JP2020069414A - Carbon dioxide separation composition - Google Patents

Carbon dioxide separation composition Download PDF

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JP2020069414A
JP2020069414A JP2018203622A JP2018203622A JP2020069414A JP 2020069414 A JP2020069414 A JP 2020069414A JP 2018203622 A JP2018203622 A JP 2018203622A JP 2018203622 A JP2018203622 A JP 2018203622A JP 2020069414 A JP2020069414 A JP 2020069414A
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zinc
carbon dioxide
separation composition
dioxide separation
polyethylene polyamine
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靖 原
Yasushi Hara
靖 原
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Tosoh Corp
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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
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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

Abstract

To provide a carbon dioxide separation composition in which amine that emits carbon dioxide at low temperature is used.SOLUTION: A composition including polyethylenepolyamine, a zinc compound and water is used for separating carbon dioxide.SELECTED DRAWING: None

Description

本発明は、二酸化炭素分離液に関する。   The present invention relates to a carbon dioxide separation liquid.

近年、地球温暖化問題のため、二酸化炭素の分離・回収が注目されており、多くの二酸化炭素吸収液の開発がなされている。   In recent years, due to the problem of global warming, attention has been paid to the separation and recovery of carbon dioxide, and many carbon dioxide absorbing liquids have been developed.

二酸化炭素の吸収液として、アミンの水溶液、特にモノエタノールアミン水溶液が最も一般的である。モノエタノールアミンは、安価で工業的に入手しやすいが、低温で吸収した二酸化炭素を１２０℃以上の高温にしないと放出しないという特性がある。そして、二酸化炭素放出温度を水の沸点以上にすると、水の高い潜熱、比熱のため、二酸化炭素の回収に多くのエネルギーを要することになる。   As the carbon dioxide absorption liquid, an amine aqueous solution, particularly a monoethanolamine aqueous solution, is most common. Although monoethanolamine is inexpensive and easy to obtain industrially, it has a characteristic that carbon dioxide absorbed at a low temperature is not released unless it is heated to a high temperature of 120 ° C. or higher. When the carbon dioxide release temperature is set to be higher than the boiling point of water, a large amount of energy is required to recover carbon dioxide due to the high latent heat and specific heat of water.

そのため、モノエタノールアミンより二酸化炭素放散温度が低く、二酸化炭素回収エネルギーの低いアミンの開発がなされている。例えば、アミノメチルプロパノール（特許文献１）、エチルアミノエタノール（特許文献２）、イソプロピルアミノエタノール（特許文献３）が提案されている。これらは、いずれもアミノ基を嵩高い置換基で保護することにより、二酸化炭素−アミン間の強固な結合の生成を阻害し、二酸化炭素の放散エネルギーを低下させることができるものであるが、低分子アミンであるため沸点が低く、蒸発による損失が大きい。また、工業的に使用するには価格が高い。高沸点のアミンとしてＮ−メチルジエタノールアミン（特許文献４）も知られているが、二酸化炭素の吸収量が低い。更に、モノエタノールアミンの金属錯体化によって、二酸化炭素の放散速度を加速する方法（非特許文献１）が知られているが、逆に二酸化炭素の吸収量が大きく低下する。   Therefore, an amine having a lower carbon dioxide emission temperature and a lower carbon dioxide recovery energy than monoethanolamine has been developed. For example, aminomethyl propanol (Patent Document 1), ethylaminoethanol (Patent Document 2), and isopropylaminoethanol (Patent Document 3) have been proposed. In any of these, by protecting the amino group with a bulky substituent, the formation of a strong carbon dioxide-amine bond can be inhibited and the carbon dioxide emission energy can be reduced. Since it is a molecular amine, it has a low boiling point and a large loss due to evaporation. Moreover, the price is high for industrial use. N-methyldiethanolamine (Patent Document 4) is also known as a high-boiling amine, but it has a low carbon dioxide absorption amount. Further, a method of accelerating the carbon dioxide emission rate by forming a metal complex of monoethanolamine (Non-Patent Document 1) is known, but on the contrary, the carbon dioxide absorption amount is greatly reduced.

