JP2016003156A5 - - Google Patents
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- JP2016003156A5 JP2016003156A5 JP2014123288A JP2014123288A JP2016003156A5 JP 2016003156 A5 JP2016003156 A5 JP 2016003156A5 JP 2014123288 A JP2014123288 A JP 2014123288A JP 2014123288 A JP2014123288 A JP 2014123288A JP 2016003156 A5 JP2016003156 A5 JP 2016003156A5
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- carbon dioxide
- heating
- sodium
- temperature
- dioxide gas
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- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 229910000529 magnetic ferrite Inorganic materials 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 16
- 229910000859 α-Fe Inorganic materials 0.000 claims description 12
- 230000002745 absorbent Effects 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 11
- 229910013553 LiNO Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000011358 absorbing material Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 13
- 229910001566 austenite Inorganic materials 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
Description
本発明は、以下のとおりである。
[１]
γ- Fe2O3とNaNO3を混合して混合粉末MP1を得る工程(a1)、又は
γ- Fe2O3とNaNO3とLiNO3及び／又はKNO3を混合して混合粉末MP2を得る工程(a2)、但し、NaNO3に対するLiNO3及び／又はKNO3のモル比は0.85:0.15〜1未満:0超の範囲である、
得られた混合粉末MP1又はMP2を570℃〜750℃の温度に加熱してα-NaFeO2又は置換型-NaFeO2を生成させる工程(b1)、又は
得られた混合粉末MP1又はMP2を550〜600℃の温度T1に加熱し、次いで、570〜750℃の温度T2(但し、T1<T2)に昇温してさらに加熱してα-NaFeO2又は置換型-NaFeO2を生成させる工程(b2)、
但し、置換型-NaFeO2は、Naの一部がLi及び／又はKで置換された化合物である、
を含むα-ナトリウムフェライト類の製造方法。
[２]
工程(b1)における混合粉末MP1又はMP2の加熱時間は40時間以上である、[１］に記載の製造方法。
[３]
工程(b2)における温度T1における混合粉末MP1又はMP2の加熱時間は1〜50時間であり、温度T2における混合粉末MP1又はMP2の加熱時間は5〜30時間の範囲である、[１］に記載の製造方法。
[４]
炭酸ガスを含む気体に[１］〜［３］のいずれかに記載の製造方法で得られたα-ナトリウムフェライト類を含有する炭酸ガス吸収材を接触させて、前記炭酸ガスを含む気体中の前記炭酸ガスと選択的に反応させる炭酸ガス吸収方法。
[５]
[１］〜［３］のいずれかに記載の製造方法で得られたα-ナトリウムフェライト類を含有する炭酸ガス吸収材と、前記炭酸ガス吸収材を収納し、炭酸ガスを導入するための炭酸ガス導入口とを具備することを含む、炭酸ガス吸収装置。
[６]
[１］〜［３］のいずれかに記載の製造方法で得られたα-ナトリウムフェライト類を含有する炭酸ガス吸収材に炭酸ガスを反応させて生成した生成物と、前記生成物を加熱し炭酸ガスを放出させるための加熱装置と、前記生成物を収納し、前記炭酸ガスを排出する生成ガス排出口とを具備することを含む、炭酸ガス分離装置。
The present invention is as follows.
[1]
Step (a1) of obtaining γ-Fe 2 O 3 and NaNO 3 to obtain mixed powder MP1, or γ-Fe 2 O 3 , NaNO 3 and LiNO 3 and / or KNO 3 to obtain mixed powder MP2 step (a2), provided that the molar ratio of LiNO 3 and / or KNO 3 for NaNO 3 0.85: less than 0.15: 0 range greater than,
Step (b1) of heating the obtained mixed powder MP1 or MP2 to a temperature of 570 ° C. to 750 ° C. to produce α-NaFeO 2 or substituted-NaFeO 2 , or the obtained mixed powder MP1 or MP2 from 550 to 550 ° C. Heating to a temperature T1 of 600 ° C., then raising the temperature to a temperature T2 of 570 to 750 ° C. (where T1 <T2) and further heating to produce α-NaFeO 2 or substituted-NaFeO 2 (b2 ),
However, substituted-NaFeO 2 is a compound in which a part of Na is substituted with Li and / or K.
For producing α- sodium ferrites.
[2]
The manufacturing method according to [1], wherein the heating time of the mixed powder MP1 or MP2 in the step (b1) is 40 hours or more.
[3]
The heating time of the mixed powder MP1 or MP2 at the temperature T1 in the step (b2) is 1 to 50 hours, and the heating time of the mixed powder MP1 or MP2 at the temperature T2 is in the range of 5 to 30 hours. Manufacturing method.
