JP2005087932A - Method for regenerating carbon dioxide absorbent - Google Patents
Method for regenerating carbon dioxide absorbent Download PDFInfo
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- JP2005087932A JP2005087932A JP2003327148A JP2003327148A JP2005087932A JP 2005087932 A JP2005087932 A JP 2005087932A JP 2003327148 A JP2003327148 A JP 2003327148A JP 2003327148 A JP2003327148 A JP 2003327148A JP 2005087932 A JP2005087932 A JP 2005087932A
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- carbon dioxide
- regenerating
- absorbing substance
- carbonate
- aqueous solution
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 65
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 37
- 239000002250 absorbent Substances 0.000 title abstract description 6
- 230000002745 absorbent Effects 0.000 title abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- 239000000126 substance Substances 0.000 claims description 45
- 239000011575 calcium Substances 0.000 claims description 23
- 238000003795 desorption Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 32
- 239000011358 absorbing material Substances 0.000 description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
本発明は、炭酸塩を含有する二酸化炭素吸収物質中の炭酸塩を分解し、二酸化炭素吸収物質を再生する二酸化炭素吸収物質の再生方法に関する。更に詳しくは、炭酸塩を含有する二酸化炭素吸収物質中の炭酸塩を高温加熱することなく湿式で化学的に分解して、発生する二酸化炭素を効果的に脱離させて、二酸化炭素吸収物質を再生する二酸化炭素吸収物質の方法に関する。 The present invention relates to a carbon dioxide-absorbing material regeneration method for decomposing a carbonate in a carbon dioxide-absorbing material containing carbonate to regenerate the carbon dioxide-absorbing material. More specifically, the carbonate in the carbon dioxide-absorbing material containing carbonate is chemically decomposed in a wet manner without heating at high temperature, and the generated carbon dioxide is effectively desorbed. It relates to a method of carbon dioxide absorbing material to be regenerated.
従来の炭酸塩を形成する二酸化炭素吸収物質を再生する方法としては、炭酸塩含有する二酸化吸収物質を高温で熱分解して二酸化炭素を脱離して酸化物にする方法が広く知られている。例えば、二酸化炭素吸収物質としてよく知られている水酸化カルシウムや酸化カルシウムは、二酸化炭素を吸収して生成する炭酸カルシウムを熱分解して酸化カルシウム（ＣａＯ）を生成するには、８００℃以上の加熱が必要である。従って、この方法は、一般に外部から多量の熱を加える必要があり、エネルギーの消費量が大きいという問題があるばかりでなく、表面積が小さくなり二酸化炭素吸収性能が低下する。 As a conventional method for regenerating a carbon dioxide-absorbing substance that forms a carbonate, a method in which a carbonate-containing dioxide-absorbing substance is thermally decomposed at a high temperature to desorb carbon dioxide to form an oxide is widely known. For example, calcium hydroxide or calcium oxide, which is well known as a carbon dioxide-absorbing substance, is not less than 800 ° C. in order to thermally decompose calcium carbonate generated by absorbing carbon dioxide to produce calcium oxide (CaO). Heating is required. Therefore, this method generally requires a large amount of heat from the outside, and not only has a problem of large energy consumption, but also reduces the surface area and reduces the carbon dioxide absorption performance.
一方、特許文献１では、より省エネルギーで炭酸カルシウムから水酸化カルシウムを製造する方法として、塩化アンモニウムを用い、水溶性の塩化カルシウム（ＣａＣｌ２）を形成し、二酸化炭素（ＣＯ２）とアンモニア（ＮＨ３）を発生させ、アンモニアと二酸化炭素との混合ガスからアンモニアを分離し、塩化カルシウムと反応させて水酸化カルシウム（Ｃａ（ＯＨ）２）を生成する、以下の反応式（１）、（２）で表されるような方法が開示されている。 On the other hand, in Patent Document 1, as a method for producing calcium hydroxide from calcium carbonate with more energy saving, ammonium chloride is used to form water-soluble calcium chloride (CaCl 2 ), and carbon dioxide (CO 2 ) and ammonia (NH 2 ). 3 ) is generated, ammonia is separated from a mixed gas of ammonia and carbon dioxide, and reacted with calcium chloride to generate calcium hydroxide (Ca (OH) 2 ). The following reaction formulas (1), (2 ) Is disclosed.
