Evaluation of the Heat Produced by the Hydrothermal Liquefaction of Wet Food Processing Residues and Model Compounds

Hydrothermal liquefaction has proven itself as a promising pathway to the valorisation of low-value wet food residues. The chemistry is complex and many questions remain about the underlying mechanism of the transformation. Little is known about the heat of reaction, or even the thermal effects, of the hydrothermal liquefaction of real biomass and its constituents. This paper explores different methods to evaluate the heat released during the liquefaction of blackcurrant pomace and brewers’ spent grains. Some model compounds have also been evaluated, such as lignin, cellulose and glutamic acid. Exothermic behaviour was observed for blackcurrant pomace and brewers’ spent grains. Results obtained in a continuous reactor are similar to those obtained in a batch reactor. The heat release has been estimated between 1 MJ/kg and 3 MJ/kg for blackcurrant pomace and brewers’ spent grains, respectively. Liquefaction of cellulose and glucose also exhibit exothermic behaviour, while the transformation of lignin and glutamic acid present a slightly endothermic behaviour.

Effect of Heat of Reaction and Charring Properties on Heat Release Rate during Combustion

The heat release rate (HRR) of fires can be determined from the relationship between the thermal pyrolysis rate of combustibles and the effective heat of combustion. To accurately determine the thermal pyrolysis rate of combustibles, it is important to understand the heat of reaction of combustibles. However, this parameter is difficult to measure for combustibles, such as wood, that produce charring during combustion because they undergo a multi-step pyrolysis reaction. In this study, the ISO 5660-1 standard method was used to perform cone calorimetry experiments to understand how the HRR is affected by the heat of reaction heat and charring properties of combustibles. To this end, the HRR calculated using FDS computational analysis was compared to the measured value from the ISO 5660-1 cone calorimetry experiments. A dehydrated Douglas-fir, an evergreen tree of the pine family, was used as a combustible material. The cone calorimetry experiment and FDS computational analysis results confirmed that increases in the heat of reaction and charring properties were directly correlated with the decrease in the HRR.

Ab initio study of the mechanism of the reaction ClO + O --> Cl + O2

Ab initio investigation on the reaction mechanism of ClO + O --> Cl + O2 reaction has been performed using correlation consistent triple zeta basis set. The geometry and frequency of the reactants, products, minimum energy geometries and transition states are obtained using MP2 method and energetics are obtained at the QCISD(T)//MP2 level of theory. Primarily, a possible reaction mechanism is obtained on the basis on IRC calculations using MP2 level of theory. To obtain true picture of the reaction path, we performed IRC calculations using CASSCF method with a minimal basis set 6-31G**. Some new equilibrium geometries and transition states have been identified at the CASSCF level. Energetics are also obtained at the QCISD(T)//CASSCF method. Possible reaction paths have been discussed, which are new in literature. Heat of reaction is found to be consistent with the experimental data. Bond dissociation energies to various dissociation paths are also reported.

Alcohol Assisted Solution-Combustion Technique for the Synthesis of Phase-Pure BaSnO3 Nanoparticles at 130 °C

Lowering the synthesis temperature to obtain phase pure BaSnO3, which is the host material for high figure-of-merit (FOM) perovskite transparent conductors (TCs), can expand the horizons for its optoelectronic applications, with an obvious reduction in the thermal budget. In this work, we have developed a novel solution combustion technique for the synthesis of BaSnO3 nanoparticles. A peroxo/superoxo precursor to the nanoparticles is first synthesized by co-precipitation of the tin and barium salts via the H2O2 assisted or the `CSMC' route. The phase evolution, under different drying conditions of the wet precursor to crystalline BaSnO3 nanoparticles is then studied. We find that the crystallization temperature of BaSnO3 is significantly reduced by adding an organic solvent such as ethanol or propanol to the precursor; temperatures as low as 130 °C yield phase pure BaSnO3 nanoparticles. We establish that the organic solvent increases the reactive O2 ligand content, which plays a pivotal role in the synthesis. Due to this, an exothermic reaction occurs around 130 °C, thereby providing the heat of reaction for conversion of the precursor to phase-pure BaSnO3. Importantly, this method should also allow for the facile incorporation of dopants, paving the way for synthesis of high FOM TCs at low temperatures. Such low synthesis temperatures enable BaSnO3 to be used in devices having temperature limitations during device processing, such as heterojunction Si solar cells or perovskite-based solar cells in an n-i-p architecture.

