JP4922326B2 - Carbon dioxide absorbent and carbon dioxide recovery method - Google Patents
Carbon dioxide absorbent and carbon dioxide recovery method Download PDFInfo
- Publication number
- JP4922326B2 JP4922326B2 JP2009038606A JP2009038606A JP4922326B2 JP 4922326 B2 JP4922326 B2 JP 4922326B2 JP 2009038606 A JP2009038606 A JP 2009038606A JP 2009038606 A JP2009038606 A JP 2009038606A JP 4922326 B2 JP4922326 B2 JP 4922326B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- water
- soluble polymer
- aqueous solution
- absorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Description
本発明は、炭酸ガス吸収剤および回収方法に関する。より詳細には、石炭火力発電所等の炭化水素を主成分とする原料や燃料を利用するエネルギープラントや化学プラントから発生する排気ガス、自動車等から発生する排気ガス、原料ガスや燃料ガス中の炭酸ガスを回収するための炭酸ガス吸収剤及び回収方法に関する。 The present invention relates to a carbon dioxide absorbent and a recovery method. More specifically, exhaust gas generated from energy plants and chemical plants using hydrocarbon-based raw materials and fuels such as coal-fired power plants, exhaust gases generated from automobiles, etc. The present invention relates to a carbon dioxide absorbent and a recovery method for recovering carbon dioxide.
昨今の地球温暖化問題への関心および規制強化の背景を受けて、石炭火力発電所からの炭酸ガス排出量の削減は急務となっている。そこで、炭酸ガス排出量の削減方法として発電所の高効率化による排出量の低減と共に、化学吸収剤による炭酸ガスの回収が大きな注目を浴びている。 Reducing carbon dioxide emissions from coal-fired power plants has become an urgent task due to the recent interest in global warming and the background of stricter regulations. Therefore, as a method for reducing the amount of carbon dioxide emissions, the collection of carbon dioxide with chemical absorbents has attracted a great deal of attention as well as the reduction of emissions due to the high efficiency of power plants.
具体的な吸収剤としては、アミンによる吸収が古くから研究されている（例えば、特許文献１）。この場合、例えば、炭酸ガスを含むガスを吸収塔内でアルカノールアミン水溶液と接触させて炭酸ガスを吸収させた後、その炭酸ガス吸収液を加熱して脱離塔で炭酸ガスを脱離回収させる。 As a specific absorbent, absorption by amine has been studied for a long time (for example, Patent Document 1). In this case, for example, the carbon dioxide gas is brought into contact with the alkanolamine aqueous solution in the absorption tower to absorb the carbon dioxide gas, and then the carbon dioxide absorption liquid is heated to desorb and recover the carbon dioxide gas in the desorption tower. .
ここでアルカノールアミンとしては、モノエタノールアミン(MEA)、ジエタノールアミン(DEA)、トリエタノールアミン(TEA)、メチルジエタノールアミン(MDEA)、ジイソプロバノールアミン(DIPA)、ジグリコールアミン(DGA)などが知られているが、通常モノエタノールアミンが用いられている。 Here, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA), diglycolamine (DGA), etc. are known as alkanolamines. However, monoethanolamine is usually used.
しかしながら、例えばMEA等のアルカノールアミンの水溶液を吸収液として用いた場合、単位体積あたりの炭酸ガス吸収容量はすぐれているものの、装置の材質の腐食性が高いため、装置に高価な耐食鋼を用いる必要があったり、吸収液中のアミン濃度をさげる必要があったりした。また、吸収し炭酸ガスを脱離しにくいために、脱離の温度を１２０℃と高い温度に加熱して脱離、回収する必要がある。 However, for example, when an aqueous solution of alkanolamine such as MEA is used as the absorbing solution, although the carbon dioxide absorption capacity per unit volume is excellent, the corrosiveness of the material of the device is high, so expensive corrosion-resistant steel is used for the device. It was necessary to reduce the amine concentration in the absorbing solution. Further, since it is difficult to absorb and desorb carbon dioxide, it is necessary to desorb and recover by heating the desorption temperature to a high temperature of 120 ° C.
一方、このような高温による加熱処理による脱離には、多大のエネルギーを必要とするため、省エネルギー及び省資源が求められる時代においては適合せず、実用化を阻む大きな要因となっている。 On the other hand, desorption by heat treatment at such a high temperature requires a large amount of energy, so it is not suitable in an era where energy saving and resource saving are required, and is a major factor hindering practical use.
上記問題を解決すべく、アルカノールアミンに対してピペラジンを加えた多種のアミンの混合物を炭酸ガス吸収剤として用いたり（特許文献２）、同様にアルカノールアミンに対して低級アルキルピペラジンを加えた混合物を炭酸ガス吸収剤として用いたりすることが試みられている（特許文献３）。また、ビニルアミンとポリビニルアミンとの架橋重合体を炭酸ガス吸着剤として用いることが試みられている（特許文献４）。 In order to solve the above problems, a mixture of various amines in which piperazine is added to alkanolamine is used as a carbon dioxide absorbent (Patent Document 2), and a mixture in which lower alkyl piperazine is similarly added to alkanolamine is used. Attempts have been made to use it as a carbon dioxide gas absorbent (Patent Document 3). Attempts have also been made to use a crosslinked polymer of vinylamine and polyvinylamine as a carbon dioxide adsorbent (Patent Document 4).
