Ab initio calculations and a continuum model have been used to study the mechanism for formation of carbamate from CO2 alkanolamines. The molecules studied are ethanolamine diethanolamine. A brief review is also made published experimental observations relevant reaction mechanism. ab inito results suggest that single-step, third-order most likely. It would seem unlikely zwitterion intermediate with significant lifetime present in system. single-step seems be good agreement data.

To understand which part of the CO2 amine-based system is mostly responsible amine degradation, MEA degradation under real capture conditions compared with two laboratory experiments; a thermal experiment representative stripper (MEA 30 wt%, loaded, α=0.5, 135 °C) and an oxidative absorber α=0.4, sparged air+CO2, 55 °C). Liquid Chromatography-Mass Spectrometry (LC-MS) was used for quantification remaining Gas (GC-MS) identification main compounds. This study suggests that in pilot plant more...

The process of post combustion CO2-capture by chemical absorption relies on large scale use chemicals, typically amines in aqueous solution. In such operations, emissions may occur through the cleaned exhaust gas, as degraded solvent and accidental spills. It is thus important that chemicals used have low or no environmental effects. To check this, standard ecotoxicity biodegradability tests for a marine environment were performed more than 40 amines, including both solvents already...

2-Ethanolamine (MEA) degradation has been studied under varying conditions of relevance to postcombustion CO2 capture. Degradation experiments performed in the laboratory were chosen be representative a capture plant facility. The thermal MEA was investigated closed-batch at 135 °C different loadings. also oxidative without additives or by adding FeSO4/fly ash. These compared with three campaigns pilot plants Tiller (Norway), Esbjerg (Denmark), and Longannet (U.K.). same analytical...

The relative carbamate stability of a series amines used in CO2 absorption processes have been studied with different solvation models and gas-phase energies calculated the B3LYP density functional method. were Monte Carlo free-energy perturbations continuum models. Comparison between experimental nuclear magnetic resonance (NMR) kinetic data shows reasonable agreement. trends apparently cannot be explained, terms any single molecular characteristic.

A method is presented to explicitly represent the first solvation shell in continuum calculations. Initial geometries were generated with classical molecular dynamics simulations. Clusters consisting of solute and 5 solvent molecules fully relaxed quantum mechanical The free energy was calculated from formation cluster, cluster models. has been implemented two models, a Poisson−Boltzmann model IEF-PCM model. Calculations carried out for set 60 ionic species. Implemented gave an unsigned...

13C NMR spectroscopic investigations were performed on aqueous solutions of diethylenetriamine (DETA) and carbon dioxide at 298.0 K. Systems with loadings ranging from 0 to 1.69 studied. Results suggest that carbamate is one the main species formed in system below 1.0. At higher (>1.0), it appears dicarbamate dominating HCO3-/CO32- are also formed. No clear evidence was found any tricarbamate system.

Molecular dynamics simulations have been carried out for ethanolamine as a pure liquid and in aqueous solution at 298 333 K. The force field has parametrized to reproduce intramolecular energies from quantum mechanical calculations experimentally determined properties of the liquid. results are presented conformer distributions, density, enthalpy vaporization, self-diffusion constant, dielectric radial distribution functions. strongly suggest that main (O-C-C-N) dihedral tends stay its...

CO2 capture with alkanolamines has been in use since 1930, where MEA is the most studied absorbent for postcombustion. In order to prevent degradation, it important understand degradation mechanisms, which turn requires knowledge of both stoichiometry and kinetics reactions. The stability products a starting point when exploring possible can be determined from Gibbs free energy net reaction. present work, quantum mechanical calculations continuum solvation models are used calculate reaction...

