 20%, N 2 80% condition) increases. Therefore, there is a demand for a carbon dioxide gas absorbent that can repeatedly absorb and release CO 2 more stably.
International Publication No. 2006/013695 Pamphlet

本願発明は、上記問題点を解決するものであり、高い温度域において炭酸ガスを吸収することが可能で、かつ、ＣＯ2の吸収・放出のサイクル数が多くなった場合にも、ＣＯ2吸収による最大重量変化量の減衰率が小さく、安定的にＣＯ2の吸収・放出を繰り返して行うことが可能な炭酸ガス吸収材、それを用いた炭酸ガス分離方法、および炭酸ガス分離装置を提供することを課題とする。 The present invention solves the above-mentioned problems, and can absorb carbon dioxide in a high temperature range, and can absorb CO 2 even when the number of CO 2 absorption / release cycles increases. Provided is a carbon dioxide absorbing material that has a small attenuation rate of the maximum weight change amount due to CO2 and can repeatedly perform absorption and release of CO 2 , a carbon dioxide separation method using the same, and a carbon dioxide separation device This is the issue.

上記課題を解決するために、本願発明（請求項１）の炭酸ガス吸収材は、
ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物を主成分とし、
Ｎｉを金属換算で０．２重量％以上含有すること
を特徴としている。 In order to solve the above problems, the carbon dioxide absorbent of the present invention (Claim 1) is:
The main component is a composite oxide containing a component substance X, which is at least one of Sr and Ba, and Ti at a molar ratio (X / Ti): 1.8 to 2.2,
Ni is contained in an amount of 0.2% by weight or more in terms of metal.

また、請求項２の炭酸ガス吸収材は、
ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物を主成分とし、
Ｎｉを金属換算で０．４〜６．０重量％の割合で含有すること
を特徴としている。 In addition, the carbon dioxide absorbent of claim 2
The main component is a composite oxide containing a component substance X, which is at least one of Sr and Ba, and Ti at a molar ratio (X / Ti): 1.8 to 2.2,
Ni is contained in a proportion of 0.4 to 6.0% by weight in terms of metal.

また、請求項３の炭酸ガス分離方法は、
請求項１または２記載の炭酸ガス吸収材を用い、
圧力：１．０×１０4〜１．０×１０6Ｐａ、
温度：５００〜９００℃
の条件で炭酸ガスを吸収させる工程と、
前記炭酸ガス吸収材に吸収させた炭酸ガスを、
圧力：１０００Ｐａ以下、
温度：７５０℃以上
の条件で放出させる工程と
を具備することを特徴としている。 Further, the carbon dioxide separation method of claim 3
Using the carbon dioxide absorbent according to claim 1 or 2,
Pressure: 1.0 × 10 4 to 1.0 × 10 6 Pa,
Temperature: 500-900 ° C
A step of absorbing carbon dioxide under the conditions of
The carbon dioxide absorbed by the carbon dioxide absorbent is
Pressure: 1000 Pa or less,
And a step of releasing at a temperature of 750 ° C. or higher.

また、請求項４の炭酸ガス分離装置は、
請求項１または２記載の炭酸ガス吸収材を、
圧力：１．０×１０4〜１．０×１０6Ｐａ、
温度：５００〜９００℃
の条件で炭酸ガスを含む気流と接触させて炭酸ガスを前記炭酸ガス吸収材に吸収させる炭酸ガス吸収機構部と、
炭酸ガスを含む気流と接触して炭酸ガスを吸収した炭酸ガス吸収材を、
圧力：１０００Ｐａ以下の減圧下、
温度：７５０℃以上
の条件で加熱して、炭酸ガスを放出させる炭酸ガス放出機構部と
を具備することを特徴としている。 Further, the carbon dioxide separator according to claim 4 is:
The carbon dioxide absorbent according to claim 1 or 2,
Pressure: 1.0 × 10 4 to 1.0 × 10 6 Pa,
Temperature: 500-900 ° C
A carbon dioxide absorption mechanism that allows carbon dioxide to be absorbed by the carbon dioxide absorbent by contacting with an air stream containing carbon dioxide under the conditions of
A carbon dioxide absorbent that absorbs carbon dioxide in contact with an air stream containing carbon dioxide,
Pressure: Under reduced pressure of 1000 Pa or less,
A temperature: 750 ° C. or higher, and a carbon dioxide gas release mechanism for releasing carbon dioxide gas.

本願発明（請求項１）の炭酸ガス吸収材は、ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物を主成分とし、これにＮｉを金属換算で０．２重量％以上含有させたものであり、ＣＯ2の吸収・放出のサイクルを繰り返すサイクル運転において、サイクル数が多くなった場合にも、ＣＯ2吸収による最大重量変化量の減衰率が小さく、耐用性に優れている。
ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物（すなわち、（Ｓｒ1-y，Ｂａy）ｘＴｉＯ4、ただし、ｘ＝１．８〜２．２）を主成分とし、 The carbon dioxide gas absorbent of the present invention (Claim 1) is composed of a component substance X, which is at least one of Sr and Ba, and Ti at a molar ratio (X / Ti): 1.8 to 2.2. In the case where the number of cycles is increased in a cycle operation in which a complex oxide containing is contained as a main component and Ni is contained in an amount of 0.2% by weight or more in terms of metal and the cycle of CO 2 absorption / release is repeated. In addition, the attenuation rate of the maximum weight change due to CO 2 absorption is small, and the durability is excellent.
A composite oxide (ie, (Sr 1-y , Ba) containing component material X, which is at least one of Sr and Ba, and Ti in a molar ratio (X / Ti): 1.8 to 2.2. y ) xTiO 4 , where x = 1.8 to 2.2) is the main component,

例えば、上述のような複合酸化物（例えば、（Ｓｒ1-y，Ｂａy）ｘＴｉＯ4、ただし、ｘ＝１．８〜２．２）に、Ｎｉを金属換算で約０．２重量％以上含有させた場合、被処理ガス組成が、ＣＯ2：２０％、Ｎ2：８０％の条件で、ＣＯ2の吸収・放出のサイクル運転を繰り返して行った場合における、ＣＯ2吸収による最大重量変化量の減衰率を３％以内に抑えることが可能になる。 For example, the composite oxide as described above (e.g., (Sr 1-y, Ba y) xTiO 4, however, x = 1.8 to 2.2) to about 0.2% by weight or more of Ni in terms of metal When contained, maximum weight change due to CO 2 absorption when the gas composition to be treated is repeatedly CO 2 absorption / release cycle operation under the conditions of CO 2 : 20% and N 2 : 80%. It is possible to suppress the amount of attenuation within 3%.

また、請求項２の炭酸ガス吸収材のように、Ｎｉを金属換算で０．４重量％以上含有させるようにした場合、ＣＯ2吸収による最大重量変化量の減衰率を１％以内に抑えることが可能になり、長期間にわたってより安定的に炭酸ガスの吸収を行うことが可能になる。 In addition, when the Ni content is 0.4% by weight or more in terms of metal as in the carbon dioxide absorbent of Claim 2, the attenuation rate of the maximum weight change due to CO 2 absorption is suppressed to within 1%. It becomes possible to absorb carbon dioxide gas more stably over a long period of time.