[4]
A gas containing carbon dioxide is brought into contact with a carbon dioxide absorbent containing α- sodium ferrite obtained by the production method according to any one of [1] to [3], and the gas containing the carbon dioxide is contained in the gas. A carbon dioxide absorption method for selectively reacting with the carbon dioxide.
[5]
A carbon dioxide absorbent containing the α- sodium ferrite obtained by the production method according to any one of [1] to [3], and carbon dioxide for containing the carbon dioxide absorbent and introducing carbon dioxide. A carbon dioxide absorption device comprising: comprising a gas inlet.
[6]
A product produced by reacting carbon dioxide with a carbon dioxide absorbent containing the α- sodium ferrite obtained by the production method according to any one of [1] to [3], and heating the product. A carbon dioxide gas separation device comprising: a heating device for releasing carbon dioxide gas; and a product gas outlet for containing the product and discharging the carbon dioxide gas.
＜α-ナトリウムフェライト類の製造方法＞
工程(a1)
工程(a1)では、γ- Fe2O3とNaNO3を混合して混合粉末MP1を得る。γ- Fe2O3とNaNO3の混合比率は、モル比で1:1であることが適当である。前記モル比が1:1から外れても目的とするα-ナトリウムフェライト類を得ることはでき、実用的には、例えば、1:0.9〜1.2の範囲とすることが好ましく、1:0.95〜1.15の範囲とすることがより好ましい。原料として用いるγ- Fe2O3及びNaNO3には特に制限はなく、市販品をそのまま用いることができる。但し、市販品の純度によっては、公知の方法にて適宜精製した後に混合粉末とすることもできる。また、γ- Fe2O3は、NaNO3との反応性を考慮すると、粒子径が比較的小さい粉末であることが好ましい場合がある。
<Method for producing α- sodium ferrites>
Step (a1)
In step (a1), γ-Fe 2 O 3 and NaNO 3 are mixed to obtain a mixed powder MP1. The mixing ratio of γ-Fe 2 O 3 and NaNO 3 is suitably 1: 1 as a molar ratio. The target α- sodium ferrites can be obtained even when the molar ratio deviates from 1: 1, and practically, for example, preferably in the range of 1: 0.9 to 1.2, and 1: 0.95 to 1.15. It is more preferable to set the range. The .gamma. Fe 2 O 3 and NaNO 3 is used as a raw material is not particularly limited, can be used as a commercial product. However, depending on the purity of the commercially available product, it can be made into a mixed powder after being appropriately purified by a known method. In addition, considering the reactivity with NaNO 3 , γ-Fe 2 O 3 may be preferably a powder having a relatively small particle size.
工程(a2)
工程(a2)では、γ- Fe2O3とNaNO3とLiNO3及び／又はKNO3を混合して混合粉末MP2を得る。γ- Fe2O3とNaNO3、LiNO3及び／又はKNO3の混合比率(γ- Fe2O3: (NaNO3+LiNO3及び／又はKNO3))は、モル比で1:1である。前記モル比が1:1から外れても目的とするα-ナトリウムフェライト類を得ることはでき、実用的には、例えば、1:0.9〜1.2の範囲とすることが好ましく、1:0.95〜1.15の範囲とすることがより好ましい。また、NaNO3に対するLiNO3及び／又はKNO3のモル比は0.85:0.15〜1未満:0超、例えば、0.999:0.001の範囲である。NaNO3に対するLiNO3及び／又はKNO3のモル比は、Li及び／又はKによるNaの置換量に応じて変化するCO2吸収特性を考慮して決定される、Li及び／又はKによるNaの希望の置換量に基づいて適宜決定できる。但し、前記モル比が0.85:0.15を外れると、下記の加熱条件において置換型-NaFeO2の生成が困難になる傾向がある。置換型-NaFeO2の合成の容易さ及びCO2吸収特性及び置換の効果がより明らかになるという観点からは、NaNO3に対するLiNO3及び／又はKNO3のモル比は0.9:0.1〜0.99:0.01の範囲である。また、γ- Fe2O3は、NaNO3、LiNO3及び／又はKNO3との反応性を考慮すると、粒子径が比較的小さい粉末であることが好ましい場合がある。
Step (a2)
In the step (a2), γ-Fe 2 O 3 , NaNO 3 and LiNO 3 and / or KNO 3 are mixed to obtain a mixed powder MP2. The mixing ratio of γ-Fe 2 O 3 and NaNO 3 , LiNO 3 and / or KNO 3 (γ-Fe 2 O 3 : (NaNO 3 + LiNO 3 and / or KNO 3 )) is 1: 1 at a molar ratio. is there. The target α- sodium ferrites can be obtained even when the molar ratio deviates from 1: 1, and practically, for example, preferably in the range of 1: 0.9 to 1.2, and 1: 0.95 to 1.15. It is more preferable to set the range. The molar ratio of LiNO 3 and / or KNO 3 for NaNO 3 0.85: less than 0.15: 0, such as more than, 0.999: in the range of 0.001. The molar ratio of LiNO 3 and / or KNO 3 for NaNO 3 is determined in consideration of the CO 2 absorption properties that change depending on the substitution of Na by Li and / or K, of Na by Li and / or K This can be determined as appropriate based on the desired substitution amount. However, when the molar ratio is out of 0.85: 0.15, it tends to be difficult to produce substituted-NaFeO 2 under the following heating conditions. From the viewpoint of ease of synthesis of substituted-NaFeO 2 and the effect of the CO 2 absorption characteristics and substitution become more apparent, the molar ratio of LiNO 3 and / or KNO 3 to NaNO 3 is 0.9: 0.1 to 0.99: 0.01. Range. In addition, in consideration of reactivity with NaNO 3 , LiNO 3 and / or KNO 3 , γ-Fe 2 O 3 may be preferably a powder having a relatively small particle size.