これらの方法によれば、炭酸ガス吸収剤に吸収された炭酸ガスを脱離する際の加熱処理温度を７０℃〜９０℃程度まで低減することができる。しかしながら、前記加熱処理は、炭酸ガスを吸収した吸収剤の全体に対して実施する必要があり、したがって、加熱処理温度を低減することはできても、前記加熱処理には依然として多大のエネルギーを必要としていた。 According to these methods, the heat treatment temperature when desorbing the carbon dioxide absorbed by the carbon dioxide absorbent can be reduced to about 70 ° C to 90 ° C. However, the heat treatment needs to be performed on the entire absorbent that has absorbed carbon dioxide gas. Therefore, although the heat treatment temperature can be reduced, the heat treatment still requires a large amount of energy. I was trying.
本発明は、上述した問題に鑑み、吸収した炭酸ガスを放出して回収する際に要するエネルギーを低減することができる炭酸ガス吸収剤及び回収方法を提供することを目的とする。 In view of the above-described problems, an object of the present invention is to provide a carbon dioxide absorbent and a recovery method that can reduce energy required for releasing and recovering absorbed carbon dioxide.
本発明の一態様は、分子量が５００から１００、０００であり、（１）〜（４）式に記載の含窒素化合物を繰り返し単位として有する水溶性高分子化合物のいずれか１つ又はポリビニルピペリジンからなる水溶性高分子化合物を含有する炭酸ガス吸収剤
また、本発明の一態様は、分子量が５００から１００、０００であり、（１）〜（４）式に記載の含窒素化合物を繰り返し単位として有する水溶性高分子化合物のいずれか１つ又はポリピペリジンからなる水溶性高分子化合物を含有する炭酸ガス吸収剤
Another embodiment of the present invention is a water-soluble polymer compound having a molecular weight of 500 to 100,000 and having a nitrogen-containing compound described in the formulas (1) to (4) as a repeating unit. Carbon dioxide gas absorbent containing water-soluble polymer compound comprising piperidine
本発明によれば、吸収した炭酸ガスを放出して回収する際に要するエネルギーを低減することができる炭酸ガス吸収剤及び回収方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the carbon dioxide absorber and recovery method which can reduce the energy required when discharge | releasing and collect | recovering the absorbed carbon dioxide gas can be provided.
以下に、本発明の内容を詳細に示す。 The contents of the present invention are shown in detail below.
（炭酸ガス吸収剤）
最初に、本態様における炭酸ガス吸収剤について説明する。本態様における炭酸ガス吸収剤は、（１）式で示される含窒素化合物を繰り返し単位として有する水溶性高分子化合物である。Ｒ１は高分子の主鎖に相当し、−ＣｓＨｔ− (１≦ｓ≦１０、ｔ＝２ｓ−１)の条件を満たした炭化水素より構成される。なお、その形態は直鎖状、分岐状のいずれの形態でも構わない。
(Carbon dioxide absorbent)
First, the carbon dioxide absorbent in this embodiment will be described. The carbon dioxide gas absorbent in this embodiment is a water-soluble polymer compound having a nitrogen-containing compound represented by the formula (1) as a repeating unit. R1 corresponds to the main chain of the polymer and is composed of hydrocarbons that satisfy the condition of -CsHt- (1≤s≤10, t = 2s-1). In addition, the form may be either linear or branched.
また、炭素数ｓを１以上１０以下とするのは、一分子辺りのＣＯ２吸収効率及び、水溶性の観点からである。同様の理由から、炭素数ｓは8以下であることが好ましい。 The reason why the carbon number s is 1 or more and 10 or less is from the viewpoint of CO 2 absorption efficiency per molecule and water solubility. For the same reason, the carbon number s is preferably 8 or less.
Ｒ１にはアミノ基が結合しており、前記水溶性高分子化合物の側鎖部分に相当する。前記アミノ基は官能基Ｒ２を有している。Ｒ２は、−Ｈ, −ＣｓＨｔＯｕＮｖ (１≦ｓ≦５、２ｓ≦ｔ≦２ｓ＋２、０≦ｕ≦３、０≦ｖ≦３)で表される官能基である。前記アミノ基は、以下に説明する炭酸ガスの回収方法において、炭酸ガスの吸収に寄与する。 An amino group is bonded to R1, and corresponds to the side chain portion of the water-soluble polymer compound. The amino group has a functional group R2. R2 is a functional group represented by -H, -CsHtOuNv (1≤s≤5, 2s≤t≤2s + 2, 0≤u≤3, 0≤v≤3). The amino group contributes to carbon dioxide absorption in the carbon dioxide recovery method described below.
Ｒ２としては、例えば、アルキル基、末端にヒドロキシル基を有する化合物、エーテル結合を有する化合物、アミンなどが挙げられる。 Examples of R2 include an alkyl group, a compound having a hydroxyl group at the terminal, a compound having an ether bond, and an amine.
入手の容易さ等を考慮すると、上記水溶性高分子化合物としては、以下に示すような化合物を例示することができる。
特に上述した化合物の中でも、化合物８を一例とするポリアリルアミン、化合物２０を一例とするポリアリールアミン、化合物２３を一例とするポリアルカノールアミン、化合物２４を一例とする、ポリビニルアミンの一種であるポリビニルピペリジンが好ましく用いることができる。この場合、上述したように、Ｒ１で表される炭化水素による効果と、上記アミノ基による効果とがより効果的に奏されるようになり、以下に説明する炭酸ガスの回収時間を短縮化することができ、回収効率を向上させることができる。 Among the above-mentioned compounds, in particular, polyallylamine having Compound 8 as an example, polyarylamine having Compound 20 as an example, polyalkanolamine having Compound 23 as an example, polyvinyl which is a kind of polyvinylamine having Compound 24 as an example Piperidine can be preferably used. In this case, as described above, the effect of the hydrocarbon represented by R1 and the effect of the amino group are more effectively achieved, and the carbon dioxide recovery time described below is shortened. Recovery efficiency can be improved.