ＣａＣＯ３＋２ＮＨ４Ｃｌ→ＣａＣｌ２＋２ＮＨ３↑＋ＣＯ２↑＋Ｈ２Ｏ …（１） CaCO 3 + 2NH 4 Cl → CaCl 2 + 2NH 3 ↑ + CO 2 ↑ + H 2 O (1)
ＣａＣｌ２＋２ＮＨ３↑＋２Ｈ２Ｏ→Ｃａ（ＯＨ）２↓＋２ＮＨ４Ｃｌ …（２） CaCl 2 + 2NH 3 ↑ + 2H 2 O → Ca (OH) 2 ↓ + 2NH 4 Cl (2)
しかし、この方法は、炭酸カルシウム（ＣａＣＯ３）が水に対して溶解度が低いという問題の他に、上記のようにアンモニアと二酸化炭素との混合ガスからアンモニアを分離する必要もある。その上、この反応を効果的に行うためには、反応式（１）では温度７０〜２００℃、圧力４００ｍｍＨｇないし水蒸気飽和圧という（ＣａＣＯ３溶解槽の）反応条件が、反応式（２）では、温度１００〜２００℃、圧力０．５ＭＰａ〜２．０ＭＰａ（５〜２０kgf/cm2）の反応条件が必要である。 However, in this method, in addition to the problem that calcium carbonate (CaCO 3 ) has low solubility in water, it is also necessary to separate ammonia from the mixed gas of ammonia and carbon dioxide as described above. In addition, in order to carry out this reaction effectively, the reaction conditions (temperature of 70 to 200 ° C., pressure of 400 mmHg or water vapor saturation pressure in the reaction formula (1) (CaCO 3 dissolution tank) are The reaction conditions of a temperature of 100 to 200 ° C. and a pressure of 0.5 MPa to 2.0 MPa (5 to 20 kgf / cm 2 ) are necessary.
また、特許文献２は、炭酸カルシウム含有鉱物を酢酸と水溶性アルコール混合水溶液の蒸気に暴露させ、含有炭酸カルシウムと該蒸気との反応生成物を加熱処理して炭酸カルシウムから水酸化カルシウムを形成する方法を開示しているが、この方法では、加熱を伴い、含有鉱物の膨潤、多孔化を目的にしている。このように、現状では炭酸塩含有二酸化炭素吸収物質を省エネルギーで且つ簡便に再生する方法は見出されていない。 Further, Patent Document 2 exposes a calcium carbonate-containing mineral to vapor of a mixed aqueous solution of acetic acid and a water-soluble alcohol, and heat-treats a reaction product of the contained calcium carbonate and the vapor to form calcium hydroxide from calcium carbonate. Although a method is disclosed, this method is accompanied by heating and is intended to swell and make the contained mineral porous. Thus, at present, no method for regenerating the carbonate-containing carbon dioxide-absorbing material in an energy saving and simple manner has been found.
本発明は、上記の問題点を克服するために下記の目的で発明されたものである。
本発明の目的は、炭酸塩を形成する二酸化炭素吸収物質の炭酸塩を常温で化学的に分解し、生成した二酸化炭素を効果的に気相中に脱離させることにより、炭酸塩を水酸化物に変換することにより、省エネルギーで且つ簡便に二酸化炭素吸収物質を再生する方法を提供することである。
The present invention has been invented for the following purposes in order to overcome the above problems.
The object of the present invention is to chemically decompose the carbonate of the carbon dioxide-absorbing substance that forms the carbonate at room temperature, and to effectively desorb the generated carbon dioxide into the gas phase, thereby hydroxylating the carbonate. An object is to provide a method for regenerating a carbon dioxide-absorbing material in an energy-saving and simple manner by converting it into a product.
本発明者は、このような課題を背景に対して、鋭意研究を重ねた結果、炭酸塩を形成する二酸化炭素吸収物質を酸水溶液で処理して炭酸塩を分解して生成する二酸化炭素を完全に除去した後、アルコール水溶液、又はアンモニア水溶液で順次処理して、炭酸塩を分解して生成する二酸化炭素を完全に除去して、水酸化物を形成することにより、高効率且つ省エネルギーで二酸化炭素吸収物質を再生することを見出し、この知見に基づいて本発明を完成させた。 As a result of intensive research on the background of such problems, the present inventor has completely treated carbon dioxide generated by decomposing carbonate by treating a carbon dioxide-absorbing substance that forms carbonate with an acid aqueous solution. After removing the carbon dioxide, it is treated with an aqueous alcohol solution or an aqueous ammonia solution in order to completely remove the carbon dioxide produced by decomposing the carbonate, thereby forming a hydroxide. The present inventors have found that the absorbent material is regenerated and completed the present invention based on this finding.