特開平０６−３４３８５８号公報Japanese Patent Laid-Open No. 06-343858 特開平０８−０８９７５６号公報Japanese Patent Laid-Open No. 08-089756 特開２００７−２１７３４４公報JP, 2007-217344, A 国際公開第９９／０５１３２６号パンフレットInternational Publication No. 99/051326 Pamphlet

Ｊｏｕｒｎａｌ ｏｆ ＣＯ２ Ｕｔｉｌｉｚａｔｉｏｎ ２１ （２０１７） １３９−１４４Journal of CO2 Utilization 21 (2017) 139-144

本発明は上記の課題に鑑みてなされたものであり、その目的は、低温で二酸化炭素を放散するアミンを使用した二酸化炭素分離組成物を提供することにある。   The present invention has been made in view of the above problems, and an object thereof is to provide a carbon dioxide separation composition that uses an amine that emits carbon dioxide at low temperatures.

本発明者は、二酸化炭素を吸収、放散するアミンについて鋭意検討した結果、ポリエチレンポリアミンと亜鉛を含む水溶液が、ポリエチレンポリアミンに比べて、二酸化炭素を高効率で吸収、放散することができるという新規な事実を見出し、本発明を完成させるに至った。   The present inventor has made extensive studies on amines that absorb and emit carbon dioxide, and as a result, an aqueous solution containing polyethylene polyamine and zinc can absorb and emit carbon dioxide with high efficiency compared to polyethylene polyamine. The facts have been found and the present invention has been completed.

すなわち、本発明は、以下に示すとおりの二酸化炭素分離組成物である。   That is, the present invention is a carbon dioxide separation composition as shown below.

［１］ポリエチレンポリアミン、亜鉛化合物、及び水を含む二酸化炭素分離組成物。   [1] A carbon dioxide separation composition containing polyethylene polyamine, a zinc compound, and water.

［２］ポリエチレンポリアミンが、ジエチレントリアミン、ピペラジン、Ｎ−（２−アミノエチル）ピペラジン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミンからなる群より選ばれる少なくとも一種である、上記［１］に記載の二酸化炭素分離組成物。   [2] The polyethylene polyamine is at least one selected from the group consisting of diethylenetriamine, piperazine, N- (2-aminoethyl) piperazine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. The carbon dioxide separating composition according to [1].

［３］水の濃度が、３０〜９５重量％である、上記［１］又は［２］に記載の二酸化炭素分離組成物。   [3] The carbon dioxide separation composition according to the above [1] or [2], wherein the concentration of water is 30 to 95% by weight.

［４］亜鉛化合物が、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛などのハロゲン化亜鉛、硝酸亜鉛、硫酸亜鉛、硫化亜鉛、炭酸亜鉛、酸化亜鉛、水酸化亜鉛、ギ酸亜鉛、酢酸亜鉛などの有機酸亜鉛からなる群より選ばれる少なくとも一種である、上記［１］〜［３］のいずれかに記載の二酸化炭素分離組成物。   [4] The zinc compound is zinc fluoride, zinc chloride, zinc bromide, zinc iodide, or another zinc halide, zinc nitrate, zinc sulfate, zinc sulfide, zinc carbonate, zinc oxide, zinc hydroxide, zinc formate, acetic acid. The carbon dioxide separation composition according to any of [1] to [3] above, which is at least one selected from the group consisting of organic acid zinc such as zinc.

［５］亜鉛化合物の量が、モル比でポリエチレンポリアミン／Ｚｎ≧４である、上記［１］〜［４］のいずれかに記載の二酸化炭素分離組成物。   [5] The carbon dioxide separation composition according to any of the above [1] to [4], wherein the amount of the zinc compound is polyethylene polyamine / Zn ≧ 4 in a molar ratio.