また、上述した水溶性高分子化合物を実際に炭酸ガスの吸収剤として使用する場合は、水溶液とする必要があるが、この場合、前記水溶性高分子化合物の１重量部から８０重量部に対して、水を２０重量部から９９重量部添加させて水溶性高分子含有水溶液とすることが好ましい。この場合、以下に示す炭酸ガスの回収方法において、疎水性の第１相と親水性の第２相とに容易に分離することができるようになる。 In addition, when the above-mentioned water-soluble polymer compound is actually used as an absorbent for carbon dioxide, it is necessary to use an aqueous solution. In this case, the water-soluble polymer compound is used in an amount of 1 to 80 parts by weight. Thus, it is preferable to add 20 to 99 parts by weight of water to obtain an aqueous solution containing a water-soluble polymer. In this case, in the carbon dioxide recovery method described below, it becomes possible to easily separate the hydrophobic first phase and the hydrophilic second phase.
さらに、前記水溶性高分子化合物の分子量が、５００から１００，０００であることが好ましい。前記分子量が５００未満であると、以下に示す炭酸ガスの回収方法において、疎水性の第１相と親水性の第２相とに分離できない場合がある。また、前記分子量が１００，０００を超えると、水に不溶となり、上記水溶性高分子含有水溶液を調整できない場合がある。 Furthermore, it is preferable that the water-soluble polymer compound has a molecular weight of 500 to 100,000. When the molecular weight is less than 500, in the following method for recovering carbon dioxide gas, it may not be possible to separate the hydrophobic first phase and the hydrophilic second phase. Moreover, when the molecular weight exceeds 100,000, the water-insoluble polymer-containing aqueous solution may not be prepared because it becomes insoluble in water.
また、前記水溶性高分子含有水溶液のｐＨが、７以上１４以下であることが好ましい。これによって、前記水溶液における炭酸ガスの吸収量を増大させることができる。なお、かかる条件は、上述したポリアリルアミン、ポリアリールアミン、ポリアルカノールアミン、及びポリビニルアミンの場合は、必然的に満足する。 Moreover, it is preferable that pH of the water-soluble polymer-containing aqueous solution is 7 or more and 14 or less. As a result, the amount of carbon dioxide absorbed in the aqueous solution can be increased. Such conditions are inevitably satisfied in the case of the above-mentioned polyallylamine, polyarylamine, polyalkanolamine, and polyvinylamine.
なお、本態様の炭酸ガス吸収剤には、上記水溶性高分子含有水溶液中に、必要に応じて吸収性能を補足する含窒素化合物、酸化防止剤、ｐH調整剤等その他化合物を任意の割合で含有させることができる。 In the carbon dioxide gas absorbent of this embodiment, other compounds such as a nitrogen-containing compound, an antioxidant, a pH adjuster and the like supplementing the absorption performance as needed are added to the water-soluble polymer-containing aqueous solution as necessary. It can be included.
（炭酸ガスの回収方法）
次に、本態様の炭酸ガスの回収方法について説明する。
最初に、（１）式に記載の含窒素化合物を繰り返し単位として有する、水溶性高分子化合物を含有する炭酸ガス吸収剤と、水とを混合して、水溶性高分子含有水溶液を調整する。この際、前記水溶性高分子化合物と前記水との混合比は、上述のように、前記水溶性高分子化合物の１重量部から８０重量部に対して、水を２０重量部から９９重量部とすることが好ましい。
(CO2 recovery method)
Next, the carbon dioxide gas recovery method of this embodiment will be described.
First, a water-soluble polymer-containing aqueous solution is prepared by mixing a carbon dioxide absorbent containing a water-soluble polymer compound having the nitrogen-containing compound described in the formula (1) as a repeating unit and water. At this time, the mixing ratio of the water-soluble polymer compound and the water is 20 to 99 parts by weight of water with respect to 1 to 80 parts by weight of the water-soluble polymer compound as described above. It is preferable that
また、前記水溶性高分子化合物の好ましい分子量は、上述したように５００から１００，０００であり、前記水溶性高分子化合物の好ましい例としても、上記同様に、ポリアリルアミン、ポリアリールアミン、ポリビニルアミン、及びポリアルカノールアミンからなる群より選ばれる少なくとも一種である。また、前記ポリビニルアミンにおいては、ポリビニルピペリジンがより好ましい。 Moreover, the preferable molecular weight of the water-soluble polymer compound is 500 to 100,000 as described above. As a preferable example of the water-soluble polymer compound, as described above, polyallylamine, polyarylamine, polyvinylamine are also used. And at least one selected from the group consisting of polyalkanolamines. Moreover, in the said polyvinylamine, polyvinyl piperidine is more preferable.
また、繰り返しになるが、上記水溶性高分子含有水溶液のｐＨは、７以上１４以下であることが好ましい。これによって、前記水溶液における炭酸ガスの吸収量を増大させることができる。なお、かかる条件は、上述したポリアリルアミン、ポリアリールアミン、ポリアルカノールアミン、及びポリビニルアミンの場合は、必然的に満足するが、必要に応じてｐＨ調整剤等を混合させることもできる。 Moreover, although it repeats, it is preferable that pH of the said water-soluble polymer containing aqueous solution is 7 or more and 14 or less. As a result, the amount of carbon dioxide absorbed in the aqueous solution can be increased. Such conditions are inevitably satisfied in the case of the above-described polyallylamine, polyarylamine, polyalkanolamine, and polyvinylamine, but a pH adjuster or the like can be mixed as necessary.
