Protonation constants and thermodynamic properties of amines for post combustion capture of CO2

Fernandes, Debra; Conway, William; Wang, Xiaoguang; Burns, Robert C.; Lawrance, Geoffrey A.; Maeder, Marcel; Puxty, Graeme

doi:10.1016/j.jct.2012.02.031

Cited by 79 publications

(79 citation statements)

References 19 publications

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“…Reaction rates and equilibrium constants for the water dissoci-122 ation (1), the hydration of CO 2 (2), dissociation of carbonic acid (3) 123 and bicarbonate (4) are known (Edsall, 1969;Pocker and Bjorkquist, 124 1977), as well as the protonation constants for many amines (5) 125 (Hamborg and Versteeg, 2009;Perrin, 1965 In contrast, the reaction between tertiary (and some steri-139 cally hindered) amines and CO 2 can be described with the base 140 catalysis of CO 2 hydration as proposed by Donaldson and Nguyen 141 (Donaldson and Nguyen, 1980;Fernandes et al, 2012) and loadings 142 of 1.0 mol CO 2 /mol amine are achieved in the following way:…”

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confidence: 99%

“…In addition, 165 ammonia (Ahn et al, 2011a,b;Holmes et al, 1998;Mani et al, 166 2006;Pellegrini et al, 2010;Rowland et al, 2011), amino acid 167 (Ciftja et al, 2013;Hartono et al, 2011;Hook, 1997;Xiang et al, 168 2012) and various other amine systems have also been examined 169 by NMR (Conway et al, 2012;Fernandes et al, 2012;García-Abuín 170 et al, 2012;Hartono et al, 2006;Kim et al, 2011a;McCann et al, 171 2011b;Mergler et al, 2011;Paul et al, 2008;Yang et al, 2012). 172 Among the latter, piperazine (PZ), a cyclic diamine, is the most 173 commonly studied (Bishnoi andRochelle, 2000, 2002;Böttinger 174 et al, 2008;Conway et al, 2013;Cullinane and Rochelle, 2005;175 Derks et al, 2010;Ermatchkov et al, 2003;Hartono et al, 2013;176 Kim et al, 2011b).…”

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confidence: 99%

“…Concerning 1 H NMR analyses, quantitative experiments are 238 combined with quantitative 13 C data in order to confirm speci-239 ation (Ballard et al, 2011;Böttinger et al, 2008;Bottinger and 240 Hasse, 2008;Kim et al, 2011a;Ma'mun et al, 2006) and some 241 kinetic and equilibrium studies on primary, secondary and steri-242 cally hindered amines deal with speciation calculated only by using 243 1 H NMR data (Conway et al, 2013(Conway et al, , 2011(Conway et al, , 2012Ermatchkov et al, 244 2003;Fernandes et al, 2012;McCann et al, 2009aMcCann et al, ,b, 2011aXiang 245 et al, 2012). As with the quantitative 13 C experiments, quantita-246 tive 1 H NMR data are also used in studies where the main goals are 247 the development of thermodynamic models (Bishnoi and Rochelle, 248 2000Rochelle, 248 , 2002Cullinane and Rochelle, 2005;Derks et al, 2010;Fan 249 et al, 2009;Hartono et al, 2013).…”

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confidence: 99%

“…In Jakobsen et al (2005) (Cullinane and Rochelle, 2005;Ermatchkov et al, 2003). , 2011a,b;Barzagli et al, 2009Barzagli et al, , 2010Barzagli et al, , 2011Mani et al, 2006), 408 3-(trimethylsilyl)-propionic acid sodium salt (Conway et al, 2012;409 Fernandes et al, 2012;McCann et al, 2009aMcCann et al, ,b, 2011bXiang et al, 410 2012) or tetramethylsilane. (Barth et al, 1984;Yamada et al, 2012;411 Jakobsen et al, 2008;Yang et al, 2009) exchanging proton species appear with a common peak.…”

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confidence: 99%

“…The calculation of carbamate stability equilibrium constants is a 763 fundamental and important task because of the crucial role played 764 by the carbamate formation reaction in the chemical systems under 765 study. It is indispensable for determining and/or modelling the 766 vapour-liquid equilibria in the CO 2 absorption process and for the 767 calculation of the thermodynamics of the carbamate formation 768 (Bishnoi and Rochelle, 2000;Conway et al, 2011;Ermatchkov et al, 769 2003;Fernandes et al, 2012;Jakobsen et al, 2005;McCann et al, 770 2011a). For equilibria in solution, activities of the chemical species 771 are related to the ideal concentration by correction factors, called 772 activity coefficients ( ), and the equilibrium constants measured 773 in an ideal solution can be used to predict equilibria in non-ideal 774 solutions.…”

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confidence: 99%

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NMR spectroscopy applied to amine–CO2–H2O systems relevant for post-combustion CO2 capture: A review

Perinu

Arstad

Jens

2014

International Journal of Greenhouse Gas Control

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confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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NMR spectroscopy applied to amine–CO2–H2O systems relevant for post-combustion CO2 capture: A review

Perinu

Arstad

Jens

2014

International Journal of Greenhouse Gas Control

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Isolation and Crystal Structure Determination of Piperazine Dicarbamate Obtained from a Direct Reaction between Piperazine and Carbon Dioxide in Methanol

