This page contains news about my research such as new publications, new project grants, happenings, collaborations, or other topics of significance which I think could be of interest to others.
Ailo Aasen defends his PhD thesis
Ailo Aasen successfully defends his PhD thesis entitled "Bulk and interfacial thermodynamics of mixtures: From aqueous systems to ultracryogenic fluids", Friday 27th of March.
The thesis deals with a variety of topics such as predicting the thermodynamic properties of fluids that exhibit strong quantum effects, such as hydrogen, helium, neon, deuterium and their mixtures. The thesis also discusses nucleation in fluid mixtures (see the following Gemini article for a popular scientific summary) and solid formation in mixtures.
I have had the privilege to be the main supervisor of Ailo, and Dr. Hammer from SINTEF Energy Research has been his co-supervisor. The main opponent at his thesis defence was Prof. Carlos Vega from the Department of Physical Chemistry at the University Complutense of Madrid in Spain, and the second opponent was Dr. Thijs van Westen from Stuttgart University in Germany. The administrator of the committee was Prof. Maria Fernandino from NTNU. Due to the ongoing virus crisis, it was impossible for the opponents to come to Norway. Moreover, since most of us is staying at home, the PhD defense was successfully executed interactively. The committee was very satisfied with the work, and stated that it belonged to the top 5% best theses in the world. I feel very grateful for all the fun that we have had these years, and it's a bit sad that the chapter of Ailos PhD has been completed. Fortunately, Ailo joins me as a colleague in SINTEF Energy Research. A couple of pictures can be found below, with Ailo and Maria, and of the opponents.
New article on thermodynamic perturbation theory
Our paper entitled Choice of reference, influence of non-additivity, and present challenges in thermodynamic perturbation theory for mixtures has just been published in the Journal of Chemical Physics.
In the article, we discuss how thermodynamic perturbation theory should be extended to fluid mixtures, and how different formulations and references will result in different accuracies. All formulations examined in the paper display challenges for Lennard-Jones mixtures with significantly different particle sizes (sigma) or significantly different well depths of their potentials (epsilon). We found that an inaccurate representation of higher order perturbation terms was the reason for this, giving a large overprediction of the pressures in the critical region. This overprediction presently causes problems in the prediction of the thermodynamic properties of fluids such as helium-neon mixtures. We are currently working to improve the theory and overcome these challenges.
The work in the paper has been done in collaboration with Morten Hammer, Ailo Aasen and Åsmund Ervik from SINTEF Energy Research.
The first accurate representation of quantum fluid mixtures
Our paper entitled Equation of state and force fields for Feynman–Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium becomes Editors pick in J. Chem. Phys.
In the paper, we extend the statistical associating fluid theory of quantum corrected Mie potentials (SAFT-VRQ Mie), previously developed for pure fluids, to fluid mixtures. In this model, particles interact via Mie potentials with Feynman–Hibbs quantum corrections of first order (Mie-FH1) or second order (Mie-FH2). This is done using a third-order Barker–Henderson expansion of the Helmholtz energy from a non-additive hard-sphere reference system. We survey existing experimental measurements and ab initio calculations of thermodynamic properties of mixtures of neon, helium, deuterium, and hydrogen and use them to optimize the Mie-FH1 and Mie-FH2 force fields for binary interactions. Simulations employing the optimized force fields are shown to follow the experimental results closely over the entire phase envelopes. SAFT-VRQ Mie reproduces results from simulations employing these force fields, with the exception of near-critical states for mixtures containing helium. This breakdown is explained in terms of the extremely low dispersive energy of helium and the challenges inherent in current implementations of the Barker–Henderson expansion for mixtures. The interaction parameters of two cubic equations of state (Soave–Redlich–Kwong and Peng–Robinson) are also fitted to experiments and used as performance benchmarks. There are large gaps in the ranges and properties that have been experimentally measured for these systems, making the force fields presented especially useful.
The paper is one of the last papers in the PhD thesis of Ailo Aasen , but several people have made significant contributions to the work, such as Morten Hammer at SINTEF Energy Research and Erich A. Müller from Imperial College in London. The figure below shows a comparison to experimental results for the Helium-Neon mixture (crosses) and the first accurate theoretical description of this mixture (bullet points). The perturbation theory for mixtures (solid lines) still needs some more development before it can cope with the challenging aspects of quantum fluid mixtures.
In a paper in Chem. Eng. Sci., we study minimum entropy production in distillation
Our paper entitled Minimum entropy production in a distillation column for air separation described by a continuous non-equilibrium model has been published in Chemical Engineering Science.
In this work, we apply the rate-based model of Taylor and Krishna to describe the separation of air in a low-pressure, packed distillation column. By use of numerical optimization, we identify the temperature profile for heat exchange with the column and its surroundings that minimizes the total entropy production. Optimal operation of the column reduces the entropy production by nearly 50%, and the total heating- and cooling duties by 30% and 50%, respectively. We find that the local entropy production is more uniform for the optimal solution than in the adiabatic column, a property that may be helpful for new designs. Using the equilibrium stage model, the state of minimum entropy production has higher cooling/heating duties than in the rate-based model case. This shows that more sophisticated models can be beneficial for the development of reliable strategies to improve the energy efficiency of distillation columns.
The work was performed mainly by Diego Kingston, a visiting PhD student from the University of Buenos Aires in Argentina and in collaboration with Signe Kjelstrup from NTNU.