即ち、本発明１の二酸化炭素吸収物質を再生する方法は、炭酸塩を形成する二酸化炭素吸収物質を酸水溶液で処理して炭酸塩を分解する炭酸塩分解工程と、生成した二酸化炭素を気相に脱離させる二酸化炭素脱離工程と、該二酸化炭素脱離工程後に、アルコール水溶液で処理して水酸化物を生成する水酸化物生成工程とを有することを特徴とする。 That is, the method for regenerating a carbon dioxide-absorbing substance of the present invention includes a carbonate decomposition step in which a carbon dioxide-absorbing substance that forms a carbonate is treated with an acid aqueous solution to decompose the carbonate, and the generated carbon dioxide is vapor-phased. A carbon dioxide desorption step for desorbing the carbon dioxide and a hydroxide generation step for generating a hydroxide by treatment with an aqueous alcohol solution after the carbon dioxide desorption step.
本発明２の二酸化炭素吸収物質を再生する方法は、炭酸塩を形成する二酸化炭素吸収物質を酸水溶液で処理して炭酸塩を分解する炭酸塩分解工程と、生成する二酸化炭素を気相に脱離させる二酸化炭素脱離工程と、該二酸化炭素脱離工程後に、アンモニア水溶液で処理して、水酸化物を生成する水酸化物生成工程とを有することを特徴とする。 The method for regenerating a carbon dioxide-absorbing substance of the present invention comprises a carbonate decomposition step of treating a carbon dioxide-absorbing substance forming a carbonate with an acid aqueous solution to decompose the carbonate, and desorbing the generated carbon dioxide to the gas phase. It is characterized by having a carbon dioxide desorption step of separating, and a hydroxide generation step of generating a hydroxide by treatment with an aqueous ammonia solution after the carbon dioxide desorption step.
本発明３の二酸化炭素吸収物質を再生する方法は、本発明１又は本発明２に記載の二酸化炭素吸収物質を再生する方法において、前記二酸化炭素脱離工程時の圧力が大気圧以下であることを特徴とする。
本発明４の二酸化炭素吸収物質を再生する方法は、本発明１〜３から選択される１発明の二酸化炭素吸収物質を再生する方法において、前記二酸化炭素脱離工程時の温度が常温であることを特徴とする。
The method for regenerating a carbon dioxide-absorbing substance according to the third aspect of the present invention is the method for regenerating a carbon dioxide-absorbing substance according to the first or second aspect, wherein the pressure during the carbon dioxide desorption step is equal to or lower than atmospheric pressure. It is characterized by.
The method for regenerating a carbon dioxide-absorbing substance according to the present invention 4 is the method for regenerating a carbon dioxide-absorbing substance according to one invention selected from the first to third aspects, wherein the temperature during the carbon dioxide desorption step is normal temperature. It is characterized by.
本発明５の二酸化炭素吸収物質を再生する方法は、本発明１〜４から選択される１発明の二酸化炭素吸収物質を再生する方法において、前記炭酸塩分解工程と前記二酸化炭素脱離工程を同時に行うことを特徴とする。
本発明６の二酸化炭素吸収物質を再生する方法は、本発明５の二酸化炭素吸収物質を再生する方法において、前記炭酸塩分解工程、及び前記二酸化炭素脱離工程時の圧力が大気圧以下であることを特徴とする。
The method for regenerating a carbon dioxide-absorbing substance according to the present invention 5 is the method for regenerating a carbon dioxide-absorbing substance according to one invention selected from the present inventions 1 to 4, wherein the carbonate decomposition step and the carbon dioxide desorption step are simultaneously performed. It is characterized by performing.
The method for regenerating a carbon dioxide-absorbing substance of the present invention 6 is the method for regenerating a carbon dioxide-absorbing substance of the present invention 5, wherein the pressure during the carbonate decomposition step and the carbon dioxide desorption step is equal to or lower than atmospheric pressure. It is characterized by that.
本発明７の二酸化炭素吸収物質を再生する方法は、本発明５の二酸化炭素吸収物質を再生する方法において、前記炭酸塩分解工程、及び前記二酸化炭素脱離工程時の温度が常温であることを特徴とする。
本発明８の二酸化炭素吸収物質を再生する方法は、本発明１〜７から選択される１発明の二酸化炭素吸収物質を再生する方法において、前記酸水溶液が硝酸、塩酸、酢酸、硫酸、リン酸から選択される１種以上の水溶液であることを特徴とする。
The method for regenerating a carbon dioxide-absorbing substance of the present invention 7 is the method for regenerating a carbon dioxide-absorbing substance of the present invention 5, wherein the temperature during the carbonate decomposition step and the carbon dioxide desorption step is normal temperature. Features.
