Andrew Francis Nordquist

Support and cluster effects on synthesis gas conversion with supported ruthenium clusters

Abstract [Ru3(CO)12] and [H4Ru4(CO)12] supported on Al2O3 and MgO exhibited differences in catalytic behavior which can be attributed to the surface organometallic chemistry of the clusters. When supported on Al2O3, [Ru3(CO)12] decomposed to Ru metal on reaction with synthesis gas, and exhibited catalytic behavior that is similar to Ru/Al2O3 prepared by classical methods. On MgO, [Ru3(CO)12] resulted in significant CH3OH production from synthesis gas. After catalysis, the anionic cluster [Ru6C(CO)16]2− was identified on the catalyst, which results from the reaction of [HR3(CO)11]− and [Ru6(CO)18]2−, originally present on the support, with CO + H2. [H4Ru4-(CO)12] supported on Al2O3 and MgO also resulted in significant oxygenate yields from CO + H2. [H3Ru4(CO)12]− was originally present on the surface and reacts with synthesis gas to give [Ru6C(CO)16]2−. The oxygenate selectivity is suggested to be a result of the presence of intact metal clusters on the surface.

N-Vinylformamide – Building Block for Novel Polymer Structures

Abstract N-Vinylformamide (NVF, N-ethenylformamide) is a precursor to amide and amine functional polymers and to other monomers, oligomers, and functional polymers. NVF shows attractive physical and toxicological properties and high reactivity, both in polymerization and in subsequent hydrolysis to cationic and reactive amine functional polymers or oligomers. NVF radical polymerization readily yields water soluble homopolymers with molecular weights from 104 to >106. Copolymerizability is similar to other vinyl amides. Unexpectedly, NVF will also undergo cationic oligomerization. Hydrolysis of polymers and copolymers with base or acid is facile, although reactions with neighboring groups (e.g., with coacrylate ester groups to give lactams) complicate copolymer hydrolysis. Reaction of NVF at the unusually acidic NH group allows reaction with isocyanates to give vinylacylureas or Michael addition to acrylates to give a family of new N-vinylformamidopropionate esters. These esters in turn react with function...

The ejector-driven monolith loop reactor — experiments and modeling

Abstract A novel catalytic gas–liquid reactor configuration, consisting of a monolithic reactor with a liquid-motive ejector as gas–liquid distributor is introduced as a retrofit or alternative to an agitated slurry reactor. The ejector distributes gas and liquid to the channels of a monolith reactor at velocities greater than those attainable with gravity-driven flow, intensifying mass transfer and reaction in a compact reactor. Pressure drops measured using this configuration do not conform to models from the literature. A strong effect of liquid coalescence properties was observed. Until fully predictive pressure drop and gas–liquid distribution models become available, successful scale-up will depend on pressure-drop data measured with industrial process conditions and fluids. Current literature models for mass transfer underpredict laboratory autoclave reaction results, indicating a need for further model development, and in the interim requiring pilot-scale testing for scale-up purposes.