工程(b2)
工程(b2)においては、得られた混合粉末MP1又はMP2を550〜600℃の温度T1に加熱し、次いで、570〜750℃の温度T2(但し、T1<T2)に昇温してさらに加熱してα-NaFeO2又は置換型-NaFeO2を生成させる。
混合粉末MP1を550℃〜600℃の温度T1に加熱しても、加熱時間が比較的短い場合にはα-NaFeO2は生成しにくいか、または生成しない。しかし、温度T1に加熱した試料を570〜750℃の温度T2(但し、T1<T2)に昇温してさらに加熱すると、比較的容易にα-NaFeO2を生成させることができる。粉末を加熱する時間は、α-NaFeO2の生成状況に基づいて適宜決定することができ、温度T1での加熱は、例えば、1〜50時間の範囲であり、温度T2での加熱は、例えば、5〜30時間の範囲とすることでα-NaFeO2を生成させることができる。より具体的には、温度T1が、550℃〜570℃未満の範囲における加熱時間は好ましくは10〜50時間の範囲であり、温度T1が、570℃以上、600℃未満の範囲における加熱時間は好ましくは1〜40時間未満である。尚、工程(b2)の温度T2における加熱においては、加熱の途中で、1回又は2回以上加熱温度を上下させることもできる。
Process (b2)
In step (b2), the obtained mixed powder MP1 or MP2 is heated to a temperature T1 of 550 to 600 ° C., and then heated to a temperature T2 of 570 to 750 ° C. (where T1 <T2). Thus, α-NaFeO 2 or substituted-NaFeO 2 is produced.
Even when the mixed powder MP1 is heated to a temperature T1 of 550 ° C. to 600 ° C., α-NaFeO 2 is hardly generated or not generated when the heating time is relatively short. However, if the sample heated to the temperature T1 is heated to a temperature T2 (where T1 <T2) of 570 to 750 ° C. and further heated, α-NaFeO 2 can be generated relatively easily. The time for heating the powder can be appropriately determined based on the production state of α-NaFeO 2 , the heating at the temperature T1 is, for example, in the range of 1 to 50 hours, and the heating at the temperature T2 is, for example, The α-NaFeO 2 can be generated by setting the time in the range of 5 to 30 hours. More specifically, the heating time in the range where the temperature T1 is 550 ° C. to less than 570 ° C. is preferably in the range of 10 to 50 hours, and the heating time in the range where the temperature T1 is 570 ° C. or more and less than 600 ° C. is Preferably it is 1 to less than 40 hours. In the heating at the temperature T2 in the step (b2), the heating temperature can be raised or lowered once or twice or more during the heating.
成形には、粒子を結合させるためのバインダ材料（結合材）を用いることができる。バインダには、無機質の材料、有機質の材料のどちらも用いることができる。例えば無機質材料としては粘土、鉱物、石灰乳などが挙げられる。また有機材料としては、澱粉、メチルセルロース、ポリビニルアルコール、パラフィンなどが挙げられる。バインダの添加量は、炭酸ガス吸収材成分（岩塩型ナトリウムフェライト）に対して０．１〜２０ｗｔ％とするのが好ましい。 For molding, a binder material (binding material) for binding particles can be used. For the binder, either an inorganic material or an organic material can be used. For example, examples of the inorganic material include clay, mineral, and lime milk. Examples of the organic material include starch, methylcellulose, polyvinyl alcohol, and paraffin. The added amount of the binder is preferably 0.1 to 20 wt% with respect to the carbon dioxide absorbent component (rock salt type sodium ferrite).
