Designing for sustainability: applications of tunable solvents, switchable solvents, and catalysis to industrial processes
Fadhel, Ali Zuhair
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The focus of this research was to improve the sustainability of various processes by employing tunable solvents, switchable solvents, and catalysis. In Chapter 2, we report applications of tunable solvents to metal and enzyme catalyzed reactions of hydrophobic substrates. Tunable solvents are defined as solvent that change properties rapidly but continuously upon the application of an external physical stimulus and we utilize these solvents to couple homogeneous reactions with heterogeneous separations. We developed organic-aqueous tunable solvents that utilize propane for efficient phase separation at moderate pressures around 1 MPa; for example the water contents in the propane-expanded THF is 3 wt% at 0.8MPa at 30°C. Also, we extended the use of CO2-organic-aqueous tunable solvents to a pharmaceutically-relevant reaction--the hydroformylation of p-methylstyrene. The homogeneous reactions provide fast rates with excellent yields. At 60°C, the reaction reaches completion after 180 minutes with 95% branched aldehyde yield. The CO2-induced heterogeneous separation of the product from the catalyst provides an efficient and simple way to remove 99% of the product, to retain 99.9% of catalyst, and to recycle the Rh-TPPMS catalyst for five consecutive reactions. In chapter 3, we investigated the use of reversible ionic liquids (RevILs) for synthesis of nanoparticles. RevILs are formed by the reversible reaction of compounds with basic nitrogen functionalities (molecular liquid) with CO2 at ambient pressure to form a liquid salt (ionic liquid). We demonstrated that RevILs form microemulsions that can be switched-on by bubbling CO2 and switched-off by heating. These microemulsions solubilize ionic compounds such as chloroauric acid. We utilized these microemulsions as a template for controlled synthesis of gold nanoparticles. With 2-component RevILs, [TMBGH]+[O2COCH3]-/N-propyl-octylsulfonamide/hexane were used to form particles in the size range of 6-20 nm with an average particles size of 11.4±3.3. With 1-component RevILs, (3-aminopropyl)-tripropylsilane was used to prepare semi-spherical gold particles with an average size of about 20nm. The 1-component RevILs systems provide a simpler method to form microemulsions when compared to the 2-componenet RevILs systems since they eliminate the need for alcohols and surfactants. In chapter 4, we developed a catalyst that efficiently decomposes hydrazine to selectively produce ammonia. This enables the use of the chemical propulsion hydrazine for electric propulsion as well. We prepared nickel, copper, cobalt, ruthenium, rhodium, and iridium nanoparticles that were supported on silica and we tested these silica-supported metals for the decomposition of hydrazine. To study the catalytic activity, we designed and constructed a continuous flow reactor. The results show that nano-nickel supported on silica is the most active and selective catalyst with 100% conversion of hydrazine and 94±3% yield of ammonia.