次いで、前記水溶性高分子含有水溶液に対して炭酸ガスを含有する気体を接触させ、前記炭酸ガスを吸収させる。この際、炭酸ガスを含有する前記気体と、前記水溶性高分子含有水溶液とが接触することができればよく、例えば、気泡攪拌槽、気泡塔によるガス分散型吸収装置、スプレー塔、噴霧室、スクラバー、濡れ壁塔、充填塔による液分散型吸収装置等、既存の炭酸ガス吸収設備を用いることができる。炭酸ガスの吸収効率の観点から、充填材を充填した炭酸ガス吸収塔を用いた吸収が好ましい。 Next, a gas containing carbon dioxide gas is brought into contact with the water-soluble polymer-containing aqueous solution to absorb the carbon dioxide gas. At this time, the gas containing carbon dioxide and the water-soluble polymer-containing aqueous solution need only be in contact with each other. For example, a bubble stirring tank, a gas dispersion type absorption device using a bubble tower, a spray tower, a spray chamber, a scrubber Further, existing carbon dioxide absorption equipment such as a liquid dispersion type absorption device using a wet wall tower or a packed tower can be used. From the viewpoint of carbon dioxide absorption efficiency, absorption using a carbon dioxide absorption tower filled with a filler is preferred.
炭酸ガス回収時の反応温度は炭酸ガスを吸収することができればいかなる温度でも構わないが、吸収速度、及び吸収効率の観点から２５℃以上、７０℃以下であることが好ましい。 The reaction temperature at the time of carbon dioxide recovery may be any temperature as long as it can absorb carbon dioxide, but is preferably 25 ° C. or higher and 70 ° C. or lower from the viewpoint of absorption speed and absorption efficiency.
次いで、上記炭酸ガスを吸収した前記水溶性高分子含有水溶液を、疎水性の第１相と親水性の第２相とに分離する。この相分離は、既存の液・液分離方法を用いることができる。液・液分離法の例としてデカンテーション、遠心分離が挙げられるが、これらに何ら限定されるものではない。 Next, the water-soluble polymer-containing aqueous solution that has absorbed the carbon dioxide gas is separated into a hydrophobic first phase and a hydrophilic second phase. For this phase separation, an existing liquid / liquid separation method can be used. Examples of the liquid / liquid separation method include decantation and centrifugation, but are not limited thereto.
また、相分離は以下に説明するように、前記水溶性高分子含有水溶液からの炭酸ガス放出時の再生エネルギー低減を目的として行うものであるため、完全に分離を行う必要は無く、前記第２相を減溶することができれば良い。相分離を行う際の温度は特に限定はされないが、２５℃以上、７０℃以下であることが好ましい。 In addition, as will be described below, the phase separation is performed for the purpose of reducing the regeneration energy when carbon dioxide gas is released from the aqueous solution containing the water-soluble polymer. Therefore, it is not necessary to completely separate the second separation. It is sufficient if the phase can be reduced. The temperature at which the phase separation is performed is not particularly limited, but is preferably 25 ° C. or higher and 70 ° C. or lower.
次いで、前記水溶性高分子含有水溶液の、前記第１相から前記炭酸ガスを放出する。前記炭酸ガスの放出方法としては、減圧、加熱、膜分離などが挙げられるが、これらに何ら限定されるものではない。但し、加熱処理による方法によれば、簡易に前記ガス放出を行うことができる。この際の温度は、前記炭酸ガスを放出することができればいかなる温度でも構わないが、４０℃以上、１５０℃以下であることが好ましい。 Next, the carbon dioxide gas is released from the first phase of the aqueous solution containing the water-soluble polymer. Examples of the method for releasing carbon dioxide include pressure reduction, heating, membrane separation, and the like, but are not limited thereto. However, according to the method by heat treatment, the gas can be easily released. The temperature at this time may be any temperature as long as the carbon dioxide gas can be released, but is preferably 40 ° C. or higher and 150 ° C. or lower.
なお、本態様では、吸収した前記炭酸ガスは、前記水溶性高分子含有水溶液の前記第１相中に含まれるようになるので、上述した加熱処理は前記第１相に対してのみ行えば良い。したがって、従来技術で述べたような、炭酸ガスを吸収した吸収剤の全体、すなわち本態様では、前記水溶性高分子含有水溶液の全体に上述した加熱処理を行う必要がない。この結果、従来技術と異なり、前記加熱処理に伴うエネルギー消費を十分に低減することができる。 In this aspect, the absorbed carbon dioxide gas is contained in the first phase of the water-soluble polymer-containing aqueous solution, so that the heat treatment described above only needs to be performed on the first phase. . Therefore, it is not necessary to perform the above-described heat treatment on the entire absorbent that has absorbed carbon dioxide gas as described in the prior art, that is, in the present embodiment, the entire aqueous solution containing the water-soluble polymer. As a result, unlike the prior art, energy consumption accompanying the heat treatment can be sufficiently reduced.
なお、上記第１相が疎水性を示すのは、主として炭酸ガスを吸収したことによる。したがって、上述のようにして炭酸ガスを放出した後は親水性を呈するようになるので、上述した第１相及び第２相は再び混合して、上記水溶性高分子含有水溶液とすることができ、再度炭酸ガス吸収剤として用いることができる。混合時に含窒素化合物、水、もしくはその他化合物を添加し、吸収性能を補うことも可能である。 The first phase exhibits hydrophobicity mainly due to absorption of carbon dioxide gas. Therefore, since the carbon dioxide gas is released as described above, it becomes hydrophilic. Therefore, the first phase and the second phase described above can be mixed again to obtain the water-soluble polymer-containing aqueous solution. Again, it can be used as a carbon dioxide gas absorbent. It is also possible to supplement the absorption performance by adding a nitrogen-containing compound, water, or other compounds during mixing.