The method for regenerating a carbon dioxide-absorbing material according to the present invention 8 is the method for regenerating a carbon dioxide-absorbing material according to one invention selected from the present invention 1-7, wherein the acid aqueous solution is nitric acid, hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid. It is 1 or more types of aqueous solution selected from these, It is characterized by the above-mentioned.
本発明９の二酸化炭素吸収物質を再生する方法は、本発明１〜８から選択される１発明の二酸化炭素吸収物質を再生する方法において、前記二酸化炭素吸収物質が、アルカリ金属、アルカリ土類金属、鉄、マグネシウムから選択される１種以上の酸化物若しくは水酸化物、又はカルシウムを含む生物体を出発物とする酸化物若しくは水酸化物であることを特徴とする。 The method for regenerating a carbon dioxide-absorbing material according to the present invention 9 is the method for regenerating a carbon dioxide-absorbing material according to one invention selected from the present inventions 1 to 8, wherein the carbon dioxide-absorbing material is an alkali metal or an alkaline earth metal. It is characterized by being one or more oxides or hydroxides selected from iron, magnesium, or oxides or hydroxides starting from organisms containing calcium.
［アルコール水溶液による水酸化物生成工程］
本発明１で用いるアルコール水溶液は、メチルアルコール及び／又はエチルアルコールを水で薄めたものである。メチルアルコールを使用する場合は、再生する二酸化炭素吸収物質として炭酸カルシウム（ＣａＣＯ３）、酸水溶液として酢酸を用いた場合には、以下の反応式（３）及び（４）により、炭酸カルシウム（ＣａＣＯ３）を化学的に分解して、カルシウム（Ｃａ）を溶解して、同時に生成する二酸化炭素を完全に気相に脱離させた後に、メチルアルコール水溶液で処理して水酸化カルシウム（Ｃａ（ＯＨ）２）を沈殿生成することにより、二酸化炭素吸収物質が再生される。
[Hydroxide generation process with aqueous alcohol solution]
The alcohol aqueous solution used in the present invention 1 is obtained by diluting methyl alcohol and / or ethyl alcohol with water. When methyl alcohol is used, calcium carbonate (CaCO 3 ) is used as the carbon dioxide absorbing material to be regenerated, and when acetic acid is used as the acid aqueous solution, calcium carbonate (CaCO 3 ) is obtained by the following reaction formulas (3) and (4). 3 ) is chemically decomposed to dissolve calcium (Ca), and simultaneously generated carbon dioxide is completely desorbed to the gas phase, and then treated with an aqueous methyl alcohol solution to obtain calcium hydroxide (Ca (OH 2 ) The carbon dioxide absorbing material is regenerated by precipitating 2 ).
ＣａＣＯ３＋２ＣＨ３ＣＯＯＨ→Ｃａ２＋＋２ＣＨ３ＣＯＯ−＋ＣＯ２↑＋Ｈ２Ｏ …（３） CaCO 3 + 2CH 3 COOH → Ca 2+ + 2CH 3 COO − + CO 2 ↑ + H 2 O (3)
Ｃａ（ＣＨ３ＣＯＯ）２＋２ＣＨ３ＯＨ→ Ｃａ（ＯＨ）２↓＋２ＣＨ３ＣＯＯＣＨ３ …（４） Ca (CH 3 COO) 2 + 2CH 3 OH → Ca (OH) 2 ↓ + 2CH 3 COOCH 3 (4)
本発明１において、二酸化炭素吸収物質の再生には、二酸化炭素吸収物質の炭酸塩を完全に分解して、溶解することと、発生する二酸化炭素を完全に気相に脱離することが重要である。従って、溶解度が低い場合は、溶液の温度を常温以上にすることもできるし、多量の水溶液を用いることもできる。発生する二酸化炭素を効果的に気相に脱離するには、常温以上にすることも有効であるが、溶液を撹拌しながら、大気圧以下にするのがより効果的である。 In the present invention 1, for the regeneration of the carbon dioxide absorbing material, it is important to completely decompose and dissolve the carbonate of the carbon dioxide absorbing material and to completely desorb the generated carbon dioxide to the gas phase. is there. Therefore, when the solubility is low, the temperature of the solution can be raised to room temperature or higher, and a large amount of aqueous solution can be used. In order to effectively desorb the generated carbon dioxide to the gas phase, it is effective to set the temperature to room temperature or higher, but it is more effective to reduce the pressure to atmospheric pressure or lower while stirring the solution.