ADVERTISEMENT RETURN TO ISSUEViewpointNEXTEmissions from Postcombustion CO2 Capture PlantsEirik Falck da Silva and Andy M. Booth*View Author Information SINTEF Materials Chemistry, Trondheim NO-7465, Norway*E-mail: [email protected]Cite this: Environ. Sci. Technol. 2013, 47, 2, 659–660Publication Date (Web):January 3, 2013Publication History Published online3 January 2013Published inissue 15 2013https://pubs.acs.org/doi/10.1021/es305111uhttps://doi.org/10.1021/es305111unewsACS...

ADVERTISEMENT RETURN TO ISSUEPREVCorrespondenceNEXTComment on "Reaction Kinetics of CO2 in Aqueous Ethylenediamine, Ethyl Ethanolamine, and Diethyl Monoethanolamine Solutions the Temperature Range 298−313 K, Using Stopped-Flow Technique"Eirik F. da Silva Hallvard SvendsenView Author Information Department Chemical Engineering, Norwegian University Science Technology, N-7491 Trondheim, Norway Cite this: Ind. Eng. Chem. Res. 2008, 47, 3, 990Publication Date (Web):December 19, 2007Publication...

Qualitative and quantitative 13C NMR studies were performed on 30 wt % aqueous solution of 2-amino-2-methyl-1-propanol (AMP) with different amount CO2 at 25 °C. The results suggested that the main species in this system are: AMP/AMPH+, AMPCO2− HCO3−/CO32−. carbamate was observed low loading stability constant calculated based only experimental concentration from analysis. Based liquid phase speciation NMR, mol fraction basis found to be about 0.47

PCM and SM8T continuum solvation models are used to study the temperature dependency of a set amines in range 273–393 K using density functional theoretical calculations. Gaseous phase calculations done B3LYP M06 functionals at 6-311++G(d,p) basis level. pKa values calculated computationally compared with experimental given region both models. The predict trends very nicely. Accurate 298 however required as input model. absolute not reproduced well by these models, correction term is...

Temperature dependent correlations for enthalpy of deprotonation, carbamate formation, and heat absorption the overall reaction between aqueous MEA MDEA gaseous CO2 are calculated on basis computational chemistry based ln K values input to Gibbs-Helmholtz equation. dependency equilibrium constants deprotonation formation reactions is with SM8T continuum solvation model coupled density functional theoretical calculations at B3LYP/6-311++G(d,p) level theory. Calculated enthalpies individual...

A study on thermal and chemical stability of amines has been performed for eleven chemicals, including ethanolamine (MEA), 2-amino-2-methylpropanol (AMP) diethanolamine (DEA), trying to identify the impact parameters such as amine function, alcohol group steric hindrance. The chemicals were studied 5 weeks at 135 °C, both with without presence CO2 (0.5 mol/mol amine) in contact metal (316 SS) well glass containers. In general, did not make an degree degradation. As degradation CO2, most...

The study of the Explicit Solvation Shell Model (ESS) presented recently [da Silva, E. F.; Svendsen, H. Merz, K. M. J. Phys. Chem. A 2009, 113, 6404.] for calculation solvation free energy ions is extended amino acids. energies and pKa a data set 10 acids calculated using ESS. selected based on their potential to be regarded as solvents postcombustion CO2 capture processes. Calculated results are compared against experimental from PCM, SM8T, DivCon continuum models. Error estimates different...

We report on a detailed study of emissions from pilot-plant for CO2 capture at Maasvlakte (in the Netherlands). Three contributions to were identified and analyzed: Gas phase emission, aerosols (also referred as mist or fog) droplets entrained solvents. For emission campaign found be major contributor overall emissions. Entrainment was very small A Brownian demister unit (BDU) tested an reducing technology. It efficient in aerosol

A computational study has been performed on predicting the pKa values for amines and alkanolamines used in CO2 absorption processes. Gas-phase energies were calculated using common basis sets at Hartree−Fock (HF), MP2, B3LYP levels. Free of solvation continuum models Monte Carlo free-energy perturbations. Results are compared with experimental data. While methods could reproduce trends between similar molecules, they failed to predict overall series involving different numbers amine-group...