Study on CO2 absorption-mineralization characteristics of mixed amine solution coupled with CaO and key influencing factors in mineralization process
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摘要: 有机胺捕集CO2是一种有效的燃烧后碳捕集(PCC)技术,同时CO2矿物碳酸化是一种安全和稳定封存CO2的方法。本研究通过将两种方式结合,以MEA/MDEA混合胺溶液作为CO2吸收剂,以CaO作为CO2矿化原料,研究了不同混合胺溶液配比、温度、反应时间和CaO添加比例等条件下混合胺溶液耦合CaO吸收-矿化CO2性能。结果表明,在常温常压下CaO可对MEA/MDEA溶液中吸收的CO2进行有效矿化并同时实现MEA/MDEA溶液的再生;并且经过五次循环吸收-矿化实验后,MEA/MDEA溶液仍保持了较高的CO2转化率(77.4%)和CO2循环负荷(1.03 mol/L)。FT-IR和XRD表征分析表明,CaO的添加向MEA/MDEA溶液中提供了大量Ca2+和OH−,可分别与溶液中的
${\rm{CO}}_3^{2-} /{\rm{HCO}}_3^- $ 、质子化胺反应生成碳酸钙沉淀和游离胺,从而同时完成对CO2的矿化和MEA/MDEA溶液的化学再生;并且得到的固体产物主要成分为碳酸钙,方解石是其主要晶型。Abstract: Amine CO2 capture is an effective post-combustion carbon capture (PCC) technology, while CO2 mineral carbonation is a safe and stable method for CO2 storage. In this paper, these two methods were combined, and the CO2 absorption-mineralization performance of mixed amine solution coupled with CaO under different ratios of mixed amine solution, temperature, reaction time and CaO addition ratio were studied by using MEA/MDEA mixed amine solution as the CO2 absorbent and using CaO as the CO2 mineralizing raw material. The results show that CaO could effectively mineralize the CO2 absorbed in MEA/MDEA solution, realizing the regeneration of MEA/MDEA solution simultaneously under normal temperature and pressure. Meanwhile, the MEA/MDEA solution can still maintain a high CO2 conversion rate (77.4%) and CO2 cycle loading (1.03 mol/L) after five cycles of absorption-mineralization experiments. The FT-IR and XRD analyses reveal that the addition of CaO makes a large amount of Ca2+ and OH- into the MEA/MDEA solution, which could react with CO$_3^{2{\rm{ - }}} $ /HCO$_3^{\rm{ - }} $ and protonated amine in the solution to form calcium carbonate precipitate and free amine respectively, thus realizing the mineralization of CO2 and the regeneration of MEA/MDEA solution. The main component of solid products obtained is calcium carbonate, and calcite is its main crystal form.-
Key words:
- CO2 /
- mixed amine /
- mineral carbonation /
- chemical regeneration /
- calcium carbonate
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图 1 CO2吸收和矿化反应系统示意图
Figure 1 (a) System of CO2 absorption, (b) system of CO2 mineralization
1: gas cylinder; 2: pressure reducing valve; 3: mass flowmeter; 4: mixing tank; 5: buffer bottle; 6: CO2 bubbling absorption device; 7: thermostatic heating magnetic stirrer; 8: pH meter; 9: serpentine condenser; 10: drying tube; 11: flue gas analyzer; 12: slurry reaction device; 13: filter unit
表 1 MEA/MDEA混合胺溶液耦合CaO吸收-矿化CO2反应过程
Table 1 CO2 reactions in the absorption-mineralization process with MEA/MDEA mixed amine solution coupling CaO
CO2 absorption process MEA RNH2 + CO2 (aq) ↔ ${\rm{RNH} }^{\text{+} } _{2 }$COO−(Zwitterion) (1) ${\rm{RNH} }^+_{2 }$COO− + RNH2 ↔ RNHCOO− +${\rm{RNH} }^ +_{3}$ (Protonated amine) (2) RNHCOO− + H2O ↔ RNH2 + ${\rm{HCO}}_{3}^{{{ - }}} $ (3) MDEA CO2 (aq) + H2O ↔ H2CO3 ↔ H+ + ${\rm{HCO}}_{3}^{{{ - }}} $ (4) R1R2R3N + H+ → R1R2R3NH+(Protonated amine) (5) CO2 mineralization process CaO(s) + H2O → Ca2+ + 2OH− (6) Ca2+ + ${\rm{HCO}}_{3}^{{\rm{ - }}} $ → CaCO3↓+ H+ (7) ${\rm{HCO}}_{3}^{{{ - }}} $ + OH− ↔ ${\rm{CO}}_{3}^{{2}{ - }} $ + H2O (8) Ca2++$ {\rm{CO}}_{3}^{{2}{\rm{ - }}} $→CaCO3↓ (9) Mixed amine chemical
regeneration processMEA $ {\rm{RNH}}_{3}^+$ + OH− ↔ RNH2 + H2O (10) MDEA R1R2R3NH+ + OH− ↔ R1R2R3N + H2O (11) Note: RNH2 represents MEA, R1R2R3N represents MDEA, and R, R1, R2 and R3 represent different alkyl side chains -
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