［アンモニア水溶液による水酸化物生成工程］
本発明２のアンモニア水溶液を用いる場合の具体的な１例として、再生する二酸化炭素吸収物質として炭酸カルシウム（ＣａＣＯ３）、酸水溶液として硝酸（ＨＮＯ３）を用いた場合には、以下の反応式（５）及び（６）より、炭酸カルシウムを化学的に分解して、カルシウム（Ｃａ）を溶解して、同時に生成する二酸化炭素を完全に気相に脱離させた後に、アンモニア水溶液で処理して水酸化カルシウム（Ｃａ（ＯＨ）２）を沈殿生成することにより、二酸化炭素吸収物質が再生される。
ＣａＣＯ３＋２ＨＮＯ３→ Ｃａ２＋＋２ＮＯ３ −＋ＣＯ２↑＋Ｈ２Ｏ …（５）
Ｃａ（ＮＯ３）２＋２ＮＨ４ＯＨ→ Ｃａ（ＯＨ）２↓＋２ＮＨ４ ＋＋２ＮＯ３ − …（６）
[Hydroxide generation process with aqueous ammonia solution]
Specific example of the case of using an aqueous ammonia solution of the present invention 2, calcium carbonate as a carbon dioxide absorbing materials to be reproduced (CaCO 3), in the case of using the nitric acid (HNO 3) as an acid aqueous solution, the following reaction formula From (5) and (6), calcium carbonate is chemically decomposed, calcium (Ca) is dissolved, and simultaneously generated carbon dioxide is completely desorbed into the gas phase, followed by treatment with an aqueous ammonia solution. Thus, the carbon dioxide-absorbing substance is regenerated by forming calcium hydroxide (Ca (OH) 2 ) by precipitation.
CaCO 3 + 2HNO 3 → Ca 2+ + 2NO 3 − + CO 2 ↑ + H 2 O (5)
Ca (NO 3 ) 2 + 2NH 4 OH → Ca (OH) 2 ↓ + 2NH 4 + + 2NO 3 − (6)
本発明では、炭酸塩を形成する二酸化炭素吸収物質の炭酸塩を常温で化学的に分解し、生成した二酸化炭素を効果的に気相中に脱離させることにより、炭酸塩を水酸化物や酸化物に変換することにより、省エネルギーで且つ簡便に二酸化炭素吸収物質を再生することができる。 In the present invention, the carbonate of the carbon dioxide-absorbing substance that forms the carbonate is chemically decomposed at room temperature, and the produced carbon dioxide is effectively desorbed into the gas phase, so that the carbonate is converted to hydroxide or By converting to an oxide, it is possible to regenerate the carbon dioxide-absorbing material with energy saving and simple.
以下、本発明の実施の形態を実施例をあげて更に具体的に説明する。本実施例では、二酸化炭素吸収物質として最も使用されている酸化カルシウム（ＣａＯ）、水酸化カルシウム（Ｃａ（ＯＨ）２）が二酸化炭素（ＣＯ２）を吸収して生成される炭酸カルシウムの再生について述べる。 Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. In the present embodiment, calcium carbonate (CaO) and calcium hydroxide (Ca (OH) 2 ), which are most used as carbon dioxide-absorbing substances, regenerate calcium carbonate produced by absorbing carbon dioxide (CO 2 ). State.
６０ｗ％の硝酸１０gと蒸留水１００ｍｌを混合して、硝酸水溶液（０．９２モル／リットル、ｐＨ：０．３）を作成する。この硝酸水溶液を撹拌させながらこれに溶解しうる炭酸カルシウムを添加して、以下の式のように完全に溶解させ、二酸化炭素を発生させる。 An aqueous nitric acid solution (0.92 mol / liter, pH: 0.3) is prepared by mixing 10 g of 60 w% nitric acid and 100 ml of distilled water. While this nitric acid aqueous solution is stirred, soluble calcium carbonate is added to the nitric acid solution and completely dissolved as shown in the following formula to generate carbon dioxide.