以下、本発明について詳細に説明する。   Hereinafter, the present invention will be described in detail.

本発明の二酸化炭素分離組成物の必須成分は、ポリエチレンポリアミン、亜鉛化合物及び水である。   The essential components of the carbon dioxide separation composition of the present invention are polyethylene polyamine, zinc compound and water.

本発明の二酸化炭素分離組成物において使用するポリエチレンポリアミンとは、複数のエチレン鎖を有し、しかもそのエチレン鎖の両端にアミノ基を有するアミンの総称である。本発明の二酸化炭素分離組成物において、ポリエチレンポリアミンのアミノ基数は多いほど、吸収した二酸化炭素を高効率で放散することができる。   The polyethylene polyamine used in the carbon dioxide separation composition of the present invention is a general term for amines having a plurality of ethylene chains and having amino groups at both ends of the ethylene chains. In the carbon dioxide separation composition of the present invention, the larger the number of amino groups in the polyethylene polyamine, the more efficiently the absorbed carbon dioxide can be released.

ポリエチレンポリアミンを例示すると、ジエチレントリアミン、ピペラジン、Ｎ−（２−アミノエチル）ピペラジン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミンなどが挙げられる。ジエチレントリアミン、ピペラジン、Ｎ−（２−アミノエチル）ピペラジンは工業的に単一化合物として入手することができるが、トリエチレンテトラミン以上のポリエチレンポリアミンは単一化合物では工業的に入手することは困難であり、蒸留では分離困難な異性体などの混合物として一般に流通している。トリエチレンテトラミンは、直鎖状のトリエチレンテトラミン、分岐したトリス（２−アミノエチル）アミン、ピペラジン環を含むＮ，Ｎ’−ビス（２−アミノエチル）ピペラジン、Ｎ−（３，６−ジアザヘキシル）ピペラジンのアミノ基数４の４種のアミン混合物として、テトラエチレンペンタミンは、直鎖状のテトラエチレンペンタミン、分岐したＮ，Ｎ−ビス（２−アミノエチル）ジエチレントリアミン、ピペラジン環を含むＮ−（３，６−ジアザヘキシル）−Ｎ’−（３−アザプロピル）ピペラジン、Ｎ−（３，６，９−トリアザノニル）ピペラジンのアミノ基数５の４種のアミン混合物として流通している。ペンタエチレンヘキサミン以上の沸点のポリエチレンポリアミンは更に多くのアミンの混合物となっているが、本発明の二酸化炭素分離組成物においては、混合物として使用しても一向に差し支えない。また、他の留分のポリエチレンポリアミン、例えばテトラエチレンペンタミンとペンタエチレンヘキサミンを混合して使用しても一向に差し支えない。   Examples of polyethylene polyamines include diethylenetriamine, piperazine, N- (2-aminoethyl) piperazine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and the like. Diethylenetriamine, piperazine, and N- (2-aminoethyl) piperazine can be industrially obtained as a single compound, but polyethylenepolyamines having triethylenetetramine or higher cannot be industrially obtained with a single compound. Generally, it is distributed as a mixture of isomers which are difficult to separate by distillation. Triethylenetetramine includes linear triethylenetetramine, branched tris (2-aminoethyl) amine, N, N′-bis (2-aminoethyl) piperazine containing a piperazine ring, and N- (3,6-diazahexyl). ) As a mixture of four amines having 4 amino groups of piperazine, tetraethylenepentamine includes linear tetraethylenepentamine, branched N, N-bis (2-aminoethyl) diethylenetriamine, and N-containing piperazine ring. (3,6-diazahexyl) -N '-(3-azapropyl) piperazine and N- (3,6,9-triazanonyl) piperazine are distributed as a mixture of four amines having 5 amino groups. Polyethylene polyamine having a boiling point of pentaethylene hexamine or higher is a mixture of more amines, but it can be used as a mixture in the carbon dioxide separation composition of the present invention. In addition, polyethylene polyamines of other fractions, for example, tetraethylene pentamine and pentaethylene hexamine may be mixed and used.