さらに、Ｎｉを金属換算で０．４〜６．０重量％の範囲内で含有させるようにした場合、ＣＯ2吸収による最大重量変化量を１０％以上にすることが可能になり、炭酸ガス吸収材の単位量あたりの炭酸ガス吸収量を多く保ち、安定的に、効率よく炭酸ガスの吸収を行うことが可能になる。 Furthermore, when Ni is contained in the range of 0.4 to 6.0% by weight in terms of metal, the maximum weight change due to CO 2 absorption can be made 10% or more, and carbon dioxide absorption A large amount of carbon dioxide absorption per unit amount of the material can be maintained, and carbon dioxide can be stably and efficiently absorbed.

また、請求項３の炭酸ガス分離方法は、請求項１または２記載の炭酸ガス吸収材を用いて、圧力：１．０×１０4〜１．０×１０6Ｐａ、温度：５００〜９００℃の条件で炭酸ガスを吸収させる工程と、前記炭酸ガス吸収材に吸収させた炭酸ガスを、圧力：１０００Ｐａ以下、温度：７５０℃以上の条件で放出させる工程とを具備しており、高温下での炭酸ガスの吸収と、吸収した炭酸ガスの放出（炭酸ガス吸収材の再生）を効率よく行うことが可能で、この方法を用いることにより、例えば、リチウムシリケートを炭酸ガス吸収材として用いた従来の方法では炭酸ガスの吸収を行うことができないような、高い温度条件下において、効率よく炭酸ガスの分離を行うことが可能になる。 Moreover, the carbon dioxide separation method of Claim 3 uses the carbon dioxide absorbent of Claim 1 or 2, Pressure: 1.0 * 10 < 4 > -1.0 * 10 < 6 > Pa, Temperature: 500-900 degreeC. And a step of releasing the carbon dioxide absorbed by the carbon dioxide absorbent under the conditions of pressure: 1000 Pa or less and temperature: 750 ° C. or more at a high temperature. It is possible to efficiently absorb the carbon dioxide gas and release the absorbed carbon dioxide gas (regeneration of the carbon dioxide gas absorbing material). By using this method, for example, conventional lithium silicate is used as the carbon dioxide gas absorbing material. In this method, carbon dioxide can be efficiently separated under high temperature conditions where carbon dioxide cannot be absorbed.

なお、本願発明の炭酸ガス吸収材を、ＴＧ−ＤＴＡ分析機を用い、例えば、ＣＯ2とＮ2の割合が、体積比でＣＯ2：２０、Ｎ2：８０の割合の混合ガス雰囲気中で、ＴＧ−ＤＴＡ分析（熱重量分析−示差熱分析）を行った場合、炭酸ガス吸収材の重量は炭酸ガスの吸収により増大し、約８００〜１０００℃で最大値となり、温度が１０２１℃以上になると炭酸ガスの放出により重量が低下し、約１０５０℃以上で元の重量に戻る。それゆえ、８００〜１０５０℃の間の温度条件下に炭酸ガスの吸収と放出とを行うことにより、最も効率よく炭酸ガスの分離を行うことが可能になる。
ただし、炭酸ガスの吸収および放出を減圧下で行うようにした場合には、好適な操作温度が低下し、加圧下で行うようにした場合には、好適な操作温度が上昇する。したがって、本願請求項３に規定するような条件下で吸収、放出を行うことにより、効率よく炭酸ガスの分離を行うことが可能になる。
なお、吸収した炭酸ガスを放出させる際の操作温度が１３００℃を超えると、炭酸ガス吸収材の焼結が進み、炭酸ガスの吸収能力を失うため好ましくない。
本願発明の炭酸ガスの分離方法は、例えば、燃料電池などに使用される水素製造プロセスにおける、燃焼前炭酸ガス分離への利用が可能である。 The carbon dioxide absorbent of the present invention is used in a mixed gas atmosphere using a TG-DTA analyzer, for example, in which the ratio of CO 2 and N 2 is a volume ratio of CO 2 : 20 and N 2 : 80. When TG-DTA analysis (thermogravimetric analysis-differential thermal analysis) is performed, the weight of the carbon dioxide absorbent increases due to the absorption of carbon dioxide, reaches a maximum value at about 800 to 1000 ° C., and the temperature is over 1021 ° C. Then, the weight decreases due to the release of carbon dioxide gas, and returns to the original weight at about 1050 ° C. or higher. Therefore, the carbon dioxide gas can be separated most efficiently by absorbing and releasing the carbon dioxide gas under a temperature condition of 800 to 1050 ° C.
However, when carbon dioxide is absorbed and released under reduced pressure, the preferred operating temperature decreases, and when it is carried out under increased pressure, the preferred operating temperature increases. Therefore, carbon dioxide gas can be efficiently separated by absorbing and releasing under the conditions specified in claim 3 of the present application.
In addition, when the operating temperature at the time of releasing the absorbed carbon dioxide gas exceeds 1300 ° C., sintering of the carbon dioxide gas absorbing material proceeds and the carbon dioxide gas absorbing ability is lost.
The carbon dioxide separation method of the present invention can be used for pre-combustion carbon dioxide separation in a hydrogen production process used in, for example, a fuel cell.

また、請求項４の炭酸ガス分離装置は、請求項１または２記載の炭酸ガス吸収材を、圧力：１．０×１０4〜１．０×１０6Ｐａ、温度：５００〜９００℃の条件で炭酸ガスを含む気流と接触させて炭酸ガスを炭酸ガス吸収材に吸収させる炭酸ガス吸収機構部と、炭酸ガスを含む気流と接触して炭酸ガスを吸収した炭酸ガス吸収材を、圧力：１０００Ｐａ以下の減圧下、温度：７５０℃以上の条件で加熱して、炭酸ガスを放出させる炭酸ガス放出機構部とを具備しており、炭酸ガス吸収機構部において、高温下での炭酸ガスの吸収を確実に行い、炭酸ガス放出機構部において、吸収した炭酸ガスの放出（炭酸ガス吸収材の再生）を確実に行うことができることから、この炭酸ガス分離装置を用いることにより、高温下での炭酸ガスの分離を経済的に、しかも効率よく行うことが可能になる。 Moreover, the carbon dioxide separator of claim 4 is the carbon dioxide absorbent according to claim 1 or 2 under the conditions of pressure: 1.0 × 10 4 to 1.0 × 10 6 Pa, temperature: 500 to 900 ° C. A carbon dioxide absorption mechanism that allows carbon dioxide gas to be absorbed by the carbon dioxide absorber by contacting with a gas stream containing carbon dioxide, and a carbon dioxide absorber that absorbs carbon dioxide by contacting the gas stream containing carbon dioxide, pressure: 1000 Pa A carbon dioxide gas release mechanism that releases carbon dioxide by heating at a temperature of 750 ° C. or higher under the following reduced pressure. The carbon dioxide absorption mechanism absorbs carbon dioxide at a high temperature. Since the carbon dioxide gas release mechanism can reliably release the absorbed carbon dioxide gas (regeneration of the carbon dioxide gas absorbent), carbon dioxide gas at high temperatures can be obtained by using this carbon dioxide gas separator. Economy of separation Moreover, it becomes possible to carry out efficiently.

以下に本願発明の実施例を示して、本願発明の特徴とするところをさらに詳しく説明する。   The features of the present invention will be described in more detail below with reference to examples of the present invention.

ＢａＴｉＯ3粉末に対して、ＢａＴｉＯ3とＢａＣＯ3のモル比が１対１になる量のＢａＣＯ3粉末を添加した。 An amount of BaCO 3 powder in which the molar ratio of BaTiO 3 and BaCO 3 was 1: 1 was added to the BaTiO 3 powder.

さらに、上述のように、モル比が１：１となるように配合されたＢａＴｉＯ3とＢａＣＯ3のすべてがＢａ2ＴｉＯ4となるように反応が生じるとした場合の理論量のＢａ2ＴｉＯ4に対して、Ｎｉの含有割合が金属換算で０〜１２．０重量％となるようにＮｉ金属粉末を添加した。 Further, as mentioned above, the molar ratio of 1: 1 to become so formulated BaTiO 3 and Ba 2 TiO 4 weight theory if all BaCO 3 was a reaction so that Ba 2 TiO 4 occurs On the other hand, Ni metal powder was added so that the Ni content would be 0 to 12.0% by weight in terms of metal.

それから、純水、ＰＳＺ玉石、分散剤、消泡剤を加え、樹脂製のポットを用いたボールミルにて１６〜２０時間の混合・粉砕を行い、原料粉末が分散したスラリーを得た。   Then, pure water, PSZ boulder, a dispersant and an antifoaming agent were added, and mixing and pulverization were performed for 16 to 20 hours in a ball mill using a resin pot to obtain a slurry in which raw material powder was dispersed.

次に、このスラリーを１２０℃で１０時間乾燥した後、得られた粉末を１０００〜１２００℃、２時間保持の条件で焼成し、複合酸化物であるＢａ2ＴｉＯ4を主成分とする炭酸ガス吸収材（セラミックス粉末）を得た。 Next, this slurry was dried at 120 ° C. for 10 hours, and then the obtained powder was fired at 1000 to 1200 ° C. for 2 hours, and carbon dioxide gas containing Ba 2 TiO 4 as a main component was a composite oxide. An absorbent material (ceramic powder) was obtained.

それから、この炭酸ガス吸収材を用い、ＣＯ2とＮ2の割合が、体積比でＣＯ2：２０、Ｎ2：８０の割合の混合ガス雰囲気中で、ＴＧ−ＤＴＡ分析（熱重量分析−示差熱分析）を行った。 Then, using this carbon dioxide absorbing material, TG-DTA analysis (thermogravimetric analysis-differential) in a mixed gas atmosphere in which the ratio of CO 2 and N 2 is a volume ratio of CO 2 : 20, N 2 : 80 Thermal analysis).

図１に、Ｎｉ金属を添加していない炭酸ガス吸収材を室温から１３００℃まで測定したＴＧ−ＤＴＡ分析結果を示す。
図１に示すように、ＣＯ2とＮ2の割合が、体積比でＣＯ2：２０、Ｎ2：８０の雰囲気ガス中で、上記炭酸ガス吸収材の重量は、約４００℃から炭酸ガスの吸収により増大し、約８００〜１０００℃で最大値となる。そして、温度が１０２１℃以上になると炭酸ガスの放出により重量が低下し、約１０５０℃以上で元の重量に戻る。
なお、図１では、具体的には、吸収開始温度は６１８℃、放出開始温度は１０２１℃、ＴＧ最大値は１０．６３％となっている。 FIG. 1 shows a TG-DTA analysis result obtained by measuring a carbon dioxide absorbent not added with Ni metal from room temperature to 1300 ° C.
As shown in FIG. 1, the weight of the carbon dioxide absorbent is from about 400 ° C. to the amount of carbon dioxide in an atmosphere gas in which the ratio of CO 2 and N 2 is CO 2 : 20 and N 2 : 80 by volume. It increases due to absorption, and reaches a maximum value at about 800 to 1000 ° C. When the temperature reaches 1021 ° C. or higher, the weight decreases due to the release of carbon dioxide, and returns to the original weight at about 1050 ° C. or higher.
In FIG. 1, specifically, the absorption start temperature is 618 ° C., the release start temperature is 1021 ° C., and the TG maximum value is 10.63%.

ここで、約８００℃と約１０５０℃の間で、重量変化量が最大（すなわち、ＴＧ最大変化量）となり、炭酸ガスの最大吸収変化量を示す。したがって、約８００℃と約１０５０℃の間で炭酸ガスを吸収・放出させれば、効率よく、炭酸ガスを分離・回収できることになる。   Here, between about 800 ° C. and about 1050 ° C., the weight change amount becomes maximum (that is, TG maximum change amount), which indicates the maximum absorption change amount of carbon dioxide gas. Therefore, if carbon dioxide is absorbed and released between about 800 ° C. and about 1050 ° C., carbon dioxide can be efficiently separated and recovered.

また、Ｎｉ金属換算で０〜１２．０重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材について、同一条件でＴＧ−ＤＴＡ分析（熱重量分析−示差熱分析）を行ったところ、上記のＮｉ金属を添加していない炭酸ガス吸収材の場合と同様に、８００℃と１０５０℃の間でＴＧ変化量が最大になることが確認された。   Moreover, about the carbon dioxide absorber which added Ni metal powder in the ratio of 0-12.0 weight% in conversion of Ni metal, when the TG-DTA analysis (thermogravimetric analysis-differential thermal analysis) was performed on the same conditions, the above-mentioned It was confirmed that the amount of change in TG was the maximum between 800 ° C. and 1050 ° C., as in the case of the carbon dioxide absorbent to which no Ni metal was added.

また、Ｎｉ金属を添加していない炭酸ガス吸収材について、ＴＧ−ＤＴＡ分析機を用い、８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させて熱重量分析を行った。その結果を図２に示す。   Moreover, about the carbon dioxide gas absorption material which has not added Ni metal, the thermogravimetric analysis was performed by making carbon dioxide gas absorb and discharge | release continuously between 800-1050 degreeC using the TG-DTA analyzer. The result is shown in FIG.

また、Ｎｉ金属換算で１．５重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材について、ＴＧ−ＤＴＡ分析機を用い、上記のＮｉ金属を添加していない炭酸ガス吸収材の場合と同一の条件で炭酸ガスを連続的に吸収・放出させ、熱重量分析を行った。その結果を図３に示す。   Moreover, about the carbon dioxide absorber which added Ni metal powder in the ratio of 1.5 weight% in Ni metal conversion, the case of the carbon dioxide absorber which does not add said Ni metal using a TG-DTA analyzer Under the same conditions, carbon dioxide was continuously absorbed and released, and thermogravimetric analysis was performed. The result is shown in FIG.

図２に示すように、Ｎｉを添加していない炭酸ガス吸収材は、３サイクル目からＴＧ最大変化量が減少し始めることが確認された。
これに対して、Ｎｉ金属換算で１．５重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材の場合には、図３に示すように、炭酸ガスの吸収・放出のサイクルが増えても、ＴＧ最大変化量は減少しないことが確認された。 As shown in FIG. 2, it was confirmed that the maximum amount of change in TG started to decrease from the third cycle in the carbon dioxide absorbent to which Ni was not added.
On the other hand, in the case of a carbon dioxide absorbent to which Ni metal powder is added at a rate of 1.5% by weight in terms of Ni metal, the cycle of carbon dioxide absorption / release is increased as shown in FIG. It was also confirmed that the maximum change in TG did not decrease.

また、Ｎｉ金属換算で０〜１２．０重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材について、炭酸ガスを連続的に吸収・放出させるサイクルを８回行い、１回目と８回目のＴＧ最大変化量［％］を調べた。
表１に、炭酸ガスを８回まで連続的に吸収・放出させた場合における、１回目と８回目のＴＧ最大変化量［％］を示す。 In addition, for the carbon dioxide absorbent to which Ni metal powder is added at a rate of 0 to 12.0% by weight in terms of Ni metal, the cycle for continuously absorbing and releasing carbon dioxide is performed 8 times, and the first and eighth times. TG maximum change [%] was examined.
Table 1 shows the TG maximum change amount [%] for the first and eighth times when carbon dioxide gas is absorbed and released continuously up to eight times.

また、下記の式(２)により、ＴＧ最大重量変化量の減衰率［％］を算出した。 減衰率［％］＝｛（８回目のＴＧ最大変化量［％］）−（１回目のＴＧ最大変化量［％］）｝／（８回目のＴＧ最大変化量［％］）×１００ ……(２)
その結果を表１に併せて示す。 Further, the attenuation rate [%] of the TG maximum weight change amount was calculated by the following equation (2). Decay rate [%] = {(8th TG maximum change [%]) − (1st TG maximum change [%])} / (8th TG maximum change [%]) × 100 (2)
The results are also shown in Table 1.

Figure 2008080211
Figure 2008080211

ただし、表１において、試料番号に＊印を付した試料は本願発明の範囲外の試料である。
表１より、Ｎｉ金属換算で０．２重量％未満の割合でＮｉ金属粉末を添加した炭酸ガス吸収材（試料番号１，２）の場合、減衰率が３％以上と大きくなることが確認された。
また、Ｎｉ金属換算で０．２重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材（試料番号３）の場合、減衰率が２．６％と小さくなることが確認された。
また、Ｎｉ金属換算で０．４重量％以上の割合でＮｉ金属粉末を添加した炭酸ガス吸収材（試料番号４〜９）の場合、減衰率が１％未満（表１では０％）に抑えられることが確認された。 However, in Table 1, a sample numbered with * is a sample outside the scope of the present invention.
From Table 1, it is confirmed that the attenuation rate increases to 3% or more in the case of the carbon dioxide absorbent (sample numbers 1 and 2) to which Ni metal powder is added in a proportion of less than 0.2% by weight in terms of Ni metal. It was.
In addition, in the case of the carbon dioxide absorbent (sample number 3) to which Ni metal powder was added at a rate of 0.2% by weight in terms of Ni metal, it was confirmed that the attenuation rate was as small as 2.6%.
Further, in the case of a carbon dioxide absorbent (sample numbers 4 to 9) to which Ni metal powder is added in a proportion of 0.4% by weight or more in terms of Ni metal, the attenuation rate is suppressed to less than 1% (0% in Table 1). It was confirmed that

一方、Ｎｉ金属換算で１２．０重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材（試料番号９）の場合、減衰率は０％であったが、ＣＯ2吸収による最大重量変化量が１０％以下と小さくなることが確認された。 On the other hand, in the case of the carbon dioxide absorbent (sample number 9) to which Ni metal powder was added at a rate of 12.0% by weight in terms of Ni metal, the decay rate was 0%, but the maximum weight change due to CO 2 absorption Was confirmed to be as small as 10% or less.

これに対し、Ｎｉ金属換算で０．２〜６．０重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材（試料番号３〜８）の場合、ＣＯ2吸収による最大重量変化量が１０％以上と大きく、安定して長期間の吸収・放出を行わせることが可能で、より望ましいことが確認された。 On the other hand, in the case of the carbon dioxide absorbent (sample numbers 3 to 8) to which Ni metal powder is added at a rate of 0.2 to 6.0% by weight in terms of Ni metal, the maximum weight change due to CO 2 absorption is 10%. It is confirmed that it is more desirable because it can absorb and release for a long period of time stably.

上記実施例１より、
(１)Ｎｉ金属を添加することにより、Ｂａ2ＴｉＯ4を主成分とする炭酸ガス吸収材の炭酸ガス吸収・放出量を安定的に確保できること、
(２)Ｎｉ金属の添加量が０．２重量％未満になると、減衰率が３％以上となり、好ましくないこと、
(３)Ｎｉ金属の添加量が０．４重量％以上になると、減衰率を１％未満（表１では０％）に抑えることが可能になること、
(４)また、Ｎｉ金属の添加量を０．２〜６．０重量％の範囲とすることにより、ＣＯ2吸収による最大重量変化量が１０％以上と大きく、安定して長期間の吸収・放出を行わせることが可能になり望ましいこと
が確認された。 From Example 1 above,
(1) By adding Ni metal, it is possible to stably secure the carbon dioxide absorption / release amount of the carbon dioxide absorbent mainly composed of Ba 2 TiO 4 ;
(2) When the addition amount of Ni metal is less than 0.2% by weight, the attenuation factor is 3% or more, which is not preferable.
(3) When the amount of Ni metal added is 0.4% by weight or more, the attenuation rate can be suppressed to less than 1% (0% in Table 1).
(4) In addition, by making the amount of Ni metal added in the range of 0.2 to 6.0% by weight, the maximum change in weight due to CO 2 absorption is as large as 10% or more, and stable absorption over a long period of time. It was confirmed that it would be desirable to be able to release.

この結果から、本願発明の炭酸ガス吸収材を用いることにより、炭酸ガス分離・回収装置システムなどにおいて、炭酸ガスを安定的に分離・回収することが可能になることが理解される。
なお、Ｎｉ金属として添加されたＮｉは、熱処理工程を経て得られる本願発明の炭酸ガス吸収材中では、主としてＮｉＯとして存在することが確認されている。 From this result, it is understood that by using the carbon dioxide absorbent of the present invention, it is possible to stably separate and collect carbon dioxide in a carbon dioxide separation / recovery device system and the like.
It has been confirmed that Ni added as Ni metal exists mainly as NiO in the carbon dioxide absorbent of the present invention obtained through the heat treatment step.

ＢａＴｉＯ3粉末に対して、ＢａＴｉＯ3とＢａＣＯ3のモル比が１対１になる量のＢａＣＯ3粉末を添加した。 An amount of BaCO 3 powder in which the molar ratio of BaTiO 3 and BaCO 3 was 1: 1 was added to the BaTiO 3 powder.

さらに、上述のように、モル比が１：１となるように配合されたＢａＴｉＯ3とＢａＣＯ3のすべてがＢａ2ＴｉＯ4となるように反応が生じるとした場合の理論量のＢａ2ＴｉＯ4に対して、酸化ニッケル（ＮｉＯ）を、含有割合が１．５重量％となるように添加した。このときのＮｉＯの割合を金属Ｎｉに換算すると１．１８重量％となる。 Further, as mentioned above, the molar ratio of 1: 1 to become so formulated BaTiO 3 and Ba 2 TiO 4 weight theory if all BaCO 3 was a reaction so that Ba 2 TiO 4 occurs On the other hand, nickel oxide (NiO) was added so that a content rate might be 1.5 weight%. When the ratio of NiO at this time is converted to metal Ni, it is 1.18% by weight.

それから、純水、ＰＳＺ玉石、分散剤、消泡剤を加え、樹脂製のポットを用いたボールミルにて１６〜２０時間の混合・粉砕を行い、原料粉末が分散したスラリーを得た。   Then, pure water, PSZ boulder, a dispersant and an antifoaming agent were added, and mixing and pulverization were performed for 16 to 20 hours in a ball mill using a resin pot to obtain a slurry in which raw material powder was dispersed.

次に、このスラリーを１２０℃で１０時間乾燥した後、得られた粉末を１０００〜１２００℃、２時間保持の条件で焼成し、複合酸化物であるＢａ2ＴｉＯ4を主成分とする炭酸ガス吸収材（セラミックス粉末）を得た。 Next, this slurry was dried at 120 ° C. for 10 hours, and then the obtained powder was fired at 1000 to 1200 ° C. for 2 hours, and carbon dioxide gas containing Ba 2 TiO 4 as a main component was a composite oxide. An absorbent material (ceramic powder) was obtained.

それから、このＮｉＯを１．５重量％（Ｎｉとして１．１８重量％）の割合で添加した炭酸ガス吸収材について、ＴＧ−ＤＴＡ分析機を用い、８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させ、熱重量分析を行った。その結果を図４に示す。   Then, carbon dioxide gas was continuously added between 800 and 1050 ° C. using a TG-DTA analyzer for the carbon dioxide absorbent to which NiO was added at a ratio of 1.5 wt% (1.18 wt% as Ni). Absorption and release were performed, and thermogravimetric analysis was performed. The result is shown in FIG.

この実施例２の、ＮｉＯを１．５重量％（Ｎｉ金属換算で１．１８重量％）の割合で添加した炭酸ガス吸収材においても、図４に示すように、炭酸ガスの吸収・放出のサイクルが増えた場合におけるＴＧ最大変化量の減少は認められないことが確認された。
なお、図２に示すように、Ｎｉを添加していない炭酸ガス吸収材では、３サイクル目からＴＧ最大変化量が減少し始めることは、上記実施例１で説明したとおりである。
また、この実施例２の炭酸ガス吸収材については、その他の点においても、上記実施例１の炭酸ガス吸収材と同等の性能を有していることが確認された。 Also in the carbon dioxide absorbing material added with NiO at a ratio of 1.5 wt% (Ni metal equivalent: 1.18 wt%) in Example 2, as shown in FIG. It was confirmed that no decrease in the maximum change in TG was observed when the cycle increased.
As shown in FIG. 2, the carbon dioxide absorbing material to which Ni is not added starts to decrease the TG maximum change amount from the third cycle as described in the first embodiment.
In addition, the carbon dioxide absorbent of Example 2 was confirmed to have the same performance as the carbon dioxide absorbent of Example 1 in other respects.

上述のように、Ｎｉを酸化物（ＮｉＯ）のかたちで添加するようにした実施例２の炭酸ガス吸収材の場合にも、Ｂａ2ＴｉＯ4を主成分とする炭酸ガス吸収材の炭酸ガス吸収・放出量を安定的に確保できることが確認された。
したがって、この実施例２の炭酸ガス吸収材を用いた場合にも、炭酸ガス分離・回収装置システムなどにおいて、炭酸ガスを安定的に分離・回収することが可能になる。 As described above, in the case of the carbon dioxide absorbent of Example 2 in which Ni is added in the form of an oxide (NiO), the carbon dioxide absorption of the carbon dioxide absorbent containing Ba 2 TiO 4 as the main component.・ It was confirmed that the release amount could be secured stably.
Therefore, even when the carbon dioxide absorbent of Example 2 is used, carbon dioxide can be stably separated and collected in a carbon dioxide separation / recovery device system or the like.

ＳｒＴｉＯ3粉末に対して、ＳｒＴｉＯ3とＳｒＣＯ3のモル比が１対１になる量のＳｒＣＯ3粉末を添加した。 An amount of SrCO 3 powder in which the molar ratio of SrTiO 3 and SrCO 3 was 1: 1 was added to the SrTiO 3 powder.

さらに、上述のように、モル比が１：１となるように配合されたＳｒＴｉＯ3とＳｒＣＯ3のすべてがＳｒ2ＴｉＯ4となるように反応が生じるとした場合の理論量のＳｒ2ＴｉＯ4に対して、Ｎｉの含有割合が金属換算で１．５重量％となるようにＮｉ金属粉末を添加した。 Further, as mentioned above, the molar ratio of 1: 1 to become so formulated SrTiO 3 and Sr 2 TiO 4 weight theory if all SrCO 3 was a reaction such that the Sr 2 TiO 4 occurs On the other hand, Ni metal powder was added so that the Ni content was 1.5% by weight in terms of metal.

それから、純水、ＰＳＺ玉石、分散剤、消泡剤を加え、樹脂製のポットを用いたボールミルにて１６〜２０時間の混合・粉砕を行い、原料粉末が分散したスラリーを得た。   Then, pure water, PSZ boulder, a dispersant and an antifoaming agent were added, and mixing and pulverization were performed for 16 to 20 hours in a ball mill using a resin pot to obtain a slurry in which raw material powder was dispersed.

次に、このスラリーを１２０℃で１０時間乾燥した後、得られた粉末を１０００〜１２００℃、２時間保持の条件で焼成し、複合酸化物であるＳｒ2ＴｉＯ4を主成分とする炭酸ガス吸収材（セラミックス粉末）を得た。 Next, this slurry was dried at 120 ° C. for 10 hours, and then the obtained powder was fired at 1000 to 1200 ° C. for 2 hours, and carbon dioxide gas containing Sr 2 TiO 4 which is a composite oxide as a main component. An absorbent material (ceramic powder) was obtained.

それから、この炭酸ガス吸収材について、ＴＧ−ＤＴＡ分析機を用い、８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させて熱重量分析を行った。その結果を図５に示す。   The carbon dioxide absorbent was subjected to thermogravimetric analysis by continuously absorbing and releasing carbon dioxide between 800 and 1050 ° C. using a TG-DTA analyzer. The result is shown in FIG.

複合酸化物であるＳｒ2ＴｉＯ4を主成分とする炭酸ガス吸収材についても、Ｎｉを上述の割合で添加したものについては、図５に示すように、炭酸ガスの吸収・放出のサイクルが増えた場合にも、ＴＧ最大変化量は減少しないことが確認された。 As for the carbon dioxide absorbing material mainly composed of Sr 2 TiO 4 , which is a composite oxide, with the addition of Ni at the above-mentioned ratio, as shown in FIG. In this case, it was confirmed that the maximum change in TG did not decrease.

なお、複合酸化物であるＳｒ2ＴｉＯ4を主成分とする炭酸ガス吸収材についても、Ｎｉを添加していないものは、３サイクル目からＴＧ最大変化量が減少し始めることが確認されている。
また、この実施例３の炭酸ガス吸収材については、その他の点においても、上記実施例１および２の炭酸ガス吸収材と同等の性能を有していることが確認されている。 It is confirmed that the carbon dioxide absorption material mainly composed of Sr 2 TiO 4 , which is a composite oxide, also begins to decrease the maximum TG change amount from the third cycle when no Ni is added. .
In addition, the carbon dioxide absorbent of Example 3 was confirmed to have the same performance as the carbon dioxide absorbents of Examples 1 and 2 in other respects.

上述のように、Ｓｒ2ＴｉＯ4を主成分とする実施例３の炭酸ガス吸収材においても、上述の割合でＮｉを添加することにより、炭酸ガスの吸収・放出量を安定的に確保できることが確認された。 As described above, also in the carbon dioxide absorbent of Example 3 containing Sr 2 TiO 4 as a main component, the amount of carbon dioxide absorbed and released can be stably secured by adding Ni at the above-described ratio. confirmed.

したがって、この実施例３の炭酸ガス吸収材を用いた場合にも、炭酸ガス分離・回収装置システムなどにおいて、炭酸ガスを安定的に分離・回収することができる。   Therefore, even when the carbon dioxide absorbent of Example 3 is used, carbon dioxide can be stably separated and recovered in a carbon dioxide separator / collector system or the like.

図６は本願発明の一実施例にかかる炭酸ガス分離方法を用いた炭酸ガスの分離装置の概略構成を示す図である。   FIG. 6 is a diagram showing a schematic configuration of a carbon dioxide separation device using the carbon dioxide separation method according to one embodiment of the present invention.

この炭酸ガス分離装置は、燃焼排ガス（炭酸ガス含有ガス）中の炭酸ガスを本願発明の炭酸ガス吸収材により吸収、分離した後、炭酸ガスを吸収した炭酸ガス吸収材から炭酸ガスを放出させて回収するための炭酸ガス分離装置であり、炭酸ガス吸収機構部および炭酸ガス放出機構部として機能する二つの機構部Ａ，Ｂと、燃焼排ガスの流れを切り替える切替弁Ｃとを備えている。   This carbon dioxide separator separates carbon dioxide in combustion exhaust gas (carbon dioxide-containing gas) with the carbon dioxide absorbent of the present invention, and then releases carbon dioxide from the carbon dioxide absorbent that has absorbed carbon dioxide. This is a carbon dioxide separator for recovery, and includes two mechanism parts A and B that function as a carbon dioxide absorption mechanism part and a carbon dioxide release mechanism part, and a switching valve C that switches the flow of combustion exhaust gas.

なお、図６は、切替弁Ｃにより、左側の機構部Ａに炭酸ガス含有ガス（原料ガス）が供給されるように設定された状態を示しており、左側の機構部Ａが炭酸ガス吸収機構部として機能し、右側の機構部Ｂが炭酸ガスを放出させる炭酸ガス放出機構部として機能する状態を示している。
各機構部ＡおよびＢはいずれも、容器１と、ヒータ２と、容器１の内部に充填された本願発明にかかる炭酸ガス吸収材３（ここでは上記実施例１の、Ｎｉ金属換算で１．５重量％の割合でＮｉ金属粉末を添加した炭酸ガス吸収材）とを備えている。 FIG. 6 shows a state in which the switching valve C is set so that carbon dioxide-containing gas (raw material gas) is supplied to the left mechanism A, and the left mechanism A is the carbon dioxide absorption mechanism. It shows a state in which the right mechanism part B functions as a carbon dioxide gas releasing mechanism part that releases carbon dioxide gas.
Each mechanism part A and B is a container 1, a heater 2, and a carbon dioxide absorbent 3 according to the present invention filled in the container 1 (here, 1. in terms of Ni metal in Example 1 above). Carbon dioxide absorbing material to which Ni metal powder is added at a ratio of 5% by weight).

そして、図６に示すように、左側の機構部Ａに燃焼排ガスが供給されるように切替弁Ｃを切り替えた状態で、燃焼排ガス（この実施例４では、圧力：常圧、温度：約８００℃、炭酸ガス（ＣＯ2）含有率：２０vol％の燃焼排ガス）を供給することにより、機構部（炭酸ガス吸収機構部）Ａで炭酸ガスの吸収が行なわれる。 Then, as shown in FIG. 6, in the state where the switching valve C is switched so that the combustion exhaust gas is supplied to the mechanism A on the left side, the combustion exhaust gas (in Example 4, pressure: normal pressure, temperature: about 800 Carbon dioxide gas is absorbed by the mechanism part (carbon dioxide absorption mechanism part) A by supplying a combustion gas (carbon dioxide gas (CO 2 ) content rate: 20 vol%) at ℃.

一方、機構部（炭酸ガス放出機構部）Ｂでは、容器１の出口側から真空吸引して、圧力を１０ｋＰａ以下の減圧状態（例えば１０００Ｐａ）とし、ヒータ２により容器１内の炭酸ガスを吸収した炭酸ガス吸収材３を１０５０℃に加熱することにより、炭酸ガス吸収材３から炭酸ガスが放出され、放出された炭酸ガスが高濃度で回収されるとともに、炭酸ガスを吸収した炭酸ガス吸収材３が再生され、再使用に供されることになる。   On the other hand, in the mechanism part (carbon dioxide gas release mechanism part) B, vacuum suction is performed from the outlet side of the container 1, the pressure is reduced to 10 kPa or less (for example, 1000 Pa), and the carbon dioxide gas in the container 1 is absorbed by the heater 2. By heating the carbon dioxide absorbent 3 to 1050 ° C., carbon dioxide is released from the carbon dioxide absorbent 3, and the released carbon dioxide is recovered at a high concentration, and the carbon dioxide absorbent 3 that has absorbed carbon dioxide is absorbed. Will be recycled and reused.

なお、炭酸ガス分離装置における、炭酸ガス吸収材による炭酸ガスの吸収反応は下記の化学式(１)の通りであり、
Ｂａ2ＴｉＯ4＋ＣＯ2 → ＢａＴｉＯ3＋ＢａＣＯ3 ……（１）
また、炭酸ガスを吸収した炭酸ガス吸収材からの炭酸ガスの放出反応は、下記の化学式(３)の通りである。
ＢａＴｉＯ3＋ＢａＣＯ3 → Ｂａ2ＴｉＯ4 ＋ＣＯ2↑ ……（３） The carbon dioxide absorption reaction by the carbon dioxide absorbent in the carbon dioxide separator is as shown in the following chemical formula (1).
Ba 2 TiO 4 + CO 2 → BaTiO 3 + BaCO 3 (1)
The release reaction of carbon dioxide from the carbon dioxide absorbent that has absorbed carbon dioxide is represented by the following chemical formula (3).
BaTiO 3 + BaCO 3 → Ba 2 TiO 4 + CO 2 ↑ (3)

そして、機構部（炭酸ガス吸収機構部）Ａに充填された炭酸ガス吸収材３の炭酸ガス吸収性能が低下すると、右側の機構部Ｂに燃焼排ガスが供給されるように切替弁Ｃを切り替え、燃焼排ガスを機構部Ｂに供給し、機構部（炭酸ガス吸収機構部）Ｂに充填された炭酸ガス吸収材３により炭酸ガスの吸収を行う。   Then, when the carbon dioxide absorption performance of the carbon dioxide absorbent 3 filled in the mechanism part (carbon dioxide absorption mechanism part) A is lowered, the switching valve C is switched so that the combustion exhaust gas is supplied to the right mechanism part B, Combustion exhaust gas is supplied to the mechanism B, and carbon dioxide is absorbed by the carbon dioxide absorbent 3 filled in the mechanism (carbon dioxide absorption mechanism) B.

一方、機構部Ａでは、容器１の出口側から真空吸引して、圧力を１０ｋＰａ以下の減圧状態（例えば１０００Ｐａ）とし、ヒータ２により容器１内の、炭酸ガスを吸収した炭酸ガス吸収材３を９００℃に加熱して、炭酸ガス吸収材３から炭酸ガスを放出させ、放出させた炭酸ガスを回収するとともに、炭酸ガスを吸収した炭酸ガス吸収材３を再生させる。なお、この実施例４では前記実施例１の炭酸ガス吸収材を用いており、この炭酸ガス吸収材は、常温では１０２１℃を超える温度条件で効率よく炭酸ガスの放出が行われるような材料であるが、上述のように、減圧状態（例えば１０００Ｐａ）とすることにより、９００℃程度の温度でも炭酸ガスを効率よく放出させることができる。   On the other hand, in the mechanism part A, vacuum suction is performed from the outlet side of the container 1, the pressure is reduced to a pressure of 10 kPa or less (for example, 1000 Pa), and the carbon dioxide absorbing material 3 that absorbs carbon dioxide in the container 1 is heated by the heater 2. Heating to 900 ° C. releases carbon dioxide from the carbon dioxide absorbent 3, collects the released carbon dioxide, and regenerates the carbon dioxide absorbent 3 that has absorbed carbon dioxide. In Example 4, the carbon dioxide absorbent of Example 1 is used. This carbon dioxide absorbent is a material that can efficiently release carbon dioxide at a temperature exceeding 1021 ° C. at room temperature. However, as described above, the carbon dioxide gas can be efficiently released even at a temperature of about 900 ° C. by using a reduced pressure state (for example, 1000 Pa).

そして、これを繰り返すことにより、長期間にわたって、安定して炭酸ガスの分離、回収を行うことが可能になる。
なお、機構部Ａと機構部Ｂを交互に炭酸ガス吸収機構部と炭酸ガス放出機構部に切り替える際の、各機構部Ａ、Ｂから排出されるガスの流路の切り替えは、切替弁Ｃを設けることで容易に行うことが可能である。
なお、図６の概略構成図では、機構部Ａと機構部Ｂが１つずつ設けられているが、少なくともいずれかを複数にして機構部を３個以上にしてもよい。 By repeating this, carbon dioxide gas can be stably separated and recovered over a long period of time.
In addition, when switching the mechanism part A and the mechanism part B to the carbon dioxide absorption mechanism part and the carbon dioxide gas release mechanism part alternately, the switching of the flow path of the gas discharged from each mechanism part A, B is performed by the switching valve C. It can be easily performed by providing.
In the schematic configuration diagram of FIG. 6, one mechanism part A and one mechanism part B are provided. However, at least one of them may be plural, and the number of mechanism parts may be three or more.

上述のように、図６に示すような炭酸ガス分離装置を用い、実施例１の炭酸ガス吸収材（主要な結晶相がＢａ2Ｆｅ2Ｏ5である炭酸ガス吸収材）を、圧力：常圧、温度：約８００℃の条件下で炭酸ガス２０vol％の燃焼排ガスと接触させて炭酸ガスを炭酸ガス吸収材に吸収させるとともに、炭酸ガスを吸収した炭酸ガス吸収材を、減圧下（１０００Ｐａ）で所定の温度（９００℃）に加熱して、炭酸ガスを放出させるようにしているので、炭酸ガス吸収機構部において、高温下での炭酸ガスの吸収を確実に行い、炭酸ガス放出機構部において、吸収した炭酸ガスの放出（炭酸ガス吸収材の再生）を確実に行うことができることから、ＬｉxＳｉyＯzで表されるリチウムシリケート系の炭酸ガス吸収材では対応することができないような高温下での炭酸ガスの分離、回収を経済的に、かつ、安定して効率よく行うことができる。 As described above, using the carbon dioxide separator as shown in FIG. 6, the carbon dioxide absorbent of Example 1 (carbon dioxide absorbent whose main crystal phase is Ba 2 Fe 2 O 5 ) is used under pressure: ordinary Pressure and temperature: The carbon dioxide absorbent is absorbed by the carbon dioxide absorbent by contacting it with the combustion exhaust gas of 20 vol% carbon dioxide under the condition of about 800 ° C., and the carbon dioxide absorbent that has absorbed the carbon dioxide is reduced in pressure (1000 Pa). The carbon dioxide gas is released by heating to a predetermined temperature (900 ° C.), so that the carbon dioxide absorption mechanism portion reliably absorbs the carbon dioxide gas at a high temperature. , such as the fact that it is possible to perform the absorption release of carbon dioxide gas (regeneration of carbon dioxide-absorbing material) securely, can not cope with the Li x Si y O z carbon dioxide gas absorbent of lithium silicate system represented by Under high temperature The separation and recovery of carbon dioxide gas can be carried out economically, stably and efficiently.

なお、上記実施例では、炭酸ガス吸収材が粉末状態である場合を例にとって説明したが、本願発明の炭酸ガス吸収材は、粉末の形態に限らず、ある程度大きな粒状の形態でも用いることが可能であり、さらには、例えば、立方体、直方体、球状などの種々の形状の成形体、シート状の成形体、さらには、それらを組み合わせた形状を有する構造体などの形態で使用することも可能である。   In the above embodiment, the case where the carbon dioxide absorbent is in a powder state has been described as an example. However, the carbon dioxide absorbent of the present invention is not limited to a powder form, and can be used in a somewhat large granular form. Furthermore, it can be used in the form of, for example, a molded body having various shapes such as a cube, a rectangular parallelepiped, and a sphere, a sheet-shaped molded body, and a structure having a combined shape. is there.

なお、本願発明は上記の各実施例の構成に限定されるものではなく、炭酸ガス吸収材の出発原料の種類、具体的な合成方法、合成条件、本願発明の炭酸ガス吸収材を用いて行う炭酸ガスの吸収条件などに関し、発明の範囲内において、種々の応用、変形を加えることが可能である。   In addition, this invention is not limited to the structure of said each Example, It carries out using the kind of starting material of a carbon dioxide absorber, a specific synthesis method, synthesis conditions, and the carbon dioxide absorber of this invention. Various applications and modifications can be made within the scope of the invention with respect to carbon dioxide absorption conditions and the like.

上述のように、本願発明の炭酸ガス吸収材は、ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物を主成分とし、Ｎｉを金属換算で０．２重量％以上、好ましくは、０．４〜６．０重量％の割合で含有するものであり、圧力：１．０×１０4〜１．０×１０6Ｐａ、温度：５００〜９００℃の条件で炭酸ガスの吸収を効率よく行い、炭酸ガス吸収材に吸収させた炭酸ガスの放出（炭酸ガス吸収材の再生）を、圧力：１０００Ｐａ以下、温度：７５０℃以上の条件で効率よく行うことが可能であり、特に、約８００℃〜１０５０℃の間では、炭酸ガスの吸収・放出をより効率よく行うことができる。
また、この炭酸ガス吸収材は、材料自体の蒸気圧が低く、耐久性にも優れており、長期間安定して使用することができる。
したがって、本願発明は、水素製造プロセスにおける燃焼前の炭酸ガスの分離、工場において発生する燃焼排ガス中の炭酸ガスの除去、自動車エンジンからの排ガス中の炭酸ガスの除去をはじめ、種々の分野で発生する炭酸ガスを含むガスからの炭酸ガスの分離に広く適用することが可能である。 As described above, the carbon dioxide absorbent of the present invention comprises component substance X, which is at least one of Sr and Ba, and Ti at a molar ratio (X / Ti): 1.8 to 2.2. And containing Ni in a proportion of 0.2% by weight or more, preferably 0.4 to 6.0% by weight in terms of metal, pressure: 1.0 × 10 4 Up to 1.0 × 10 6 Pa, temperature: Carbon dioxide is efficiently absorbed under the conditions of 500 to 900 ° C., and the release of carbon dioxide absorbed by the carbon dioxide absorbent (regeneration of carbon dioxide absorbent) is performed under pressure. : 1000 Pa or less, temperature: 750 ° C. or more can be carried out efficiently. In particular, carbon dioxide gas can be absorbed and released more efficiently between about 800 ° C. and 1050 ° C.
In addition, this carbon dioxide absorbing material has a low vapor pressure of the material itself, is excellent in durability, and can be used stably for a long period of time.
Therefore, the present invention is generated in various fields such as separation of carbon dioxide before combustion in the hydrogen production process, removal of carbon dioxide in combustion exhaust gas generated in a factory, removal of carbon dioxide in exhaust gas from an automobile engine. The present invention can be widely applied to the separation of carbon dioxide from a gas containing carbon dioxide.