ＣａＣＯ３＋２ＨＮＯ３→ Ｃａ２＋＋２ＮＯ３ −＋ＣＯ２↑＋Ｈ２Ｏ CaCO 3 + 2HNO 3 → Ca 2+ + 2NO 3 − + CO 2 ↑ + H 2 O
次に、この水溶液を撹拌しながらアスピレータ（水流ポンプ）で気相を４００ｍｍＨｇの圧力に保って排気しながら、生成した二酸化炭素を完全に気相に脱離させる。この二酸化炭素を完全に気相に脱離させた後、２８ｗｔ％のアンモニア水を添加し、以下の反応を進行させる。 Next, the produced carbon dioxide is completely desorbed into the gas phase while this aqueous solution is stirred and evacuated with an aspirator (water flow pump) while maintaining the gas phase at a pressure of 400 mmHg. After the carbon dioxide is completely desorbed into the gas phase, 28 wt% ammonia water is added to proceed with the following reaction.
Ｃａ（ＮＯ３）２＋２ＮＨ４ＯＨ→ Ｃａ（ＯＨ）２↓＋２ＮＨ４ ＋＋２ＮＯ３ −
約１時間後、水酸化カルシウムの白色沈殿を得た。この沈殿物の濾過・洗浄を３回繰り返した後、これを１２０℃で乾燥した。
Ca (NO 3 ) 2 + 2NH 4 OH → Ca (OH) 2 ↓ + 2NH 4 + + 2NO 3 −
After about 1 hour, a white precipitate of calcium hydroxide was obtained. This filtration and washing of the precipitate was repeated three times, and then this was dried at 120 ° C.
６０ｗ％の硝酸１０gと蒸留水１００ｍｌを混合して、硝酸水溶液（０．９２モル／リットル、ｐＨ：０．３）を作成する。この硝酸水溶液を撹拌させて、アスピレータ（水流ポンプ）で気相を４００ｍｍＨｇの圧力に保って排気しながら、溶解しうる炭酸カルシウムを添加して、完全に溶解させ、同時に生成した二酸化炭素を完全に気相に脱離させた。 An aqueous nitric acid solution (0.92 mol / liter, pH: 0.3) is prepared by mixing 10 g of 60 w% nitric acid and 100 ml of distilled water. While stirring this nitric acid aqueous solution and exhausting it while keeping the gas phase at a pressure of 400 mmHg with an aspirator (water flow pump), soluble calcium carbonate is added and completely dissolved, and at the same time, the generated carbon dioxide is completely removed. Desorbed into the gas phase.
ＣａＣＯ３＋２ＨＮＯ３→ Ｃａ２＋＋２ＮＯ３ −＋ＣＯ２↑＋Ｈ２Ｏ …（３） CaCO 3 + 2HNO 3 → Ca 2+ + 2NO 3 − + CO 2 ↑ + H 2 O (3)
この二酸化炭素（ＣＯ２）を気相に完全に脱離させた後、２８ｗｔ％のアンモニア水を添加し、以下の反応を進行させる。 After the carbon dioxide (CO 2 ) is completely desorbed into the gas phase, 28 wt% ammonia water is added to proceed with the following reaction.
Ｃａ（ＮＯ３）２＋２ＮＨ４ＯＨ→ Ｃａ（ＯＨ）２↓＋２ＮＨ４ ＋＋２ＮＯ３ −
…（４）
約１時間後、水酸化カルシウムの白色沈殿を得た。実施例１と同様にこの沈殿物の濾過・洗浄を３回繰り返した後、これを１２０℃で乾燥した。
Ca (NO 3 ) 2 + 2NH 4 OH → Ca (OH) 2 ↓ + 2NH 4 + + 2NO 3 −
(4)
After about 1 hour, a white precipitate of calcium hydroxide was obtained. The precipitate was filtered and washed three times in the same manner as in Example 1, and then dried at 120 ° C.
酢酸水溶液１００ｍｌを撹拌させながら炭酸カルシウムを添加して、完全に溶解出来る程度の酢酸カルシウムを生成させる。 While stirring 100 ml of an acetic acid aqueous solution, calcium carbonate is added to produce calcium acetate that can be completely dissolved.