以下に実施例を示す。 Examples are shown below.
（実施例１）
化合物８に示すポリアミン(分子量約５０００)２０重量部を水８０重量部に溶解させ、１００mlの水溶液とした。水溶液のｐHは１１であった。得られた水溶液を４０℃に加熱し、炭酸ガスを約１０％含有するガスを流速１Ｌ/ｍｉｎで通気した。約２０分で吸収は飽和し、吸収量は約０．２８ｍｏｌであった。炭酸ガス吸収後のポリアリルアミン水溶液は２相に分離した。これをデカンテーションによって分離を行い、ポリアリルアミンを含む疎水性相を回収した。回収したポリアリルアミン含有疎水性相を約２０分間９０℃に加熱した。放出は飽和し、約０．２５ｍｏｌの炭酸ガスが回収された。
Example 1
20 parts by weight of polyamine (molecular weight of about 5000) shown in Compound 8 was dissolved in 80 parts by weight of water to make a 100 ml aqueous solution. The pH of the aqueous solution was 11. The obtained aqueous solution was heated to 40 ° C., and a gas containing about 10% of carbon dioxide gas was aerated at a flow rate of 1 L / min. Absorption was saturated in about 20 minutes, and the amount absorbed was about 0.28 mol. The polyallylamine aqueous solution after carbon dioxide absorption was separated into two phases. This was separated by decantation, and the hydrophobic phase containing polyallylamine was recovered. The recovered polyallylamine-containing hydrophobic phase was heated to 90 ° C. for about 20 minutes. The release was saturated and about 0.25 mol of carbon dioxide gas was recovered.
（実施例２）
化合物２０に示すポリアリルアミン（分子量約５０００）を用いて実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．２１molであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．１７ｍｏｌの炭酸ガスが回収された。
(Example 2)
When the same experiment as in Example 1 was performed using polyallylamine (molecular weight: about 5000) shown in Compound 20, the absorption was saturated in about 20 minutes and the absorption was about 0.21 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.17 mol of carbon dioxide was recovered.
（実施例３）
化合物２３に示すポリアルカノールアミン（分子量約５０００）を用いて実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．１４ｍｏｌであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．１１ｍｏｌの炭酸ガスが回収された。
(Example 3)
When a polyalkanolamine (molecular weight: about 5000) shown in Compound 23 was used and the same experiment as in Example 1 was performed, the absorption was saturated in about 20 minutes and the absorption was about 0.14 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.11 mol of carbon dioxide gas was recovered.
（実施例４）
化合物２４に示すポリ環状アミン（分子量約５０００）を用いて実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．１１ｍｏｌであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．０８ｍｏｌの炭酸ガスが回収された。
Example 4
When the same experiment as in Example 1 was performed using the polycyclic amine (molecular weight: about 5000) shown in Compound 24, the absorption was saturated in about 20 minutes and the absorption was about 0.11 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.08 mol of carbon dioxide was recovered.
（実施例５）
化合物２０に示すポリアリルアミン（分子量約５０００）１重量部に対して、水を９９重量部添加し、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．０２ｍｏｌであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．０１７ｍｏｌの炭酸ガスが回収された。
(Example 5)
When 99 parts by weight of water was added to 1 part by weight of polyallylamine (molecular weight of about 5000) shown in Compound 20 and the same experiment as in Example 1 was performed, the absorption was saturated in about 20 minutes, About 0.02 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.017 mol of carbon dioxide was recovered.
（実施例６）
化合物２０に示すポリアリルアミン（分子量約５０００）を８０重量部に対して水２０重量部添加し、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．８５ｍｏｌであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．７５ｍｏｌの炭酸ガスが回収された。
(Example 6)
When 20 parts by weight of water was added to 80 parts by weight of polyallylamine shown in Compound 20 (molecular weight: about 5000), the same experiment as in Example 1 was performed. As a result, the absorption was saturated in about 20 minutes, and the absorption amount was about The amount was 0.85 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.75 mol of carbon dioxide gas was recovered.
（実施例７）
化合物２０に示すポリアリルアミン（分子量約５００）を用いて、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．２１ｍｏｌであった。炭酸ガス吸収後、ポリアリルアミン水溶液は２相に分離した。２０分間９０℃に加熱したところ、放出は飽和し、約０．１５ｍｏｌの炭酸ガスが回収された。
(Example 7)
When the same experiment as in Example 1 was performed using polyallylamine (molecular weight: about 500) shown in Compound 20, the absorption was saturated in about 20 minutes and the absorption was about 0.21 mol. After carbon dioxide absorption, the polyallylamine aqueous solution separated into two phases. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.15 mol of carbon dioxide was recovered.
（実施例８）
化合物２０に示すポリアリルアミン（分子量約２００００）を用いて、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．２１ｍｏｌであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．１８ｍｏｌの炭酸ガスが回収された。
(Example 8)
When the same experiment as Example 1 was conducted using polyallylamine (molecular weight about 20000) shown in Compound 20, the absorption was saturated in about 20 minutes and the absorption amount was about 0.21 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.18 mol of carbon dioxide gas was recovered.
（実施例９）
化合物２０に示すポリアリルアミン（分子量約１００，０００）を用いて、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．２１ｍｏｌであった。２０分間９０℃に加熱したところ、放出は飽和し、約０．１８ｍｏｌの炭酸ガスが回収された。
Example 9
When the same experiment as in Example 1 was performed using polyallylamine (molecular weight: about 100,000) shown in Compound 20, the absorption was saturated in about 20 minutes and the absorption was about 0.21 mol. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.18 mol of carbon dioxide gas was recovered.
