Exergy optimisation for cascaded thermal storage

Cascaded thermal storage, consisting of multiple Phase Change Materials (PCMs) with different melting temperatures, has been proposed to solve the problem of poor heat transfer caused by unavoidable decrease of temperature differences during heat exchange process. This paper conducts a theoretical study of the overall thermal performance for a cascaded thermal storage system. Both heat transfer rate and exergy efficiency are taken into account. The main findings are: the cascaded arrangement of PCMs enhances the heat transfer rate by up to 30%, whilst it does not always improve the exergy efficiency (-15 to +30%). Enhanced heat transfer and reduced exergy efficiency can both be attributed to the larger temperature differences caused by the cascaded arrangement. A new parameter hex (exergy transfer rate) has been proposed to measure the overall thermal performance. It is defined as the product of heat transfer rate and exergy efficiency, representing the transfer rate of the utilisable thermal energy. The simulation results indicate that the cascaded thermal storage has higher overall thermal performance than the single-staged storage despite of higher exergy efficiency loss

Automatic discovery and optimization of chemical processes

This paper presents the first overview of recent developments in techniques and methods that enable closed-loop optimization, also sometimes called ‘self optimization’, as well as discovery in different areas of molecular sciences. The closed-loop experimental platforms offer tremendous new opportunities by significantly increasing productivity, as well as enabling completely new types of experiments to be performed. Such experiments involve three main enabling technology areas: automated experimental systems, analytical instruments connected to automated chemoinformatics software and optimization or decision-making algorithms. We review the most exciting developments concerning robotic experiments, 3D printed lab-ware, experimental systems with multiple analytical instruments and advanced optimization algorithms based on machine learning approaches. A range of different chemical problems is described, which show the breadth of potential applications of this emerging experimental approach.This work was in part funded by EPSRC project “Closed Loop Optimization for Sustainable Chemical Manufacture” [EP/L003309/1].This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.coche.2015.07.00

Interpretation of the vibrational spectra of glassy polymers using coarse-grained simulations

The structure and vibrational density of states (VDOS) of polymer glasses are investigated using numerical simulations based on the classical Kremer-Grest bead-spring model. We focus on the roles of chain length and bending stiffness, the latter being set by imposing three-body angular potentials along chain backbones. Upon increasing the chain length and bending stiffness, structural reorganisation leads to volumetric expansion of the material and build-up of internal stresses. The VDOS has two dominant bands: a low frequency one corresponding to inter- and intra-chain non-bonding interactions and a high frequency one corresponding principally to vibrations of bonded beads that constitute skeletal chain backbones. Upon increasing the steepness of the angular potential, vibrational modes associated with chain bending gradually move from the low-frequency to the high-frequency band. This redistribution of modes is reflected in a reduction of the so-called Boson peak upon increasing chain stiffness. Remarkably, the finer structure and the peaks of the high-frequency band, and their variations with stiffness, can, for short chains, be explained using an analytical solution derived for a model triatomic molecule. For longer chains, the qualitative evolution of the VDOS with chain stiffness is similar, although the distinct peaks observed for short chains become increasingly smoothed-out. Our findings can be used to guide a systematic approach to interpretation of Brillouin and Raman scattering spectra of glassy polymers in future work, with applications in polymer processing diagnostics.Comment: To appear in Macromolecule

Feasibility of the Simultaneous Determination of Monomer Concentrations and Particle Size in Emulsion Polymerization Using in Situ Raman Spectroscopy.

An immersion Raman probe was used in emulsion copolymerization reactions to measure monomer concentrations and particle sizes. Quantitative determination of monomer concentrations is feasible in two-monomer copolymerizations, but only the overall conversion could be measured by Raman spectroscopy in a four-monomer copolymerization. The feasibility of measuring monomer conversion and particle size was established using partial least-squares (PLS) calibration models. A simplified theoretical framework for the measurement of particle sizes based on photon scattering is presented, based on the elastic-sphere-vibration and surface-tension models.The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (EC FP7) Grant Agreement n. [NMP2-SL-2012-280827] and Engineering and Physical Sciences Research Council under grant EP/L003309/1.This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.iecr.5b0275

Hydrodynamic assembly of two-dimensional layered double hydroxide nanostructures.

Formation mechanisms of two-dimensional nanostructures in wet syntheses are poorly understood. Even more enigmatic is the influence of hydrodynamic forces. Here we use liquid flow cell transmission electron microscopy to show that layered double hydroxide, as a model material, may form via the oriented attachment of hexagonal nanoparticles; under hydrodynamic shear, oriented attachment is accelerated. To hydrodynamically manipulate the kinetics of particle growth and oriented attachment, we develop a microreactor with high and tunable shear rates, enabling control over particle size, crystallinity and aspect ratio. This work offers new insights in the formation of two-dimensional materials, provides a scalable yet precise synthesis method, and proposes new avenues for the rational engineering and scalable production of highly anisotropic nanostructures

Carbon neutral manufacturing via on-site CO2 recycling.

The chemical industry needs to significantly decrease carbon dioxide (CO2) emissions in order to meet the 2050 carbon neutrality goal. Utilization of CO2 as a chemical feedstock for bulk products is a promising way to mitigate industrial emissions; however, CO2-based manufacturing is currently not competitive with the established petrochemical methods and its deployment requires creation of a new value chain. Here, we show that an alternative approach, using CO2 conversion as an add-on to existing manufactures, can disrupt the global carbon cycle while minimally perturbing the operation of chemical plants. Proposed closed-loop on-site CO2 recycling processes are economically viable in the current market and have the potential for rapid introduction in the industries. Retrofit-based CO2 recycling can reduce annually between 4 and 10 Gt CO2 by 2050 and contribute to achieving up to 50% of the industrial carbon neutrality goal

Feasibility of Using 2,3,3,3-Tetrafluoropropene (R1234yf) as a Solvent for Solid–Liquid Extraction of Biopharmaceuticals

Tetrafluoropropene (R1234yf) is the most likely replacement for tetrafluoroethane (R134a), a widely used refrigerant, propellant and solvent, characterised by very high global warming potential. In this study solvation properties of R1234yf were studied experimentally and computationally for solubility of artemisinin, a precursor to the important bio-pharmaceutical API, and extraction of artemisinin from biomass. R1234yf was shown to be a poorer solvent than R134a for artemisinin. COSMO-RS calculations of solvation in R1234yf suggest that the decrease in performance is likely to be due to entropic effects. However, R1234yf was effectively used in solid liquid extraction of Artemisia annua. The new solvent has shown an increased selectivity to the target metabolite artemisinin. This should allow for design of more selective separation processes based on the new solvent molecule with a low global warming potential of 4 relative to CO2.This work was funded under iCON feasibility projects scheme of EPSRC “Centre for Continuous Manufacturing (CMAC)”, EP/IO33459/1. We acknowledge past funding from Medicine for Malaria Ventures for HPLC instrument and funding by University of Cambridge for the LCMS system