Sim

Jhon

et al. 2016

Bulletin Korean Chem Soc

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Separation of CO 2 in the flue gas emitted from coal-fired power plants is the first technological step toward reducing the CO 2 concentration in atmosphere, and eventually for mitigating the global climate change. 1,2 In this respect, postcombustion processes employing CO 2 -absorbing agents or CO 2 sorbents have been actively developed. 3 Aqueous 30 wt % monoethanolamine (MEA, HO(CH 2 ) 2 NH 2 ) solution is a representative sorbent, which quickly absorbs and separates CO 2 from flue gas through forming an MEA carbamate salt [HO(CH 2 ) 2 NH 3 + ][HO(CH 2 ) 2 NHCOO − ]. 4-6 In this way, more than 95% of CO 2 in flue gas can be captured with preventing CO 2 from being emitted to atmosphere. The current problem underlying in the aqueous amine sorbent process is that the stripping step consumes a large amount of energy in regenerating the amines for repeated usages. Therefore, extensive research efforts are currently being devoted to developing efficient amines or their mixtures with aiming at enhancing their key properties involving CO 2 absorption rates and capacities, and in particular desorption temperature. [6][7][8][9][10][11] Piperazine (PZ), a cyclic secondary amine, has a working capacity of 0.90 mol CO 2 /mol greater than 0.43 mol CO 2 / mol of MEA. 12 The larger CO 2 -absorbing capacity of PZ than MEA is due to the fact that there are two potentially reactive secondary amine groups in PZ whereas MEA has only one. In addition, although PZ has more sterically congested reactive sites than MEA, it can absorb and desorb CO 2 much faster than MEA. 13 Accordingly, PZ is also regarded as one of the promising amine sorbents, and, in fact, is suggested as a main component of the KS-1 sorbent currently used in the established Mitsubishi process. 14 As an additive, PZ can play a role in promoting the absorption rate of others, e.g., sterically hindered 2-amino-2-methyl-1propanol (AMP) or even tertiary amines. 14,15 Because of these interesting properties, PZ has attracted great attention for their applications to various CO 2 absorption reactions. However, PZ involves many reaction pathways in aqueous solution, and on account of the complex chemistry the consensus on the reaction mechanisms has not been achieved thus far. 16 In this regard, herein our experimental results on the isolation of PZ-dicarbamate, and the elucidation of its crystal structure will contribute to further understanding of the PZ-involved CO 2 -absorption reactions.In aqueous solution, PZ involves successive protonation and CO 2 -absorption reactions ( Figure S1, Supporting Information). At 25 C, the first and second protonation constants of PZ are reported to be log K = 9.77 and 5.60 M −1 , respectively, 17 and thus protonated PZ (HPZ + ) is able to accept one more proton to give doubly protonated PZ (H 2 PZ 2+ ). The protons are released during the carbamate formation reaction; e.g., PZ reacts with CO 2 to give PZcarbamate (PZC − ), accompanied by a proton release to a base. The mono-protonated PZ (HPZ + ) still has a reactive site which can ...

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Insights into the interaction between typical amines and alkaline minerals for improved CO₂ absorption and mineralization

Liu

et al. 2022

Greenhouse Gases

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Amine scrubbing is a mature technology to cut down CO2 emissions from human activities but suffers from a high energy consumption of solvent regeneration. The integrated CO2 absorption and mineralization (IAM) process can effectively reduce the energy consumption of amine regeneration by replacing traditional thermal regeneration with chemical regeneration via CO2 mineralization. However, a fundamental understanding of the interaction between typical amines and alkaline minerals was still lacking. In this paper, the effects of amine types on amine regeneration, alkaline metal leaching, and CaCO3 precipitation during the IAM process were explored by using five typical amines and Ca(OH)2/Mg(OH)2. Results showed very different regeneration kinetics and efficiencies were observed in five selected amine solutions, which displayed a decreased performance in the order TEA > MDEA > DEA > AMP > MEA. The regeneration performance was significantly affected by the dissolution of Ca(OH)2/Mg(OH)2 which was inversely proportional to the trend of their pKa values. TEA displayed the largest regeneration efficiency of about 95% by Ca(OH)2 and 83% by Mg(OH)2, which was much larger than other amines reported in the open literature, due to its lower pKa value than other selected amines. More interestingly, the particle size of CaCO3 produced from amine solutions was smaller than that from CaCl2 solution reported in the literature. There was a rough linear relationship between CaCO3 particle size and amine pKa values. TEA induced the formation of nano scaled CaCO3, which might be attributed to the adsorbing of TEA on the CaCO3 crystal and inhibiting the crystal growth. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.

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Protonation constants and thermodynamic properties of amines for post combustion capture of CO2

Cited by 79 publications

References 19 publications

NMR spectroscopy applied to amine–CO2–H2O systems relevant for post-combustion CO2 capture: A review

NMR spectroscopy applied to amine–CO2–H2O systems relevant for post-combustion CO2 capture: A review

Isolation and Crystal Structure Determination of Piperazine Dicarbamate Obtained from a Direct Reaction between Piperazine and Carbon Dioxide in Methanol

Insights into the interaction between typical amines and alkaline minerals for improved CO₂ absorption and mineralization

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Protonation constants and thermodynamic properties of amines for post combustion capture of CO2

Cited by 79 publications

References 19 publications

NMR spectroscopy applied to amine–CO2–H2O systems relevant for post-combustion CO2 capture: A review

NMR spectroscopy applied to amine–CO2–H2O systems relevant for post-combustion CO2 capture: A review

Isolation and Crystal Structure Determination of Piperazine Dicarbamate Obtained from a Direct Reaction between Piperazine and Carbon Dioxide in Methanol

Insights into the interaction between typical amines and alkaline minerals for improved CO2 absorption and mineralization

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Product

Resources

About

Insights into the interaction between typical amines and alkaline minerals for improved CO₂ absorption and mineralization