ＣａＣＯ３＋２ＣＨ３ＣＯＯＨ→ Ｃａ２＋＋２ＣＨ３ＣＯＯ−＋ＣＯ２↑＋Ｈ２Ｏ CaCO 3 + 2CH 3 COOH → Ca 2+ + 2CH 3 COO − + CO 2 ↑ + H 2 O
次に、この水溶液を撹拌しながらアスピレータ（水流ポンプ）で気相を４００ｍｍＨｇに排気し、生成した二酸化炭素を完全に気相に脱離させる。二酸化炭素が気相に完全に脱離させた後、メチルアルコール水溶液を添加し、以下の反応を進行させる。 Next, while stirring the aqueous solution, the gas phase is exhausted to 400 mmHg by an aspirator (water flow pump), and the generated carbon dioxide is completely desorbed to the gas phase. After carbon dioxide is completely desorbed into the gas phase, an aqueous methyl alcohol solution is added to proceed with the following reaction.
Ｃａ２＋＋２ＣＨ３ＣＯＯ−＋ＣＨ３ＯＨ→Ｃａ（ＯＨ）２↓＋２ＣＨ３ＣＯＯＣＨ３ Ca 2+ + 2CH 3 COO − + CH 3 OH → Ca (OH) 2 ↓ + 2CH 3 COOCH 3
得られた水酸化カルシウムの白色沈殿の濾過・洗浄を３回繰り返した後、１２０℃で乾燥した。実施例１〜３で得られた水酸化カルシウムは、二酸化炭素吸収物質として使用することができるが、この水酸化カルシウムを５００℃近傍まで加熱処理をして酸化カルシウムにして二酸化炭素吸収物質として使用することもできる。 The obtained white precipitate of calcium hydroxide was repeatedly filtered and washed three times, and then dried at 120 ° C. The calcium hydroxide obtained in Examples 1 to 3 can be used as a carbon dioxide-absorbing substance, but this calcium hydroxide is heated to around 500 ° C. to form calcium oxide and used as a carbon dioxide-absorbing substance. You can also
一般に、二酸化炭素吸収物質は、二酸化炭素を吸収して炭酸塩を形成するが、高温処理により炭酸塩は分解される、二酸化炭素の吸収と再生を繰り返すと、次第に二酸化炭素吸収性能は低下してくる。物性的には、二酸化炭素吸収と再生を繰り返すことにより表面積、ポア容積（細孔容積）は低下していく。従って、二酸化炭素吸収性能の低下はこれらの物性変化によると考えられる。本発明では二酸化炭素吸収性能の低下した二酸化炭素吸収物質から生じた炭酸カルシウムを使用して、本発明による方法で再生を行うと、水酸化カルシウム、酸化カルシウムの初期の表面積、ポア容積が再生され、初期の二酸化炭素吸収性能も得られた。
In general, carbon dioxide-absorbing substances absorb carbon dioxide to form carbonates, but carbonates are decomposed by high-temperature treatment. When carbon dioxide absorption and regeneration are repeated, the carbon dioxide absorption performance gradually decreases. come. In terms of physical properties, the surface area and pore volume (pore volume) decrease as carbon dioxide absorption and regeneration are repeated. Therefore, the decrease in carbon dioxide absorption performance is considered to be due to these physical property changes. In the present invention, when calcium carbonate generated from a carbon dioxide-absorbing substance having reduced carbon dioxide absorption performance is used and regenerated by the method according to the present invention, the initial surface area and pore volume of calcium hydroxide and calcium oxide are regenerated. The initial carbon dioxide absorption performance was also obtained.
Claims (9)
生成した二酸化炭素を気相に脱離させる二酸化炭素脱離工程と、
該二酸化炭素脱離工程後に、アルコール水溶液で処理して水酸化物を生成する水酸化物生成工程と
を有することを特徴とする二酸化炭素吸収物質を再生する方法。 A carbonate decomposition step in which a carbon dioxide-absorbing substance that forms carbonate is treated with an acid aqueous solution to decompose carbonate;
A carbon dioxide desorption process for desorbing the generated carbon dioxide into the gas phase;
A method for regenerating a carbon dioxide-absorbing substance, comprising: a hydroxide generation step of generating a hydroxide by treatment with an aqueous alcohol solution after the carbon dioxide desorption step.
生成する二酸化炭素を気相に脱離させる二酸化炭素脱離工程と、
該二酸化炭素脱離工程後に、アンモニア水溶液で処理して、水酸化物を生成する水酸化物生成工程と
を有することを特徴とする二酸化炭素吸収物質を再生する方法。 A carbonate decomposition step in which a carbon dioxide-absorbing substance that forms carbonate is treated with an acid aqueous solution to decompose carbonate;
A carbon dioxide desorption process for desorbing the generated carbon dioxide into the gas phase;
A method of regenerating a carbon dioxide-absorbing substance, comprising: a hydroxide generation step of generating a hydroxide by treating with an aqueous ammonia solution after the carbon dioxide desorption step.