（実施例１０）
化合物２０に示すポリアリルアミン（分子量約５０００）を用いて、溶液のｐHが７となるように調整し、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．１４ｍｏｌであった。炭酸ガス吸収後、ポリアリルアミン水溶液は２相に分離した。２０分間９０℃に加熱したところ、放出は飽和し、約０．１０ｍｏｌの炭酸ガスが回収された。
(Example 10)
Using polyallylamine (molecular weight of about 5000) shown in Compound 20 and adjusting the pH of the solution to be 7, the same experiment as in Example 1 was conducted. As a result, the absorption was saturated in about 20 minutes. Was about 0.14 mol. After carbon dioxide absorption, the polyallylamine aqueous solution separated into two phases. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.10 mol of carbon dioxide was recovered.
（実施例１１）
化合物２０に示すポリアリルアミン（分子量約５０００）を用いて、溶液のｐHが９となるように調整し、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．１８ｍｏｌであった。炭酸ガス吸収後、ポリアリルアミン水溶液は２相に分離した。２０分間９０℃に加熱したところ、放出は飽和し、約０．１５ｍｏｌの炭酸ガスが回収された。
(Example 11)
Using polyallylamine (molecular weight of about 5000) shown in Compound 20, the solution was adjusted to have a pH of 9, and the same experiment as in Example 1 was performed. As a result, the absorption was saturated in about 20 minutes. Was about 0.18 mol. After carbon dioxide absorption, the polyallylamine aqueous solution separated into two phases. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.15 mol of carbon dioxide was recovered.
（実施例１２）
化合物２０に示すポリアリルアミン（分子量約５０００）を用いて、溶液のｐHが１４となるように調整し、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．２１molであった。炭酸ガス吸収後、ポリアリルアミン水溶液は２相に分離した。２０分間９０℃に加熱したところ、放出は飽和し、約０．１８ｍｏｌの炭酸ガスが回収された。
(Example 12)
Using polyallylamine (molecular weight of about 5000) shown in Compound 20 and adjusting the pH of the solution to be 14, the same experiment as in Example 1 was conducted. As a result, the absorption was saturated in about 20 minutes. Was about 0.21 mol. After carbon dioxide absorption, the polyallylamine aqueous solution separated into two phases. When heated to 90 ° C. for 20 minutes, the release was saturated and about 0.18 mol of carbon dioxide gas was recovered.
（実施例１３）
化合物２０に示すポリアリルアミン（分子量約５０００）２０重量部を水８０重量部に溶解させ、１０Lの水溶液を調整した。水溶液のｐHは１１であった。得られた水溶液を用いて、１０％炭酸ガスを流量１０L/min、４０℃の条件で充填材を充填した充填塔を用いて吸収させた。約３０分間で２１molの炭酸ガスを吸収した。炭酸ガス吸収後のポリアリルアミン水溶液は２相に分離した。これを比重差を利用して分離し、ポリアリルアミンを含む疎水性相を回収した。回収したポリアリルアミン含有疎水性相を約３０分間９０℃に加熱した。放出は飽和し、約１７molの炭酸ガスが回収された。
(Example 13)
20 parts by weight of polyallylamine (molecular weight of about 5000) shown in Compound 20 was dissolved in 80 parts by weight of water to prepare a 10 L aqueous solution. The pH of the aqueous solution was 11. Using the obtained aqueous solution, 10% carbon dioxide gas was absorbed using a packed tower filled with a filler under the conditions of a flow rate of 10 L / min and 40 ° C. In about 30 minutes, 21 mol of carbon dioxide gas was absorbed. The polyallylamine aqueous solution after carbon dioxide absorption was separated into two phases. This was separated using the difference in specific gravity, and the hydrophobic phase containing polyallylamine was recovered. The recovered polyallylamine-containing hydrophobic phase was heated to 90 ° C. for about 30 minutes. The release was saturated and about 17 mol of carbon dioxide was recovered.
（実施例１４）
化合物２０に示すポリアリルアミン（分子量約５０００）２０重量部を水８０重量部に溶解させ、１０Lの水溶液を調整した。水溶液のｐHは１１であった。得られた水溶液を用いて、１０％炭酸ガスを流量１０Ｌ／ｍｉｎ、４０℃の条件でスプレー塔を用いて吸収させた。約３０分間で２１ｍｏｌの炭酸ガスを吸収した。炭酸ガス吸収後のポリアリルアミン水溶液は２相に分離した。これを比重差を利用して分離し、ポリアリルアミンを含む疎水性相を回収した。回収したポリアリルアミン含有疎水性相を約３０分間９０℃に加熱した。放出は飽和し、約１６．５molの炭酸ガスが回収された。
(Example 14)
20 parts by weight of polyallylamine (molecular weight of about 5000) shown in Compound 20 was dissolved in 80 parts by weight of water to prepare a 10 L aqueous solution. The pH of the aqueous solution was 11. Using the obtained aqueous solution, 10% carbon dioxide gas was absorbed using a spray tower under the conditions of a flow rate of 10 L / min and 40 ° C. In about 30 minutes, 21 mol of carbon dioxide gas was absorbed. The polyallylamine aqueous solution after carbon dioxide absorption was separated into two phases. This was separated using the difference in specific gravity, and the hydrophobic phase containing polyallylamine was recovered. The recovered polyallylamine-containing hydrophobic phase was heated to 90 ° C. for about 30 minutes. The release was saturated and about 16.5 mol of carbon dioxide was recovered.