本発明の二酸化炭素分離組成物には、亜鉛化合物を使用する。特に、アミンと反応し得る亜鉛化合物を使用する。アミンと反応し得る亜鉛化合物としては、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛などのハロゲン化亜鉛、硝酸亜鉛、硫酸亜鉛、硫化亜鉛、炭酸亜鉛、酸化亜鉛、水酸化亜鉛、ギ酸亜鉛、酢酸亜鉛などの有機酸亜鉛が例示され、好ましくはハロゲン化亜鉛、酸化亜鉛、水酸化亜鉛である。   A zinc compound is used in the carbon dioxide separation composition of the present invention. In particular, zinc compounds which can react with amines are used. Examples of zinc compounds capable of reacting with amines are zinc fluoride, zinc chloride, zinc bromide, zinc iodide, and other zinc halides, zinc nitrate, zinc sulfate, zinc sulfide, zinc carbonate, zinc oxide, zinc hydroxide, and formic acid. Examples of organic acid zinc such as zinc and zinc acetate are preferable, and zinc halide, zinc oxide, and zinc hydroxide are preferable.

本発明の二酸化炭素分離組成物において亜鉛化合物を使用すると、二酸化炭素の吸収、放散が促進される。ポリエチレンポリアミンの複数のアミノ基の中で、二酸化炭素と強固な結合を形成し、二酸化炭素の放散を阻害するアミノ基の一部が亜鉛錯塩を形成し、二酸化炭素の放散エネルギーが低下する。また、ポリエチレンポリアミンを亜鉛錯塩にすることにより、ポリエチレンポリアミン分子が伸展し、アミノ基が有効に利用され、二酸化炭素の吸収が容易になる。   When a zinc compound is used in the carbon dioxide separation composition of the present invention, absorption and emission of carbon dioxide are promoted. Among a plurality of amino groups of polyethylene polyamine, a strong bond with carbon dioxide is formed, and a part of the amino group which inhibits the emission of carbon dioxide forms a zinc complex salt, and the emission energy of carbon dioxide decreases. In addition, by using polyethylene polyamine as a zinc complex salt, polyethylene polyamine molecules are extended, amino groups are effectively used, and carbon dioxide is easily absorbed.

本発明の二酸化炭素分離組成物は水溶液として使用する。水はポリエチレンポリアミンの溶媒として、また二酸化炭素を炭酸塩にするために必要である。水を使用しない、又は水が不十分であると、ポリエチレンポリアミンが二酸化炭素と反応した時に、液が粘調になったり、固化したりして、装置閉塞などのトラブルが生じやすくなる。また、アミンと二酸化炭素がカルバミン酸塩を形成し、二酸化炭素の放散エネルギーが高くなる。   The carbon dioxide separating composition of the present invention is used as an aqueous solution. Water is needed as a solvent for the polyethylene polyamine and to convert carbon dioxide to carbonate. If water is not used or if water is insufficient, when the polyethylene polyamine reacts with carbon dioxide, the liquid becomes viscous or solidifies, and troubles such as device clogging are likely to occur. Further, the amine and carbon dioxide form a carbamate, and the energy for radiating carbon dioxide increases.

本発明の二酸化炭素分離組成物の水の濃度は３０〜９５重量％であり、好ましくは５０〜９０重量％である。水が３０重量％未満であると液が粘調になり、装置トラブルが生じやすくなり、９５重量％を超えると二酸化炭素の吸収量が工業的でないほど少なくなる傾向にある。   The concentration of water in the carbon dioxide separation composition of the present invention is 30 to 95% by weight, preferably 50 to 90% by weight. If the amount of water is less than 30% by weight, the liquid becomes viscous, and troubles with the apparatus are likely to occur.