Measurement and Thermodynamic Modeling for CO2 Solubility in the N-(2-Hydroxyethyl) Piperazine + Water System

Amine scrubbing is the most important technique for capturing CO2. The cyclic diamine N-(2-Hydroxyethyl)-piperazine (HEPZ), a derivative of piperazine, with good mutual solubility in aqueous solution, a low melting point, and a high boiling point, has the potential to replace PZ as an activator added in the mixed amine system to capture CO2. In this study, the solubility of CO2 in aqueous HEPZ solutions was determined for three HEPZ concentrations and four temperatures. The VLE data for HEPZ-H2O were obtained using a gas–liquid double circulation kettle at pressure 30–100 kPa, and the thermodynamic model for the HEPZ-H2O-CO2 system was built in Aspen Plus based on the electrolytic non-random two-liquid (ENRTL) activity model. The physical parameters for HEPZ and the interaction parameters for ENRTL, along with reaction constants of carbamate reactions, were regressed. Using the thermodynamic model, the CO2 cyclic capacity, speciation with loading, and heat of reaction for the CO2 capture system by the aqueous HEPZ solution are predicted and analyzed.

Continuum Thermodynamics of Constrained Reactive Mixtures

Mixture theory models continua consisting of multiple constituents with independent motions. In constrained mixtures all constituents share the same velocity but they may have different reference configurations. The theory of constrained reactive mixtures was formulated to analyze growth and remodeling in living biological tissues. It can also reproduce and extend classical frameworks of damage mechanics and viscoelasticity under isothermal conditions, when modeling bonds that can break and reform. This study focuses on establishing the thermodynamic foundations of constrained reactive mixtures under more general conditions, for arbitrary reactive processes where temperature varies in time and space. By incorporating general expressions for reaction kinetics, it is shown that the residual dissipation statement of the Clausius-Duhem inequality must include a reactive power density, while the axiom of energy balance must include a reactive heat supply density. Both of these functions are proportional to the molar production rate of a reaction, and they depend on the chemical potentials of the mixture constituents. We present novel formulas for the classical thermodynamic concepts of energy of formation and heat of reaction, making it possible to evaluate the heat supply generated by reactive processes from the knowledge of the specific free energy of mixture constituents as well as the reaction rate. We illustrate these novel concepts with mixtures of ideal gases, and isothermal reactive damage mechanics and viscoelasticity, as well as reactive thermoelasticity. This framework facilitates the analysis of reactive tissue biomechanics and physiological and biomedical engineering processes where temperature variations cannot be neglected.

SealWasteSafe: materials technology, monitoring techniques, and quality assurance for safe sealing structures in underground repositories

Within the project SealWasteSafe, we advance construction materials and monitoring concepts of sealing structures applied for underground disposal of nuclear or toxic waste. As these engineered barriers have high demands concerning integrity, an innovative alkali-activated material (AAM) is improved and tested on various laboratory scales. This AAM has low reaction kinetics related to a preferential slow release of the heat of reaction in comparison to alternative salt concretes based on Portland cement or magnesium oxychloride cements. Hence, crack formation due to thermally induced strain is reduced. After successful laboratory scale analysis (Sturm et al., 2021), the AAM is characterised on a larger scale by manufacturing test specimens (100–300 L). Conventional salt concrete (DBE, 2004) and the newly developed AAM are compared using two specimen geometries, i.e. cylindrical and cuboid. A comprehensive multisensor monitoring scheme is developed to compare the setting process of AAM and salt concrete for these manufactured specimens. The analysed parameters include temperature and humidity of the material, acoustic emissions, and strain variations. Passive sensor systems based on radiofrequency identification technology (RFID) embedded in the concrete, enable wireless access to temperature and humidity measurements and are compared to conventional cabled systems. Additionally, fibre-optic sensors (FOS) are embedded to record strain, but also have potential to record temperature and moisture conditions. Part of this project aims at demonstrating the high reliability of sensors and also their resistance to highly alkaline environments and to water intrusion along cables or at sensor locations. Further technical improvements were implemented so that first results clearly show the scalability of the setting process from previous small-scale AAM experiments and particularly the high potential of the newly developed approaches. Furthermore, ultrasonic methods are used for quality assurance to detect obstacles, potential cracks and delamination. On the one hand, both active and passive ultrasonic measurements complement the results obtained from the multisensor monitoring scheme for the produced specimens. On the other hand, the unique large aperture ultrasonic system (LAUS) provides great depth penetration (up to nearly 10 m) and can thus be applied at in situ sealing structures built as a test site in Morsleben by the Federal Company for Radioactive Waste Disposal (Bundesgesellschaft für Endlagerung, BGE) as shown by Effner et al. (2021). An optimised field lay-out identified from forward modelling studies and advanced imaging techniques applied to the measured data will further improve the obtained results. To characterise the inside of the test engineered barrier and achieve a proof-of-concept, an ultrasonic borehole probe is developed to enable phased arrays that can further improve the detection of potential cracks. Modelling results and first analysis of semispherical specimens confirmed the reliability of the directional response caused by the phased arrays of the newly constructed ultrasonic borehole probe. Overall, the project SealWasteSafe improves the construction material, multisensor monitoring concepts and ultrasonics for quality assurance. This will help to develop safe sealing structures for nuclear waste disposal. The outcomes are particularly valuable for salt as a host rock but partly also transferrable to alternative conditions.