吸収反応及び放出反応のどちらの場合においても、反応容器は接触効率を考慮すると流動床式反応容器を利用することもできる。
In both the absorption reaction and the release reaction, a fluidized bed reaction vessel can be used as the reaction vessel in consideration of contact efficiency.
Claims (6)
得られた混合粉末MP1又はMP2を570℃〜750℃の温度に加熱してα-ナトリウムフェライト又は置換型α-ナトリウムフェライトを生成させる工程(b1)、又は得られた混合粉末MP1又はMP2を550〜600℃の温度T1に加熱し、次いで、570〜750℃の温度T2(但し、T1<T2)に昇温してさらに加熱してα-ナトリウムフェライト又は置換型α-ナトリウムフェライトを生成させる工程(b2)、
を含むことを特徴とする請求項１〜３のいずれかに記載の炭酸ガス吸収材の製造方法。 .gamma. Fe 2 O 3 and NaNO 3 to obtain a mixed powder MP1 and mixing step (a1), or to obtain a γ- Fe 2 O 3, NaNO 3 and LiNO 3 and / or KNO 3 were mixed mixed powder MP2 as in step (a2),
Step (b1) of heating the obtained mixed powder MP1 or MP2 to a temperature of 570 ° C. to 750 ° C. to produce α-sodium ferrite or substituted α-sodium ferrite , or 550 of the obtained mixed powder MP1 or MP2 Heating to a temperature T1 of ~ 600 ° C, then raising the temperature to a temperature T2 of 570 to 750 ° C (where T1 <T2) and further heating to produce α-sodium ferrite or substituted α-sodium ferrite (b2),
The method for producing a carbon dioxide absorbent according to any one of claims 1 to 3, wherein:
Priority Applications (1)
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| JP2014123288A JP6383188B2 (en) | 2014-06-16 | 2014-06-16 | Method for producing α-sodium ferrites |
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| JP2016003156A JP2016003156A (en) | 2016-01-12 |
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| JP6383188B2 JP6383188B2 (en) | 2018-08-29 |
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| KR20220112802A (en) | 2019-12-10 | 2022-08-11 | 도다 고교 가부시끼가이샤 | Sodium ferrite particle powder and its manufacturing method |
| WO2022030338A1 (en) | 2020-08-04 | 2022-02-10 | 戸田工業株式会社 | Solid recovery material for carbon dioxide and method for producing same |
| EP4353353A1 (en) * | 2021-06-07 | 2024-04-17 | Toda Kogyo Corp. | Solid material for recovering carbon dioxide, and method for producing same |
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| JP3418023B2 (en) * | 1994-12-16 | 2003-06-16 | 松下電器産業株式会社 | Non-aqueous electrolyte lithium secondary battery |
| JP3053362B2 (en) * | 1995-08-01 | 2000-06-19 | 株式会社東芝 | Separation method of carbon dioxide gas Foam carbon dioxide gas absorbent and carbon dioxide gas separation device |
| JP2931961B2 (en) * | 1996-08-27 | 1999-08-09 | 工業技術院長 | Method for producing layered rock-salt type lithium ferrite by solvothermal ion exchange method |
| JP3420036B2 (en) * | 1997-09-16 | 2003-06-23 | 株式会社東芝 | Carbon dioxide absorbing material and carbon dioxide absorbing method |
| JP3930331B2 (en) * | 2002-01-25 | 2007-06-13 | 東芝三菱電機産業システム株式会社 | Fuel reforming method and system |
| JP3857667B2 (en) * | 2003-07-01 | 2006-12-13 | 株式会社東芝 | Carbon dioxide absorbing material, carbon dioxide absorbing material manufacturing method, carbon dioxide absorbing method, carbon dioxide separating method and carbon dioxide separating device |
| JP5031192B2 (en) * | 2004-03-31 | 2012-09-19 | 準一 山木 | Method for producing positive electrode active material for non-aqueous electrolyte sodium secondary battery |
| JP4621887B2 (en) * | 2005-01-21 | 2011-01-26 | 独立行政法人物質・材料研究機構 | Carbon dioxide absorbing material |
| JP2007090207A (en) * | 2005-09-28 | 2007-04-12 | Toshiba Corp | Carbon dioxide absorber and its manufacturing method |
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