（比較例１）
化合物３１に示す３級ポリアルカノールアミン（分子量約５０００）を用いて、実施例１と同様の実験を行ったところ、約３０分で吸収は飽和し、吸収量は約０．１ｍｏｌであった。しかし、炭酸ガス吸収後も２相分離は観察されなかった。吸収液全量を９０℃に加熱し、炭酸ガスの放出を行った。放出の飽和に４５分要し、約０．０７molの炭酸ガスが回収された。
When the same experiment as in Example 1 was performed using a tertiary polyalkanolamine (molecular weight: about 5000) shown in Compound 31, the absorption was saturated in about 30 minutes and the absorption was about 0.1 mol. However, no two-phase separation was observed after carbon dioxide absorption. The total amount of the absorbing solution was heated to 90 ° C. to release carbon dioxide. It took 45 minutes to saturate the release and about 0.07 mol of carbon dioxide was recovered.
（比較例２）
化合物３２に示すポリエチレンオキサイド誘導ポリアミン（分子量約５０００）を用いて、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．１６ｍｏｌであった。しかし、炭酸ガス吸収後も２相分離は観察されなかった。吸収液全量を９０℃に加熱し、炭酸ガスの放出を行った。放出の飽和に４０分要し、約０．１２molの炭酸ガスが回収された。
When the same experiment as in Example 1 was performed using the polyethylene oxide-derived polyamine (molecular weight: about 5000) shown in Compound 32, the absorption was saturated in about 20 minutes and the absorption was about 0.16 mol. However, no two-phase separation was observed after carbon dioxide absorption. The total amount of the absorbing solution was heated to 90 ° C. to release carbon dioxide. It took 40 minutes to saturate the release and about 0.12 mol of carbon dioxide was recovered.
（比較例３）
モノエタノールアミン２０重量部に対して水８０重量部添加し、実施例１と同様の実験を行ったところ、約２０分で吸収は飽和し、吸収量は約０．２molであった。しかし、炭酸ガス吸収後も２相分離は観察されなかった。吸収液全量を９０℃に加熱し、炭酸ガスの放出を行った。放出の飽和に４０分要し、約０．１１molの炭酸ガスが回収された。
(Comparative Example 3)
When 80 parts by weight of water was added to 20 parts by weight of monoethanolamine and the same experiment as in Example 1 was performed, the absorption was saturated in about 20 minutes and the absorption amount was about 0.2 mol. However, no two-phase separation was observed after carbon dioxide absorption. The total amount of the absorbing solution was heated to 90 ° C. to release carbon dioxide. It took 40 minutes to saturate the release and about 0.11 mol of carbon dioxide was recovered.
（比較例４）
化合物３３に示す、ポリ（N-イソプロピルアクリルアミド）(分子量５０００００)を用いて実施例１と同様の実験を行った。水溶液のｐHは５であった。その結果、炭酸ガスの吸収は観察されなかった。
The same experiment as in Example 1 was performed using poly (N-isopropylacrylamide) (molecular weight: 500,000) shown as Compound 33. The pH of the aqueous solution was 5. As a result, carbon dioxide absorption was not observed.
以上、実施例から明らかなように、本発明に従った実施例においては、９０℃に加熱して炭酸ガスを放出する際に、２０分程度から３０分程度の加熱時間で足りるのに対し、本発明と異なる比較例では、９０℃に加熱して炭酸ガスを放出する際に４０分程度の加熱時間を要することが判明した。したがって、実施例における炭酸ガスの放出に要するエネルギーは比較例における炭酸ガスの放出に要するエネルギーよりも十分に小さいことが分かる。すなわち、炭酸ガスの放出に伴うエネルギー消費を十分に低減できることが分かる。 As can be seen from the examples, in the examples according to the present invention, when the carbon dioxide gas is released by heating to 90 ° C., a heating time of about 20 to 30 minutes is sufficient, In a comparative example different from the present invention, it was found that a heating time of about 40 minutes was required when releasing carbon dioxide gas by heating to 90 ° C. Therefore, it can be seen that the energy required for releasing the carbon dioxide gas in the example is sufficiently smaller than the energy required for releasing the carbon dioxide gas in the comparative example. That is, it turns out that the energy consumption accompanying discharge | release of a carbon dioxide gas can fully be reduced.
また、比較例４に示すような化合物を炭酸ガス吸収剤として使用した場合は、炭酸ガス自体が吸収されないことが判明した。 It was also found that when a compound as shown in Comparative Example 4 was used as a carbon dioxide absorbent, carbon dioxide itself was not absorbed.
以上、本発明を上記具体例に基づいて詳細に説明したが、本発明は上記態様に限定されるものではなく、本発明の範疇を逸脱しない限りにおいてあらゆる変更や変形が可能である。 As mentioned above, although this invention was demonstrated in detail based on the said specific example, this invention is not limited to the said aspect, All the changes and deformation | transformation are possible unless it deviates from the category of this invention.