前記二酸化炭素脱離工程時の圧力が大気圧以下である
ことを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 1 or 2,
A method for regenerating a carbon dioxide-absorbing substance, wherein the pressure during the carbon dioxide desorption step is equal to or lower than atmospheric pressure.
前記二酸化炭素脱離工程時の温度が常温である
ことを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 1 selected from claims 1 to 3,
A method for regenerating a carbon dioxide-absorbing substance, wherein the temperature during the carbon dioxide desorption step is room temperature.
前記炭酸塩分解工程と前記二酸化炭素脱離工程を同時に行う
ことを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 1 selected from claims 1 to 4,
The method for regenerating a carbon dioxide-absorbing substance, wherein the carbonate decomposition step and the carbon dioxide desorption step are performed simultaneously.
前記炭酸塩分解工程、及び前記二酸化炭素脱離工程時の圧力が大気圧以下である
ことを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 5,
A method for regenerating a carbon dioxide-absorbing substance, wherein the pressure during the carbonate decomposition step and the carbon dioxide desorption step is equal to or lower than atmospheric pressure.
前記炭酸塩分解工程、及び前記二酸化炭素脱離工程時の温度が常温である
ことを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 5,
A method for regenerating a carbon dioxide-absorbing substance, wherein the temperature during the carbonate decomposition step and the carbon dioxide desorption step is room temperature.
前記酸水溶液が硝酸、塩酸、酢酸、硫酸、リン酸から選択される１種以上の水溶液であることを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 1 selected from claims 1 to 7,
A method for regenerating a carbon dioxide-absorbing substance, wherein the acid aqueous solution is at least one aqueous solution selected from nitric acid, hydrochloric acid, acetic acid, sulfuric acid, and phosphoric acid.
前記二酸化炭素吸収物質が、アルカリ金属、アルカリ土類金属、鉄、マグネシウムから選択される１種以上の酸化物若しくは水酸化物、又はカルシウムを含む生物体を出発物とする酸化物若しくは水酸化物であることを特徴とする二酸化炭素吸収物質を再生する方法。 The method for regenerating a carbon dioxide-absorbing substance according to claim 1 selected from claims 1 to 8,
The carbon dioxide-absorbing substance is one or more oxides or hydroxides selected from alkali metals, alkaline earth metals, iron and magnesium, or oxides or hydroxides starting from organisms containing calcium A method for regenerating a carbon dioxide-absorbing substance, characterized in that
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100186591A1 (en) * | 2007-06-21 | 2010-07-29 | Statoil Asa | System and process for handling a co2 comprising waste gas and separation of co2 |
| GB2467921A (en) * | 2009-02-19 | 2010-08-25 | Origo Ind Ltd | Carbon dioxide absorption and desorption |
| US8435330B2 (en) | 2007-11-01 | 2013-05-07 | Alstom Technology Ltd | Carbon capture system and process |
| WO2019211714A1 (en) * | 2018-04-30 | 2019-11-07 | National Cheng Kung University | Method for regeneration of carbon dioxide absorbent |
| CN116832580A (en) * | 2023-08-21 | 2023-10-03 | 天府永兴实验室 | Low energy carbon dioxide capture composition with hydrogen ion self-regulating property, capture method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100186591A1 (en) * | 2007-06-21 | 2010-07-29 | Statoil Asa | System and process for handling a co2 comprising waste gas and separation of co2 |
| US8435330B2 (en) | 2007-11-01 | 2013-05-07 | Alstom Technology Ltd | Carbon capture system and process |
| KR101329149B1 (en) * | 2007-11-01 | 2013-11-14 | 알스톰 테크놀러지 리미티드 | Carbon capture system and process |
| GB2467921A (en) * | 2009-02-19 | 2010-08-25 | Origo Ind Ltd | Carbon dioxide absorption and desorption |
| WO2019211714A1 (en) * | 2018-04-30 | 2019-11-07 | National Cheng Kung University | Method for regeneration of carbon dioxide absorbent |
| CN116832580A (en) * | 2023-08-21 | 2023-10-03 | 天府永兴实验室 | Low energy carbon dioxide capture composition with hydrogen ion self-regulating property, capture method and application |
| CN116832580B (en) * | 2023-08-21 | 2024-03-15 | 天府永兴实验室 | Low energy carbon dioxide capture composition with hydrogen ion self-regulating property, capture method and application |
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