本発明の二酸化炭素分離組成物における亜鉛化合物の量は、ポリエチレンポリアミンの量に影響されるため、限定することは困難であるが、亜鉛化合物の量がモル比でポリエチレンポリアミン／Ｚｎ≧４であることが好ましい。ポリエチレンポリアミン／Ｚｎ＜４であると、二酸化炭素の吸収、放散促進効果が少なくなる。   The amount of zinc compound in the carbon dioxide separation composition of the present invention is difficult to limit because it is influenced by the amount of polyethylene polyamine, but the amount of zinc compound is polyethylene polyamine / Zn ≧ 4 in molar ratio. It is preferable. When polyethylenepolyamine / Zn <4, the effect of promoting absorption and emission of carbon dioxide decreases.

本発明の二酸化炭素分離組成物には、他のよく知られたアミン、例えばモノエタノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、アミノメチルプロパノール、イソプロピルアミノエタノールなどを添加しても良い。また、アルコール類やエチレングリコール、グリセリンなどのポリオール、ポリエチレングリコールなどを添加しても良い。   Other well-known amines such as monoethanolamine, diethanolamine, N-methyldiethanolamine, aminomethylpropanol and isopropylaminoethanol may be added to the carbon dioxide separating composition of the present invention. Further, alcohols, polyols such as ethylene glycol and glycerin, and polyethylene glycol may be added.

本発明の二酸化炭素分離組成物には、亜鉛以外の金属成分を添加しても良い。ニッケル、コバルト、銅などは高価であるため工業的に使用するのは問題があるが、亜鉛と同様にアミンと錯塩を形成しやすく、亜鉛と同様の効果が期待できる。   A metal component other than zinc may be added to the carbon dioxide separation composition of the present invention. Although nickel, cobalt, copper and the like are expensive, they are problematic for industrial use, but like zinc, they easily form a complex salt with an amine, and the same effect as zinc can be expected.

本発明の二酸化炭素分離組成物は、化学吸収法として広く知られた二酸化炭素分離方法に適用できる。化学吸収法は二酸化炭素分離組成物と二酸化炭素を含む気体を接触させ、二酸化炭素を選択的に吸収させた後、高温又は減圧することにより二酸化炭素を放散させる。一般的に二酸化炭素を放散させる温度は１００℃以上であるが、本発明の二酸化炭素分離組成物を使用した場合には、１００℃未満の温度でも二酸化炭素を放散させることができる。   The carbon dioxide separation composition of the present invention can be applied to a carbon dioxide separation method widely known as a chemical absorption method. In the chemical absorption method, a carbon dioxide separation composition and a gas containing carbon dioxide are brought into contact with each other to selectively absorb the carbon dioxide, and then the carbon dioxide is diffused by increasing the temperature or reducing the pressure. Generally, the temperature at which carbon dioxide is released is 100 ° C. or higher, but when the carbon dioxide separation composition of the present invention is used, carbon dioxide can be released even at a temperature below 100 ° C.

本発明の二酸化炭素分離組成物は、吸収した二酸化炭素を高効率で放散することができるため、低エネルギーで二酸化炭素を分離でき、工業的に極めて有用である。   INDUSTRIAL APPLICABILITY The carbon dioxide separating composition of the present invention can dissipate absorbed carbon dioxide with high efficiency, so that carbon dioxide can be separated with low energy and is industrially extremely useful.

本発明を以下の実施例により更に詳細に説明するが、本発明はこれらに限定されるものではない。なお、表記を簡潔にするため、以下の略記号を使用した。   The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The following abbreviations are used for the sake of brevity.