Claims (7)
前記水溶性高分子含有水溶液に対して炭酸ガスを含有する気体を接触させ、前記炭酸ガスを吸収させるステップと、
前記水溶性高分子含有水溶液を、疎水性の第１相と親水性の第２相とに分離するステップと、
前記水溶性高分子含有水溶液の、前記第１相から前記炭酸ガスを放出するステップと、を具えることを特徴とする、炭酸ガス回収方法。 A water-soluble polymer compound having a molecular weight of 500 to 100,000 and comprising any one of water-soluble polymer compounds having a nitrogen-containing compound described in the formulas (1) to (4) as a repeating unit or polyvinylpiperidine; Contains carbon dioxide absorbent
Contacting a gas containing carbon dioxide with the water-soluble polymer-containing aqueous solution to absorb the carbon dioxide;
Separating the water-soluble polymer-containing aqueous solution into a hydrophobic first phase and a hydrophilic second phase;
Releasing the carbon dioxide gas from the first phase of the water-soluble polymer-containing aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009038606A JP4922326B2 (en) | 2009-02-20 | 2009-02-20 | Carbon dioxide absorbent and carbon dioxide recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009038606A JP4922326B2 (en) | 2009-02-20 | 2009-02-20 | Carbon dioxide absorbent and carbon dioxide recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010194378A JP2010194378A (en) | 2010-09-09 |
| JP4922326B2 true JP4922326B2 (en) | 2012-04-25 |
Family
ID=42819683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009038606A Expired - Fee Related JP4922326B2 (en) | 2009-02-20 | 2009-02-20 | Carbon dioxide absorbent and carbon dioxide recovery method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4922326B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2913092A1 (en) * | 2014-02-28 | 2015-09-02 | Kabushiki Kaisha Toshiba | Carbon dioxide recovery apparatus and carbon dioxide recovery method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5646892B2 (en) * | 2010-07-01 | 2014-12-24 | 旭化成株式会社 | Carbon dioxide absorbent and method for separating carbon dioxide using the same |
| JP5700668B2 (en) * | 2010-07-01 | 2015-04-15 | 旭化成株式会社 | Polymer for absorbing carbon dioxide, and method for separating and recovering carbon dioxide using the polymer |
| JP5652786B2 (en) * | 2011-02-23 | 2015-01-14 | 日東紡績株式会社 | Method for promoting photosynthesis of photosynthetic organisms |
| JP6460974B2 (en) * | 2015-12-22 | 2019-01-30 | 株式会社神戸製鋼所 | Absorbent, method for producing the same, and method for separating and recovering carbon dioxide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61227821A (en) * | 1985-04-01 | 1986-10-09 | Kawasaki Heavy Ind Ltd | Removing method for carbonic acid gas |
| IT1244686B (en) * | 1991-01-24 | 1994-08-08 | Snam Progetti | PROCESS FOR THE PUSH REMOVAL OF ACID GASES FROM GASEOUS MIXTURES |
| JPH1179253A (en) * | 1997-09-01 | 1999-03-23 | Mitsui Chem Inc | Package and packing material |
| FR2877858B1 (en) * | 2004-11-12 | 2007-01-12 | Inst Francais Du Petrole | METHOD FOR DEACIDIFYING A GAS WITH A FRACTIONED REGENERATION ABSORBENT SOLUTION |
| EP1919610A4 (en) * | 2005-08-09 | 2011-08-10 | Exxonmobil Res & Eng Co | Polyalkyleneimines and polyalkyleneacrylamide salt for acid gas scrubbing process |
-
2009
- 2009-02-20 JP JP2009038606A patent/JP4922326B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2913092A1 (en) * | 2014-02-28 | 2015-09-02 | Kabushiki Kaisha Toshiba | Carbon dioxide recovery apparatus and carbon dioxide recovery method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010194378A (en) | 2010-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vega et al. | Solvents for carbon dioxide capture | |
| JP5238487B2 (en) | Carbon dioxide recovery agent and carbon dioxide recovery method | |
| AU2011296309B2 (en) | Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream | |
| JP4865530B2 (en) | Mixed absorbent for carbon dioxide separation | |
| KR101157141B1 (en) | CO2 absorbent based on alkali carbonate solution promoted by hindered cyclic amines and CO2 removing method using the same | |
| Lin et al. | Absorption of carbon dioxide by the absorbent composed of piperazine and 2-amino-2-methyl-1-propanol in PVDF membrane contactor | |
| US20170173518A1 (en) | Composite method of trapping carbon dioxide in gas mixture | |
| KR101239380B1 (en) | An absorbent for capturing carbon dioxide comprising amino acid having multi amine groups and metal hydrate | |
| JP2013542060A (en) | Method of scrubbing CO2 with alkanolamine | |
| JP4922326B2 (en) | Carbon dioxide absorbent and carbon dioxide recovery method | |
| JPWO2011121633A1 (en) | Acid gas absorbent, acid gas removal device, and acid gas removal method | |
| EP3074488A1 (en) | Hybrid solvent formulations for selective h2s removal | |
| US11185814B2 (en) | Absorption agent, method of manufacturing same, and method for separation and recovery of acidic compound | |
| CN105745007A (en) | Method for removing dust and sulphur oxides from process gases | |
| KR101955752B1 (en) | Liquid for absorbing and collecting carbon dioxide in gas, and method for collecting carbon dioxide with use of same | |
| JP5603873B2 (en) | Carbon dioxide absorption liquid | |
| KR101038764B1 (en) | Appraratus and method for solvent scrubbing co2 capture system | |
| JP2009213974A (en) | Aqueous solution and method of absorbing and desorption-recovering effectively carbon dioxides in gas | |
| CN102989295A (en) | Absorbent which gathers carbon dioxide in flue gas or synthesis gas | |
| US9713790B2 (en) | Compound including oxalate, carbon dioxide absorbent including the same, method of preparing carbon dioxide absorbent and method of removing carbon dioxide | |
| EP3204142A1 (en) | Aqueous solution of 2-dimethylamino-2-hydroxymethyl-1, 3-propanediol useful for acid gas removal from gaseous mixtures | |
| CN103239970B (en) | A kind of for CO in regeneration fume from catalytic cracking2The composite absorber of trapping | |
| KR20190057586A (en) | Acid gas sorbent and acid gas separation method based on ionic liquid | |
| CN101766947B (en) | Composite absorber for catching CO2 gas of membrane contactor | |
| CN102051244B (en) | High-efficiency purification desulfurizer for high-acid oil and gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110207 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110603 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111004 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111114 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20111114 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20111114 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120110 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120203 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |