International audienceSolar thermal energy represents an increasingly attractive renewable source.However,to provide continuous availability of this energy,it must be stored. This paper presents the state of the art on high temperature(573-1273K)solar thermal energy storage based on chemical reactions,which seems to be the most advantageous one for long-term storage. The paper summarizes the numerical,experimental and technological studies done so far. Each system is described and the advantages and drawbacks of each reaction couple are considered

This paper analyses a thermochemical energy storage process using a CaO/Ca(OH) 2 chemical loop. A single circulating fluidized bed reactor is proposed to carry out the hydration-dehydration alternating reactions. During the energy discharge step, steam is fed to the reactor and used as a fluidizing gas and as a reactant with the CaO coming from a silo, enabling heat to be recovered at a sufficiently high temperature (around 743 K) from the hydration reaction taking place in the fluidized bed. During the dehydration of Ca(OH) 2 (energy charging step), heat (i.e. from a concentrated solar field) is stored in thermochemical form as CaO by using steam as a fluidizing gas. A basic process integration scheme for a reference case with a power output of 100 MW t is analysed in this work, by solving the mass and energy balances during charging and discharging steps and by calculating the volume of the silos and characteristic dimensions of the fluidized bed reactor. The effective energy storage densities of the CaO silo is shown to 2 be over 260 kWh/m 3 with reasonable activities of the solids when storing CaO solids in the silo at around 813 K.

International audienceThe use of heat exchanger/reactors (HEX/reactors) is a promising way to overcome the barrier of poor heat transfer in batch reactors. However to reach residence time long enough to complete the chemistry,low Reynolds number has to be combined with both a plug flow behaviour and the intensification of heat and mass transfers. This work concerns the experimental approach used to characterize an innovative HEX/reactor. The pilot is made of three process plates sandwiched between five utility plates. The process stream flows in a 2 mm corrugated channel. Pressure drop and residence time distribution characterizations aim at studying the flow hydrodynamics. Identified Darcy correlations point out the transition between laminar and turbulent flow around a Reynolds number equal to 200. Moreover the flow behaves like a quasi-plug flow (Pe > 185). The heat transfer and mixing time have also been investigated. The ratio between the reaction kinetics and the mixing time is over 100 and the intensification factor ranges from5000 to 8000 kW m−3K−1. As a consequence, no limitations were identified which allows the implementation of an exothermic reaction. It has been successfully performed under severe temperature and concentration conditions, batchwise unreachable. Thus, it highlights the interest of using this continuous HEX/reactor

OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao.univ-toulouse.fr/ Eprints ID : 15980To link to this article : Michel Ca(OH)2/CaO reversible reaction in a fluidized bed reactor for thermochemical heat storage. AbstractThermal energy storage (TES) is a key factor for increasing the efficiency of concentrated solar power plants. TES using a reversible chemical reaction appears to be a promising technology for high energy density thermal storage (100-500 kW h m À3 ), at high temperature (up to 1000°C) and during a long period (24 h to several months). This paper details an experimental study to carry out the reversible reaction Ca(OH) 2(s) + DH r () CaO (s) + H 2 O (g) in a fluidized bed (FB) reactor. The 4 lm Ca(OH) 2 powder fluidization has been performed with an appropriate proportion of inert easy-to-fluidize particles. Then, Ca(OH) 2 dehydration and CaO hydration have been implemented in a FB reactor and 50 cycles have been reached. The mean energy density obtained is 60 kW h m À3 solid_mixture which amounts to a promising energy density of 156 kW h m À3 Ca(OH) 2 -bulk if the reactants and the easy-to-fluidize particles are separated. The results demonstrated the feasibility of the implementation of the Ca(OH) 2 /CaO thermochemical heat storage in a fluidized bed reactor.

In the global context of process intensification, heat exchanger/reactors are promising apparatuses to implement exothermic chemical syntheses. However, unlike heat exchange processes, the implementation of chemical syntheses requires to control the residence time to complete the chemistry. A way to combine the laminar regime (i.e. enough residence time) with a plug flow and the intensification of both heat and mass transfers is the corrugation of the reaction path. In this work, the experimental setup is based on plate heat exchanger/reactor technology. 7 millichannel corrugated geometries varying the corrugation angle, the curvature radius, the developed length, the hydraulic diameter and the aspect ratio have been designed and experimentally characterized (heat transfer, mixing times, pressure drops, RTD). The objectives were to assess their respective performances to derive some correlations depending on the channel design. The results confirmed the benefits of the reaction channel corrugation. Heat and mass transfers have been intensified while maintaining a plug flow behaviour in the usually laminar flow regime. Moreover, whatever the meandering channel's curvature radius, the results highlighted the relevance of considering the Dean number as the scale-up parameter. This dimensionless number, more than the Reynolds number, seems to govern the flow in the wavy channels.

In recent years, many biocatalytic processes have been developed for the production of chemicals and pharmaceuticals. In this context, enzyme immobilization methods have attracted attention for their advantages, such as continuous production and increased stability. Here, enzyme immobilization methods and a collection of nitrilases from biodiversity for the conversion of 3‐cyanopyridine to nicotinic acid were screened. Substrate conversion over 10 conversion cycles was monitored to optimize the process. The best immobilization conditions were found with cross‐linking using glutaraldehyde to modify the PMMA beads. This method showed good activity over 10 cycles in a batch reactor at 30 and 40°C. Finally, production with a new thermostable nitrilase was examined in a continuous packed bed reactor, showing very high stability of the biocatalytic process at a flow rate of 0.12 ml min–1 and a temperature of 50°C. The complete conversion of 3‐cyanopyridine was obtained over 30 days of operation. Future steps will concern reactor scale‐up to increase the production rate with reasonable pressure drops.

OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao.univ-toulouse.fr/ Eprints ID : 17719 A B S T R A C TWhen viscous fluids are involved, laminar hydraulic conditions and heat and mass transfer intensification are conflicting phenomena. A channel geometry based on Split-And-Recombine (SAR) patterns is experimentally investigated. The principle implements the Baker's transformation and 'chaotic' structures are generated to promote heat and mass transfer. This work assesses the energy efficiency of different heat exchanger/reactors integrating these SAR patterns.The heat transfer capacity is assessed and compared with the energy consumption of each mock-up. It is sensitive to the cooling mode and to the number of SAR patterns per length unit as well.The continuous oxidation of sodium thiosulfate with hydrogen peroxide has been implemented. Conversions up to 99% are reached according to the utility fluid temperature and the residence time.Finally, the whole performances of the SAR geometries are compared to a plate-type heat exchanger/ reactor with a corrugated pattern. The more viscous the fluid, the more the energy efficiency of the SAR design increases compared to the corrugated design because of the balance between advection and diffusion mechanisms. The interest in terms of energy efficiency in working with SAR heat exchanger/ reactor appears from Reynolds numbers below 50.

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