ＭＥＡ：モノエタノールアミン
ＤＥＴＡ：ジエチレントリアミン
ＴＥＴＡ：トリエチレンテトラミン混合物（東ソー株式会社製）
ＴＥＰＡ：テトラエチレンペンタミン混合物（東ソー株式会社製）
ＰＥＨＡ：ペンタエチレンヘキサミン主成分のポリエチレンポリアミン混合物（東ソー株式会社製）
Ｓ−ＰＥＨＡ：ペンタエチレンヘキサミンより高沸点アミンを含むポリエチレンポリアミン混合物（東ソー株式会社製）
実施例１
Ｓ−ＰＥＨＡ１５ｇ、純水３５ｇに塩化亜鉛を２ｇ加え、二酸化炭素吸収液を調製した。これを１２５ｍＬのムインケ式ガス吸収瓶に入れ、水浴で４０℃にした。これに２００ｍＬ／分の二酸化炭素と３００ｍＬ／分の窒素の混合気体を１時間吹き込み、ガス流量計でガスの吸収量を測定したところ、吸収液１ｋｇあたり標準状態で二酸化炭素を４６．１Ｌ吸収した。 MEA: monoethanolamine DETA: diethylenetriamine TETA: triethylenetetramine mixture (manufactured by Tosoh Corporation)
TEPA: Tetraethylene pentamine mixture (manufactured by Tosoh Corporation)
PEHA: Pentaethylenehexamine-based polyethylene polyamine mixture (manufactured by Tosoh Corporation)
S-PEHA: Polyethylene polyamine mixture containing amine having a higher boiling point than pentaethylene hexamine (manufactured by Tosoh Corporation)
Example 1
2 g of zinc chloride was added to 15 g of S-PEHA and 35 g of pure water to prepare a carbon dioxide absorption liquid. This was put into a 125 mL Muinke-type gas absorption bottle and heated to 40 ° C. in a water bath. A mixed gas of 200 mL / min of carbon dioxide and 300 mL / min of nitrogen was blown into this for 1 hour, and the amount of gas absorbed was measured with a gas flowmeter. .

次に、ガス吸収瓶を８０℃の水浴に入れ、３００ｍＬ／分の窒素ガスを１時間吹き込み、ガス流量計でガスの放散量を測定したところ、吸収液１ｋｇあたり標準状態で二酸化炭素を１９．５Ｌ放散した。低温で二酸化炭素を放散できる比率を示すガス放散量とガス吸収量の比は０．４２だった。   Next, the gas absorption bottle was put in a water bath at 80 ° C., 300 mL / min of nitrogen gas was blown therein for 1 hour, and the amount of gas released was measured by a gas flow meter. 5L was emitted. The ratio of the amount of released gas to the amount of absorbed gas, which shows the ratio of releasing carbon dioxide at low temperature, was 0.42.

実施例２
塩化亜鉛を１ｇ使用した他は実施例１と同じ方法で二酸化炭素吸収液を調製した。この液について実施例１と同じ方法で二酸化炭素の吸収量と放散量を測定した。その結果、吸収液１ｋｇあたり標準状態で二酸化炭素を４４．８Ｌ吸収し、１９．１Ｌ放散した。このガス放散量とガス吸収量の比は０．４６だった。 Example 2
A carbon dioxide absorbent was prepared in the same manner as in Example 1 except that 1 g of zinc chloride was used. The absorption amount and the emission amount of carbon dioxide of this liquid were measured by the same method as in Example 1. As a result, 44.8 L of carbon dioxide was absorbed per 1 kg of the absorbing solution in a standard state, and 19.1 L was emitted. The ratio of the gas emission amount to the gas absorption amount was 0.46.

比較例１
塩化亜鉛を加えなかった他は実施例１と同じ方法で二酸化炭素吸収液を調製した。この液について実施例１と同じ方法で二酸化炭素の吸収量と放散量を測定した。その結果、吸収液１ｋｇあたり標準状態で二酸化炭素を４３．７Ｌ吸収し、１６．３Ｌ放散した。このガス放散量とガス吸収量の比は０．３７だった。 Comparative Example 1
A carbon dioxide absorbent was prepared in the same manner as in Example 1 except that zinc chloride was not added. The absorption amount and the emission amount of carbon dioxide of this liquid were measured by the same method as in Example 1. As a result, 43.7 L of carbon dioxide was absorbed in a standard state per 1 kg of the absorbing liquid, and 16.3 L was diffused. The ratio of the gas emission amount to the gas absorption amount was 0.37.

