Organic reactions in supercritical fluids: Continuous, selective and green

Supercritical fluids (SCFs) offer a wide range of opportunities as media for chemical reactions and supercritical CO2, ScCO2, is becoming increasingly important as a benign replacement for more toxic solvents.1 High pressure reactions, however, are more capital intensive than conventional low pressure processes. Therefore, supercritical fluids will only gain widespread acceptance in those areas where the fluids give real chemical advantages as well as environmental benefits. This lecture gives a brief account of the use of flow reactors for continuous reactions in supercritical fluids, particularly those of interest for the manufacture of fine chemicals.

Flexible conversion ratio fast reactors: Overview

Conceptual designs of lead-cooled and liquid salt-cooled fast flexible conversion ratio reactors were developed. The performance achievable by the unity conversion ratio cores of these reactors was compared to an existing supercritical carbon dioxide-cooled (S-CO2) fast reactor design and an uprated version of an existing sodium-cooled fast reactor. All concepts have cores rated at 2400 MWt. The cores of the liquid-cooled reactors are placed in a large-pool-type vessel with dual-free level, which also contains four intermediate heat exchangers (IHXs) coupling a primary coolant to a compact and efficient supercritical CO2 Brayton cycle power conversion system. The S-CO2 reactor is directly coupled to the S-CO2 Brayton cycle power conversion system. Decay heat is removed passively using an enhanced reactor vessel auxiliary cooling system (RVACS) and a passive secondary auxiliary cooling system (PSACS). The selection of the water-cooled versus air-cooled heat sink for the PSACS as well as the analysis of the probability that the PSACS may fail to complete its mission was performed using risk-informed methodology. In addition to these features, all reactors were designed to be self-controllable. Further, the liquid-cooled reactors utilized common passive decay heat removal systems whereas the S-CO2 uses reliable battery powered blowers for post-LOCA decay heat removal to provide flow in well defined regimes and to accommodate inadvertent bypass flows. The multiple design limits and challenges which constrained the execution of the four fast reactor concepts are elaborated. These include principally neutronics and materials challenges. The neutronic challenges are the large positive coolant reactivity feedback, small fuel temperature coefficient, small effective delayed neutron fraction, large reactivity swing and the transition between different conversion ratio cores. The burnup, temperature and fluence constraints on fuels, cladding and vessel materials are elaborated for three categories of material - materials currently available, available on a relatively short time scale and available only with significant development effort. The selected fuels are the metallic U-TRU-Zr (10% Zr) for unity conversion ratio and TRU-Zr (75% Zr) for zero conversion ratio. The principal selected cladding and vessel materials are HT-9 and A533 or A508, respectively, for current availability, T-91 and 9Cr-1Mo steel for relatively short-term availability and oxide dispersion strengthened ferritic steel (ODS) available only with significant development. © 2009 Elsevier B.V. All rights reserved.

Recycle of transuranium elements in light water reactors for reduction of geological storage requirements

This paper presents results of a feasibility study aimed at developing a zero-transuranic-discharge fuel cycle based on the U-Th-TRU ternary cycle. The design objective is to find a fuel composition (mixture of thorium, enriched uranium, and recycled transuranic components) and fuel management strategy resulting in an equilibrium charge-discharge mass flow. In such a fuel cycle scheme, the quantity and isotopic vector of the transuranium (TRU) component is identical at the charge and discharge time points, thus allowing the whole amount of the TRU at the end of the fuel irradiation period to be separated and reloaded into the following cycle. The TRU reprocessing activity losses are the only waste stream that will require permanent geological storage, virtually eliminating the long-term radiological waste of the commercial nuclear fuel cycle. A detailed three-dimensional full pressurized water reactor (PWR) core model was used to analyze the proposed fuel composition and management strategy. The results demonstrate the neutronic feasibility of the fuel cycle with zero-TRU discharge. The amount of TRU and enriched uranium loaded reach equilibrium after about four TRU recycles. The reactivity coefficients were found to be within a range typical for a reference PWR core. The soluble boron worth is reduced by a factor of ∼2 from a typical PWR value. Nevertheless, the results indicate the feasibility of an 18-month fuel cycle design with an acceptable beginning-of-cycle soluble boron concentration even without application of burnable poisons.