An automated microfluidic system for the investigation of asphaltene deposition and dissolution in porous media.

Asphaltenes, among the most complex components of crude oil, vary in their molecular structure, composition, and self-assembly in porous media. This complexity makes them challenging in laboratory characterization methods. In the present work, a novel microfluidic device was designed to access in situ transient, high-fidelity information on asphaltene deposition and dissolution within porous media. The automated microfluidic device features three independent 4.5 µL packed-bed microreactors on the same chip. The deposition of asphaltenes was investigated at five different temperatures (ranging from 25-65 °C) in addition to dissociation with xylenes. Our findings demonstrate a decrease in the dispersity of asphaltene nanoaggregates in the porous media when the deposition temperature is increased. Furthermore, the direct quantification of the dissociation solvent was made possible by in situ Raman spectroscopy. The average occupancy of xylenes and xylene-free porous media (or unrecognized sites) was estimated to be 0.41 and 0.66, respectively. It was observed that asphaltenes deposited at higher deposition temperatures are more difficult to dissociate by xylenes than those deposited at lower temperatures. In order to develop efficient remediation treatments in energy production operations, the convoluted behaviours of asphaltenes in porous media must be understood on a molecular level. Automated microfluidic systems have the potential to streamline treatment designs, improve their efficiency, and enable the design of green chemistry in conventional energy production operations.

Tetramethylammonium hydroxide as a reagent for complex mixture analysis by negative ion electrospray ionization mass spectrometry.

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) enables the direct characterization of complex mixtures without prior fractionation. High mass resolution can distinguish peaks separated by as little as 1.1 mDa), and high mass accuracy enables assignment of elemental compositions in mixtures that contain tens of thousands of individual components (crude oil). Negative electrospray ionization (ESI) is particularly useful for the speciation of the most acidic petroleum components that are implicated in oil production and processing problems. Here, we replace conventional ammonium hydroxide by tetramethylammonium hydroxide (TMAH, a much stronger base, with higher solubility in toluene) to more uniformly deprotonate acidic components of complex mixtures by negative ESI FTICR MS. The detailed compositional analysis of four crude oils (light to heavy, from different geographical locations) reveals that TMAH reagent accesses 1.5-6 times as many elemental compositions, spanning a much wider range of chemical classes than does NH4OH. For example, TMAH reagent produces abundant negative electrosprayed ions from less acidic and neutral species that are in low abundance or absent with NH4OH reagent. More importantly, the increased compositional coverage of TMAH-modified solvent systems maintains, or even surpasses, the compositional information for the most acidic species. The method is not limited to petroleum-derived materials and could be applied to the analysis of dissolved organic matter, coal, lipids, and other naturally occurring compositionally complex organic mixtures.