Firoz Alam Chowdhury

Ab initio study of CO2 capture mechanisms in aqueous monoethanolamine: reaction pathways for the direct interconversion of carbamate and bicarbonate.

Ab initio molecular orbital calculations combined with the polarizable continuum model (PCM) formalism have been carried out for a comprehensive understanding of the mechanism of carbon dioxide (CO2) absorption by aqueous amine solutions. CO2 is captured by amines to generate carbamates and bicarbonate. We have examined the direct interconversion pathways of these two species (collectively represented by a reversible hydrolysis of carbamate) with the prototypical amine, monoethanolamine (MEA). We evaluate both a concerted and a stepwise mechanism for the neutral hydrolysis of MEA carbamate. Large activation energies (ca. 36 kcal/mol) and lack of increase in catalytic efficiency with the inclusion of additional water molecules are predicted in both the mechanisms. We also examined the mechanism of alkaline hydrolysis of MEA carbamate at high concentrations of amine (high pH). The addition of OH(-) ion to carbamate anion was theoretically not allowed due to the reduction in the nucleophilicity of the former as a result of microsolvation. We propose an alternative pathway for hydrolysis: a proton transfer from protonated MEA to carbamate to generate the carbamic acid that initially undergoes a nucleophilic addition of OH(-) and subsequent low-barrier reactions leading to the formation of bicarbonate and free MEA. On the basis of the calculated activation energies, this pathway would be the most efficient route for the direct interconversion of carbamate and bicarbonate without the intermediacy of the free CO2, while the actual contributions will be dependent on the concentrations of protonated MEA and OH(-) ions.

Computational investigation of carbon dioxide absorption in alkanolamine solutions.

We investigated CO2 absorption in aqueous alkanolamine solutions using density functional theory with dielectric continuum solvation models (SMD/IEF-PCM and COSMO-RS). We varied the alkyl chain length (m = 2, 3, 4) and the alcohol chain length (n = 2, 3, 4) in the alkanolamine structures, H(CH2)mNH(CH2)nOH. Using the SMD/IEF-PCM/B3LYP/6-311++G(d,p) and COSMO-RS/BP/TZVP levels of theory, our calculations predict that the product of CO2 absorption (carbamate or bicarbonate) is strongly affected by the alcohol length but does not differ significantly by varying the alkyl chain length. This prediction was confirmed experimentally by 13C-NMR. The observed sensitivity to the alcohol chain length can be attributed to hydrogen bonding effects. The intramolecular hydrogen bonds of HN · · · HO, NH2+ · · · OH, and NCOO− · · · HO induce ring structure formation in neutral alkanolamines, protonated alkanolamines, and carbamate anions, respectively. The results from our studies demonstrate that intramolecular hydrogen bonds play a key role in CO2 absorption reactions in aqueous alkanolamine solutions.

Experimental study into carbon dioxide solubility and species distribution in aqueous alkanolamine solutions

We investigated the solubility of CO2 in aqueous solutions of alkanolamines at 40C and 120C over CO2 partial pressures ranging from a few kPa to 100 kPa to evaluate the potential for CO2 capture from flue gas. CO2 capacities were compared between monoethanolamine, N-ethyl ethanolamine and N-isopropyl ethanolamine. Speciation analyses were conducted in the alkanolamine solutions at different CO2 loadings by accurate quantitative 13 C nuclear magnetic resonance spectroscopy. N-isopropyl ethanolamine showed a large capacity for CO2 because of the formation of bicarbonate. However, we also found that at a lower CO2 loading a significant amount of carbamate was present in the aqueous N-isopropyl ethanolamine solutions.

Sustainable Aspects of Ultimate Reduction of CO2 in the Steelmaking Process (COURSE50 Project), Part 2: CO2 Capture

COURSE50 (ultimate reduction of CO2 in the steelmaking process through innovative technology for Cool Earth 50) aims to capture, separate, and recover CO2 from blast furnace gas. From a practical realization viewpoint, three points are important. The first is energy consumption to regenerate the absorbent, second is the energy cost of the heat for regeneration, and third is the facility cost. The advantage afforded by the COURSE50 approach in relation to the CO2 capture process is the utilization of unused waste heat from the steel mills. Energy consumption to regenerate the absorbent is determined mainly by three factors: the regeneration reaction determined primarily by the structure of the chemical absorbent, the energy required to heat that volume of absorption liquid, which is affected by the absorption rate of the agent, and the heat loss from the processes. The most influential factor is the energy required for the regeneration reaction. We discovered high-performance absorbents with the advantages of high absorption rates, high cyclic capacities, and low heats of reaction, and we then compared these with monoethanolamine (MEA) and N-methyldiethanolamine (MDEA). The newly discovered absorbents performed well in terms of absorption rates and cyclic capacities. Among these absorbents, some showed lower heats of reaction than MDEA. These results provide a basic guideline for the discovery of potential amine-based absorbents that may lead to the development of new absorbent systems for CO2 capture.

Polymeric membranes composed of polystyrenes tethering amino acids for preferential CO 2 separation over H 2

Various N-tert-butoxycarbonyl (N-Boc) amino acids, such as glycine, valine, and serine, were combined to 4-chloromethylstyrene. The resulted monomers were readily polymerized to give polystyrenes tethering an amino acid by a conventional free radical polymerization technique. After deprotection of the N-Boc group with trifluoroacetic acid, the obtained polystyrene derivatives were soluble in ethanol and spin-coated on a commercial poly(ether sulfone) porous membrane to fabricate a composite membrane for CO2 separation over H2. The CO2 selective layer of synthesized PSt was ca. 200 nm thick, and the composite membranes showed preferential CO2 separation over H2, while parent polystyrene passed through H2 rather than CO2. Especially, the separation factor

Synthesis and selection of hindered new amine absorbents for CO2 capture

\alpha_{{{\text{CO}}_{ 2} /{\text{H}}_{ 2} }}

Prediction of the Basicity of Aqueous Amine Solutions and the Species Distribution in the Amine−H2O−CO2 System Using the COSMO-RS Method

was raised after alkaline treatment to form free primary amine on the terminus of graft chain. Serine tethered polystyrene showed the highest