In a letter in Phys. Rev. Lett., we address the challenges of binary nucleation
Our letter entitled Curvature corrections remove the inconsistencies of binary classical nucleation theory has been accepted for publication in Phys. Rev. Lett.
In the letter we have studied the condensation process in vapors of supersatured alcohol—water mixtures. The nanoscopic droplets forming in such vapors have highly curved surfaces, making their surface tension very different from that of a macroscopic, planar surface. We developed a method to estimate curvature effects on surface tension, and found that it has a dramatic impact on model predictions for the rate of formation of such droplets. Current models, that do not account for curvature effects, yield rate predictions that deviate many orders of magnitude from experiments, and are moreover marred by physical inconsistencies. A key inconsistency is that classical nucleation theory (CNT) can give a negative number of particles of some of the components in the critical cluster. We show in the letter that incorporating curvature effects removes these inconsistencies and restores near-quantitative agreement with experiments. The figure below shows the characteristic "hump" in the activity plot from CNT for the highly surface active water-propanol mixture, which due to the first nucleation theorem means that one of the components has a negative number of particles in the critical cluster. The figure further shows that curvature corrected nucleation theory removes this peak and restores good agreement with experiments. We also show that this is true for the water-methanol and water-ethanol mixtures.
New article on the heat exchangers of a large-scale hydrogen liquefaction process
Our article entitled Comparing exergy losses and evaluating the potential of catalyst-filled plate-fin and spiral-wound heat exchangers in a large-scale Claude hydrogen liquefaction process has been published in the International Journal of Hydrogen Energy.
In the article, we determine detailed heat exchanger designs by matching intermediate temperatures in a large-scale Claude refrigeration process for liquefaction of hydrogen with a capacity of 125 tons/day. A comparison is made of catalyst filled plate-fin and spiral-wound heat exchangers by use of a flexible and robust modeling framework for multi-stream heat exchangers that incorporates conversion of ortho-to para-hydrogen in the hydrogen feed stream, accurate thermophysical models and a distributed resolution of all streams and wall temperatures. Maps of the local exergy destruction in the heat exchangers are presented, which enable the identification of several avenues to improve their performances. The heat exchanger duties vary between 1 and 31 MW and their second law energy efficiencies vary between 72.3% and 96.6%. Due to geometrical constraints imposed by the heat exchanger manufacturers, it is necessary to employ between one to four parallel plate-fin heat exchanger modules, while it is possible to use single modules in series for the spiral-wound heat exchangers. Due to the lower surface density and heat transfer coefficients in the spiral-wound heat exchangers, their weights are 2–14 times higher than those of the plate-fin heat exchangers. In the first heat exchanger, hydrogen feed gas is cooled from ambient temperature to about 120 K by use of a single mixed refrigerant cycle. Here, most of the exergy destruction occurs when the high-pressure mixed refrigerant enters the single-phase regime. A dual mixed refrigerant or a cascade process holds the potential to remove a large part of this exergy destruction and improve the efficiency. In many of the heat exchangers, uneven local exergy destruction reveals a potential for further optimization of geometrical parameters, in combination with process parameters and constraints. The framework presented makes it possible to compare different sources of exergy destruction on equal terms and enables a qualified specification on the maximum allowed pressure drops in the streams. The mole fraction of para-hydrogen is significantly closer to the equilibrium composition through the entire process for the spiral-wound heat exchangers due to the longer residence time. This reduces the exergy destruction from the conversion of ortho-hydrogen and results in a higher outlet mole fraction of para-hydrogen from the process. We show that because of the higher surface densities of the plate-fin heat exchangers, they are the preferred technology for hydrogen liquefaction, unless a higher conversion to heat exchange ratio is desired. A figure showing the evolution of the para-hydrogen mole fraction through all the heat exchangers can be found below.
The work was done in collaboration with G. Skaugen and D. Berstad, both from SINTEF Energy Research.
Three articles on the most downloaded list in Fluid Phase Equilibria
Three of our recent articles are now on the list of the most downloaded papers in the excellent journal Fluid Phase Equilibria:
We are very happy that our articles are well received by the competent readers of Fluid phase equilibria. This is very motivating and encourages us to continue our research on thermodynamics.
New project granted on moisture migration through porous media
The competence building project “PredictCUI: Prediction of water liquid and vapour migration for mitigating corrosion under insulation” received funding by the Norwegian Research Council. Here, I will in collaboration with Prof. Alex Hansen from NTNU/Porelab, researchers from SINTEF Energy Research and the industry deal with one of the major challenges at the Norwegian Continental Shelf, Corrosion under insulation (CUI). The piping in process plants is frequently insulated. CUI occurs under externally clad or jacketed insulation due to the penetration of water. It constitutes a major challenge for the oil and gas industry. If not mitigated, CUI leads to structural failure with serious consequences, ranging from leakages to explosions. One out of five major oil and gas incidents within the EU since 1984 and 50% of hydrocarbon leaks on the Norwegian Continental Shelf have been caused by CUI. Hence, to mitigate CUI is very important. The figure below shows how water can be adsorbed by a porous insulation material (taken by Åsmund Ervik from SINTEF Energy Research). The typical insulation material resembles the negative image of a porous rock: the porosity is very high (above 90%), and the pore space resides around interwoven fibers. In the project, one of the goals is to develop a predictive model for transport of water vapor and liquid through the highly porous insulation material in order to understand where the moisture migrates and where corrosion could potentially occur. One PhD will be educated on this topic in the group.