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Solvents play a vital role in chemical processes such as solubilizing reactants, facilitating product/catalyst separation, increasing reaction rates, enhancing solubilities of gaseous reactants (such as O2, CO, H2) and providing heat capacity to manage the heat of reaction. However, solvent use can also cause adverse environmental impacts by increasing the carbon footprint and/or emitting harmful vapors. This chapter highlights such roles of solvents in multiphase catalytic processes such as hydroformylation, carbonylation, hydrogenation and oxidation through industrial examples. It also discusses how the pressure-tunable properties of supercritical fluids (SCFs) and gas-expanded liquids (GXLs) can be harnessed to develop greener chemical technologies through efficient feedstock utilization, process intensification, enhanced process safety and reduced use of volatile organic solvents. Emerging feedstocks, such as plant-based biomass, shale gas and sequestered CO2 offer excellent opportunities for using such tunable solvents.
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