比較例２
ポリエチレンポリアミン、塩化亜鉛の代わりにＭＥＡを１５ｇ使用した以外は、実施例１と同じ方法で二酸化炭素の吸収量と放散量を測定した。その結果、吸収液１ｋｇあたり標準状態で二酸化炭素を５９．２Ｌ吸収したが、二酸化炭素の放散量は８．７Ｌにすぎなかった。このガス放散量とガス吸収量の比は０．１５だった。 Comparative example 2
The absorption amount and emission amount of carbon dioxide were measured by the same method as in Example 1 except that 15 g of MEA was used instead of polyethylene polyamine and zinc chloride. As a result, 59.2 L of carbon dioxide was absorbed in a standard state per 1 kg of the absorbing liquid, but the emission amount of carbon dioxide was only 8.7 L. The ratio of the gas emission amount and the gas absorption amount was 0.15.

実施例３〜６
表１に記載の亜鉛化合物２ｇ、ポリエチレンポリアミン１５ｇ及び純水３５ｇで二酸化炭素吸収液を調製した。この液について実施例１と同じ方法で二酸化炭素の吸収量と放散量を測定した。その結果を表１に示した。 Examples 3-6
A carbon dioxide absorption liquid was prepared from 2 g of the zinc compound shown in Table 1, 15 g of polyethylene polyamine and 35 g of pure water. The absorption amount and the emission amount of carbon dioxide of this liquid were measured by the same method as in Example 1. The results are shown in Table 1.

Claims (5)

ポリエチレンポリアミン、亜鉛化合物、及び水を含む二酸化炭素分離組成物。 A carbon dioxide separation composition comprising polyethylene polyamine, a zinc compound, and water. ポリエチレンポリアミンが、ジエチレントリアミン、ピペラジン、Ｎ−（２−アミノエチル）ピペラジン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミンからなる群より選ばれる少なくとも一種である請求項１に記載の二酸化炭素分離組成物。 The polyethylene polyamine is at least one selected from the group consisting of diethylenetriamine, piperazine, N- (2-aminoethyl) piperazine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. Carbon dioxide separation composition. 水の濃度が、３０〜９５重量％である請求項１又は２に記載の二酸化炭素分離組成物。 The carbon dioxide separation composition according to claim 1 or 2, wherein the concentration of water is 30 to 95% by weight. 亜鉛化合物が、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛などのハロゲン化亜鉛、硝酸亜鉛、硫酸亜鉛、硫化亜鉛、炭酸亜鉛、酸化亜鉛、水酸化亜鉛、ギ酸亜鉛、酢酸亜鉛などの有機酸亜鉛からなる群より選ばれる少なくとも一種である請求項１〜３のいずれかに記載の二酸化炭素分離組成物。 Zinc compounds include zinc halides such as zinc fluoride, zinc chloride, zinc bromide and zinc iodide, zinc nitrate, zinc sulfate, zinc sulfide, zinc carbonate, zinc oxide, zinc hydroxide, zinc formate and zinc acetate. The carbon dioxide separation composition according to claim 1, which is at least one selected from the group consisting of organic acid zinc. 亜鉛化合物の量が、モル比でポリエチレンポリアミン／Ｚｎ≧４である請求項１〜４のいずれかに記載の二酸化炭素分離組成物。 The carbon dioxide separation composition according to claim 1, wherein the amount of the zinc compound is polyethylene polyamine / Zn ≧ 4 in a molar ratio.
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JP2020157211A (en) * 2019-03-26 2020-10-01 東ソー株式会社 Carbon dioxide separation composition
JP7251251B2 (en) 2019-03-26 2023-04-04 東ソー株式会社 Carbon dioxide separation composition

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