Cold-Start Modeling and On-Line Optimal Control of the Three-Way Catalyst

We present a three-way catalyst (TWC) cold-start model, calibrate the model based on experimental data from multiple operating points, and use the model to generate a Pareto-optimalcold-start controller suitable for implementation in standard engine control unit hardware. The TWC model is an extension of a previously presented physics-based model that predicts carbon monoxide, hydrocarbon, and nitrogen oxides tailpipe emissions. The model axially and radially resolves the temperatures in the monolith using very few state variables, thus allowing for use with control-policy based optimal control methods. In this paper, we extend the model to allow for variable axial discretization lengths, include the heat of reaction from hydrogen gas generated from the combustion engine, and reformulate the model parameters to be expressed in conventional units. We experimentally measured the temperature and emission evolution for cold-starts with ten different engine load points, which was subsequently used to tune the model parameters (e.g. chemical reaction rates, specific heats, and thermal resistances). The simulated cumulative tailpipe emission modeling error was found to be typically − 20% to + 80% of the measured emissions. We have constructed and simulated the performance of a Pareto-optimal controller using this model that balances fuel efficiency and the cumulative emissions of each individual species. A benchmark of the optimal controller with a conventional cold-start strategy shows the potential for reducing the cold-start emissions.

A Numerical Investigation of Electrically-Heated Methane Steam Reforming Over Structured Catalysts

The use of electric energy as an alternative system to provide heat of reaction enables the cut-off of CO2 emissions of several chemical processes. Among these, electrification of steam methane reforming results in a cleaner production method of hydrogen. In this work, we perform for the first time a numerical investigation of a compact steam reforming unit that exploits the electrical heating of the catalyst support. First, for such unit we consider the optimal thermodynamic conditions to perform the power to hydrogen conversion; the process should be run at atmospheric pressure and in a close temperature range. Then, among possible materials currently used for manufacturing structured supports we identify silicon carbide as the best material to run electrified steam reforming at moderate voltages and currents. The temperature and concentration profiles in idealized units are studied to understand the impact of the catalyst geometry on the process performances and open-cell foams, despite lower surface to volume show the best potential. Finally, the impact of heat losses is analyzed by considering different operative conditions and reactor geometries, showing that it is possible to obtain relatively high thermal efficiencies with the proposed methodology.

Heat effects in the reaction of sulfuric acid with ilmenites influenced by initial temperature and acid concentration

The influence of temperature and sulfuric acid concentration on the enthalpy and the rate of heat release during the reaction of Norwegian and Australian ilmenites with sulfuric acid was determined. The experimental results obtained from calorimetric measurements were compared with theoretical calculations based on the oxide composition and the phase composition of the raw material. Experimentally determined heat of reaction for Norwegian ilmenite (900–940 kJ/kg) and Australian ilmenite (800–840 kJ/kg) showed good agreement with theoretical calculations based on the phase composition of the raw material. It was found that the enthalpy of ilmenites decomposition reaction does not depend on the concentration of sulfuric acid in the concentration range from 83% to 93%. It was also demonstrated that the temperature and concentration of sulfuric acid have a significant impact on the thermokinetics of the decomposition process, increasing the value of the average rate of temperature change.