本願発明の実施例において、Ｎｉを含有していない炭酸ガス吸収材について行った、ＴＧ−ＤＴＡ分析の結果を示す図である。In the Example of this invention, it is a figure which shows the result of the TG-DTA analysis performed about the carbon dioxide gas absorbent which does not contain Ni. 本願発明の実施例において、Ｎｉ金属を添加していない炭酸ガス吸収材について８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させて熱重量分析を行った結果を示す図である。In the Example of this invention, it is a figure which shows the result of having carried out the thermogravimetric analysis by making carbon dioxide gas absorb and discharge | release continuously between 800-1050 degreeC about the carbon dioxide absorber which has not added Ni metal. 本願発明の一実施例にかかる、Ｎｉ金属１．５重量％を添加した炭酸ガス吸収材について８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させて熱重量分析を行った結果を示す図である。The result of carrying out the thermogravimetric analysis by absorbing and releasing carbon dioxide continuously between 800 to 1050 ° C. for the carbon dioxide absorbent to which 1.5% by weight of Ni metal is added according to one embodiment of the present invention is shown. FIG. 本願発明の他の実施例にかかる、ＮｉＯを１．５重量％（Ｎｉとして１．１８重量％）添加した炭酸ガス吸収材について８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させて熱重量分析を行った結果を示す図である。According to another embodiment of the present invention, carbon dioxide absorbing material added with 1.5% by weight of NiO (1.18% by weight as Ni) is allowed to continuously absorb and release carbon dioxide between 800-1050 ° C. It is a figure which shows the result of having performed the thermogravimetric analysis. 本願発明のさらに他の実施例にかかる炭酸ガス吸収材について８００〜１０５０℃間で炭酸ガスを連続的に吸収・放出させて熱重量分析を行った結果を示す図である。It is a figure which shows the result of having performed the thermogravimetric analysis by making carbon dioxide gas absorb and discharge | release continuously between 800-1050 degreeC about the carbon dioxide absorber concerning the further another Example of this invention. 本願発明の実施例にかかる炭酸ガス分離装置の概略構成を示す図である。It is a figure which shows schematic structure of the carbon dioxide gas separation device concerning the Example of this invention.

符号の説明Explanation of symbols

１ 容器
２ ヒータ
３ 炭酸ガス吸収材
Ａ，Ｂ 機構部
Ｃ 切替弁 1 Container 2 Heater 3 Carbon Dioxide Absorber A, B Mechanism C Switch Valve

Claims (4)

ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物を主成分とし、
Ｎｉを金属換算で０．２重量％以上含有すること
を特徴とする炭酸ガス吸収材。 The main component is a composite oxide containing a component substance X, which is at least one of Sr and Ba, and Ti at a molar ratio (X / Ti): 1.8 to 2.2,
A carbon dioxide absorbent comprising Ni in an amount of 0.2% by weight or more in terms of metal. ＳｒおよびＢａの少なくとも１種である成分物質Ｘと、Ｔｉとを、モル比（Ｘ／Ｔｉ）：１．８〜２．２の割合で含む複合酸化物を主成分とし、
Ｎｉを金属換算で０．４〜６．０重量％の割合で含有すること
を特徴とする炭酸ガス吸収材。 The main component is a composite oxide containing a component substance X, which is at least one of Sr and Ba, and Ti at a molar ratio (X / Ti): 1.8 to 2.2,
A carbon dioxide absorbent comprising Ni in a proportion of 0.4 to 6.0% by weight in terms of metal. 請求項１または２記載の炭酸ガス吸収材を用い、
圧力：１．０×１０4〜１．０×１０6Ｐａ、
温度：５００〜９００℃
の条件で炭酸ガスを吸収させる工程と、
前記炭酸ガス吸収材に吸収させた炭酸ガスを、
圧力：１０００Ｐａ以下、
温度：７５０℃以上
の条件で放出させる工程と
を具備することを特徴とする炭酸ガス分離方法。 Using the carbon dioxide absorbent according to claim 1 or 2,
Pressure: 1.0 × 10 4 to 1.0 × 10 6 Pa,
Temperature: 500-900 ° C
A step of absorbing carbon dioxide under the conditions of
The carbon dioxide absorbed by the carbon dioxide absorbent is
Pressure: 1000 Pa or less,
And a step of releasing at a temperature of 750 ° C. or higher. 請求項１または２記載の炭酸ガス吸収材を、
圧力：１．０×１０4〜１．０×１０6Ｐａ、
温度：５００〜９００℃
の条件で炭酸ガスを含む気流と接触させて炭酸ガスを前記炭酸ガス吸収材に吸収させる炭酸ガス吸収機構部と、
炭酸ガスを含む気流と接触して炭酸ガスを吸収した炭酸ガス吸収材を、
圧力：１０００Ｐａ以下の減圧下、
温度：７５０℃以上
の条件で加熱して、炭酸ガスを放出させる炭酸ガス放出機構部と
を具備することを特徴とする炭酸ガス分離装置。 The carbon dioxide absorbent according to claim 1 or 2,
Pressure: 1.0 × 10 4 to 1.0 × 10 6 Pa,
Temperature: 500-900 ° C
A carbon dioxide absorption mechanism that allows carbon dioxide to be absorbed by the carbon dioxide absorbent by contacting with an air stream containing carbon dioxide under the conditions of
A carbon dioxide absorbent that absorbs carbon dioxide in contact with an air stream containing carbon dioxide,
Pressure: Under reduced pressure of 1000 Pa or less,
A carbon dioxide gas separation device comprising: a carbon dioxide gas release mechanism for releasing carbon dioxide gas by heating at a temperature of 750 ° C. or higher.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014189006A1 (en) * 2013-05-21 2014-11-27 株式会社村田製作所 Catalyst for reforming hydrocarbon-based gas and method for reforming hydrocarbon-based gas using same
US20190308134A1 (en) * 2018-04-05 2019-10-10 Hamilton Sundstrand Corporation Fuel tank inerting system

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014189006A1 (en) * 2013-05-21 2014-11-27 株式会社村田製作所 Catalyst for reforming hydrocarbon-based gas and method for reforming hydrocarbon-based gas using same
US20190308134A1 (en) * 2018-04-05 2019-10-10 Hamilton Sundstrand Corporation Fuel tank inerting system
US11040306B2 (en) * 2018-04-05 2021-06-22 Hamilton Sunstrand Corporation Fuel tank inerting system

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