Solvent-mediated modification of thermodynamics and kinetics of monoethanolamine regeneration reaction in amine-stripping carbon capture: computational chemistry study

A major limitation of amine-based post-combustion carbon capture technology is the necessity to regenerate amines at high temperatures, which dramatically increases the operating costs. This paper concludes the effect of solvent choice as a possible route to modify the thermodynamics and kinetics characterizing the involved amine 6 regeneration reactions, and discusses whether these modifications can be economically beneficial. We report experimentally-benchmarked computational chemistry calculations of monoethanolamine (MEA) regeneration reactions employing aqueous and non-aqueous solvents with a wide range of dielectric constants. Unlike previous studies, our improved computational chemistry framework could accurately reproduce the right experimental activation energy of zwitterion formation. From the predicted reactions thermodynamics and kinetics, the use of non-aqueous solvents with small dielectric constants led to reductions in regeneration Gibbs free energies, activation barriers and enthalpy changes. This can reduce energy consumption, and gives an opportunity to run desorption columns at relatively lower temperatures, thus offering the possibility of relying on low-grade waste heat as an energy input

Monte Carlo simulation of ammonia adsorption in high-silica zeolites for refrigeration applications

Climate change and the continual rise in cooling demand means more efficient and environmentally friendly refrigeration technologies are required more than ever. One attractive route to reducing future demand is to improve adsorption refrigeration technologies based on natural refrigerants such as ammonia. The choice of ammonia adsorbent plays an important role in achieving improved refrigeration efficiency and suitable operating conditions. This paper reports a detailed study on the suitability of zeolites as an adsorbent of ammonia in refrigeration applications. Systematic Monte Carlo simulations were conducted to study ammonia adsorption in five high-silica zeolites with a wide range of pores sizes and porosities. Simulations were carried out at temperatures between -50 and 50°C and pressures up to 4.0 bar. It is found that zeolites, in particular the ones with large porosities, could be very good ammonia adsorbents for adsorption refrigeration applications, since their use allows for large refrigeration capacities and tuneable operating conditions with good coefficients of performance (COP)

Secondary nucleation in symmetric binary SALR mixtures

Monte Carlo simulation is used to study secondary nucleation, fissioning, or ‘reproduction’, of giant clusters in a symmetric binary model fluid with competing short-range (SA) and long-range (LR) interactions. Previous work [M. B. Sweatman (2017), Molecular Physics 116, 1945-1952] suggests that a pure SALR fluid can exhibit secondary nucleation if the solute concentration is slowly increased. We show this is also true for a binary symmetric SALR mixture where the cross-interactions can be tuned to generate clusters with three different kinds of structure; i) independent clusters of each component, ii) contact clusters of different components, and iii) mixed clusters. In each case, the overall concentration of each component is identical. This binary model is an initial step towards using SALR fluids to model the intra-cellular space of biological cells that contain a wide range of membraneless organelles and the chemical ‘soup’ at the origin of life

Molecular dynamics investigation of giant clustering in small-molecule solutions: the case of aqueous PEHA

[Image: see text] The importance of the formation of giant clusters in solution, in nature and industry, is increasingly recognized. However, relatively little attention has been paid to the formation of giant clusters in solutions of small, relatively soluble but nonamphiphilic molecules. In this work, we present a general methodology based on molecular dynamics that can be used to investigate such systems. As a case study, we focus on the formation of apparently stable clusters of pentaethylenehexamine (PEHA) in water. These clusters have been used as templates for the construction of bioinspired silica nanoparticles. To better understand clustering in this system, we study the effect of PEHA protonation state (neutral, +1, and +2) and counterion type (chloride or acetate) on PEHA clustering in dilute aqueous solutions (200 and 400 mM) using large-scale classical molecular dynamics. We find that large stable clusters are formed by singly charged PEHA with chloride or acetate as the counterion, although it is not clear for the case with acetate whether bulk phase separation, that might lead to precipitation, would eventually occur. Large clusters also appear to be stable for doubly charged PEHA with acetate, the less soluble counterion. We attribute this behavior to a form of complex coacervation, observed here for relatively small and highly soluble molecules (PEHA + counterion) rather than the large polyions usually found to form such coacervates. We discuss whether this behavior might also be described by an effective SALR (short-range attraction, long-range repulsion) interaction. This work might help future studies of additives for the design of novel bioinspired templated nanomaterials and of giant clustering in small-molecule solutions more generally

The self-referential method for linear rigid bodies : application to hard and Lennard-Jones dumbbells

The self-referential (SR) method incorporating thermodynamic integration (TI) [Sweatman et al., J. Chem. Phys. 128, 064102 (2008)] is extended to treat systems of rigid linear bodies. The method is then applied to obtain the canonical ensemble Helmholtz free energy of the alpha-N2 and plastic face centered cubic phases of systems of hard and Lennard-Jones dumbbells using Monte Carlo simulations. Generally good agreement with reference literature data is obtained, which indicates that the SR-TI method is potentially very general and robust

Molecular dynamics simulations for the prediction of the dielectric spectra of alcohols, glycols, and monoethanolamine

The response of molecular systems to electromagnetic radiation in the microwave region (0.3–300 GHz) has been principally studied experimentally, using broadband dielectric spectroscopy. However, relaxation times corresponding to reorganisation of molecular dipoles due to their interaction with electromagnetic radiation at microwave frequencies are within the scope of modern molecular simulations. In this work, fluctuations of the total dipole moment of a molecular system, obtained through molecular dynamics simulations, are used to determine the dielectric spectra of water, a series of alcohols and glycols, and monoethanolamine. Although the force fields employed in this study have principally been developed to describe thermodynamic properties, most them give fairly good predictions of this dynamical property for these systems. However, the inaccuracy of some models and the long simulation times required for the accurate estimation of the static dielectric constant can sometimes be problematic. We show that the use of the experimental value for the static dielectric constant in the calculations, instead of the one predicted by the different models, yields satisfactory results for the dielectric spectra, and hence the heat absorbed from microwaves, avoiding the need for extraordinarily long simulations or re-calibration of molecular models

Decoding Gobekli Tepe with archaeoastronomy: What does the fox say?

We have interpreted much of the symbolism of Göbekli Tepe in terms of astronomical events. By matching low-relief carvings on some of the pillars at Göbekli Tepe to star asterisms we find compelling evidence that the famous ‘Vulture Stone’ is a date stamp for 10950 BC ± 250 yrs, which corresponds closely to the proposed Younger Dryas event, estimated at 10890 BC. We also find evidence that a key function of Göbekli Tepe was to observe meteor showers and record cometary encounters. Indeed, the people of Göbekli Tepe appear to have had a special interest in the Taurid meteor stream, the same meteor stream that is proposed as responsible for the Younger-Dryas event. Is Göbekli Tepe the ‘smoking gun’ for the Younger-Dryas cometary encounter, and hence for coherent catastrophism