The development of chemically compatible microsystems that can operate across expanded process conditions, such as high pressures (HP) and high temperatures (HT), is of great interest for many applications, including high pressure chemistry and hydrothermal and supercritical fluid processes. We present a methodology for the successful design and use of HP/HT microsystems. Key parameters for the fabrication of microreactors and modular fluidic packaging able to withstand severe pressure and temperature conditions (30 MPa, 400 °C) are described. Applications of these HP/HT plug and play microsystems are illustrated with examples, including multiphase flow visualization through the transition of liquid-liquid immiscible hexane-water segmented flow to homogeneous supercritical flow, on chip supercritical water oxidation, and synthesis of iron oxide nanoparticles.

The development and operation of the synthesis and workup steps of a fully integrated, continuous manufacturing plant for synthesizing aliskiren, a small molecule pharmaceutical, are presented. The plant started with advanced intermediates, two synthetic steps away from the final active pharmaceutical ingredient, and ended with finished tablets. The entire process was run on several occasions, with the data presented herein corresponding to a 240 h run at a nominal throughput of 41 g h–1 of aliskiren. The first reaction was performed solvent-free in a molten condition at a high temperature, achieving high yields (90%) and avoiding solid handling and a long residence time (due to higher concentrations compared to dilute conditions when run at lower temperatures in a solvent). The resulting stream was worked-up inline using liquid–liquid extraction with membrane-based separators that were scaled-up from microfluidic designs. The second reaction involved a Boc deprotection, using aqueous HCl that was rapidly quenched with aqueous NaOH using an inline pH measurement to control NaOH addition. The reaction maintained high yields (90–95%) under closed-loop control despite process disturbances.

U(VI) adsorption on aerosol-synthesized hematite particles ranging in size from 12 to 125 nm was studied to explore nanoscale size effects on uranium adsorption. Adsorption on 70 nm aqueous-synthesized particles was also investigated to examine the effect of the synthesis method on reactivity. Equilibrium adsorption was measured over pH 3-11 at two U(VI) loadings. Surface complexation modeling, combined with adjustment of adsorption equilibrium constants to be independent of site density and surface area, provided a quantitative reaction-based framework for evaluating adsorption affinity and capacity. Among the aerosol-synthesized particles, the adsorption affinity decreased as the particle size increased from 12 to 125 nm with similar intermediate affinities for 30 and 50 nm particles. X-ray absorption fine structure spectroscopy measurements suggest that the differences in adsorption affinity and capacity are not the result of substantially different coordination environments of adsorbed U(VI).

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The rates of microbial Fe(III) reduction of three sizes of hematite nanoparticles by Geobacter sulfurreducens were measured under two H2 partial pressures (0.01 and 1 atm) and three pH (7.0, 7.5, and 8.0) conditions. Hematite particles with mean primary particle sizes of 10, 30, and 50 nm were synthesized by a novel aerosol method that allows tight control of the particle size distribution. The mass-normalized reduction rates of the 10 and 30 nm particles were comparable to each other and higher than the rate for the 50 nm particles. However, the surface area-normalized rate was highest for the 30 nm particles. Consistent with a previously published model, the reduction rates are likely to be proportional to the bacteria-hematite contact area and not to the total hematite surface area. Surface area-normalized iron reduction rates were higher than those reported in previous studies, which may be due to the sequestration of Fe(II) through formation of vivianite. Similar initial reduction rates were observed under all pH and H2 conditions studied.