Asphaltenes are known to be interfacially active in many circumstances such as at toluene-water interfaces. Furthermore, the term micelle has been used to describe the primary aggregation of asphaltenes in good solvents such as toluene. Nevertheless, there has been significant uncertainty regarding the critical micelle concentration (CMC) of asphaltenes and even whether the micelle concept is appropriate for asphaltenes. To avoid semantic debates we introduce the terminology critical nanoaggregate concentration (CNAC) for asphaltenes. In this report, we investigate asphaltenes and standard surfactants using high-Q, ultrasonic spectroscopy in both aqueous and organic solvents. As expected, standard surfactants are shown to exhibit a sharp break in sonic velocity versus concentration at known CMCs. To prove our methods, we measured known surfactants with CMCs in the range from 0.010 g/L to 2.3 g/L in agreement with the literature. Using density determinations, we obtain micelle compressibilities consistent with previous literature reports. Asphaltenes are also shown to exhibit behavior similar to that of ultrasonic velocity versus concentration as standard surfactants; asphaltene CNACs in toluene occur at roughly 0.1 g/L, although the exact concentration depends on the specific (crude oil) asphaltene. Furthermore, using asphaltene solution densities, we show that asphaltene nanoaggregate compressibilities are similar to micellar compressibilities obtained with standard nonionic surfactants in toluene. These results strongly support the contention that asphaltenes in toluene can be treated roughly within the micelle framework, although asphaltenes may exhibit small levels of aggregation (dimers, etc.) below their CNAC. Furthermore, our extensive results on known surfactants agree with the literature while the asphaltene CNACs reported here are one to two orders of magnitude lower than most previously published results. (Previous work utilized the terminology "micelle" and "CMC" for asphaltenes.) We believe that the previously reported high concentrations for asphaltene CMCs do not correspond to primary aggregation; perhaps they refer to higher levels of aggregation or perhaps to a particular surface structure.

The goal of predictive science is to establish structure−function relations for a system of interest. The obvious first step is to determine the structure of the system. Predictions in asphaltene science have been greatly inhibited, because of disagreement regarding molecular weight and molecular structure. With substantial progress on both structural fronts, structure−function relationships can be explored. Here, high quality factor (high-Q) ultrasonics is used to demonstrate asphaltene nanoaggregation at ∼100 mg/L. Fluorescence quenching measurements corroborate these results. Simple concepts regarding asphaltene molecular structure can be used to understand asphaltene nanoaggregation. These relations are seen to apply for asphaltene samples of very different origin. The implications of this understanding on larger-scale asphaltene aggregation and solubility are discussed.

Oil shale is a petroleum source rock that has not undergone the natural processes required to convert its organic matter to oil and gas. However, oil shale kerogen can be converted artificially to liquid and gaseous hydrocarbons by pyrolysis. Heating oil shale in place (in situ) has a number of operational, economic, and environmental advantages over surface retorts, particularly when the shale is too deep to mine. This work describes experiments conducted at temperatures and pressures appropriate to commercially viable in situ pyrolysis. The data are needed to construct models to plan, interpret, and optimize field experiments and commercial operations. The experiments also provide insights into the chemical compositions of the native state shale and all the products of pyrolysishydrocarbon and nonhydrocarbon gases, oil, bitumen, remaining pyrolyzable kerogen, residual organic matter, and inorganic matteras functions of thermal maturation. Numerous studies of Green River oil shale pyrolysis have been published over the years. Most of these have focused on the richest interval, the Mahogany (R-7) zone and have been performed in either open (atmospheric pressure) or closed (bomb) apparatus. The new elements of this work are as follows: (1) samples were taken from the deepest of the kerogen-rich layers of the Green River Formation, the mineralogically distinct R-1 zone; (2) experiments were performed under semi-open (controlled pressure) conditions. The data generated are therefore appropriate input to models used in conjunction with in situ controlled-pressure production tests of R-1 shale. In agreement with previous work, this investigation finds that processing shale at relatively low temperatures, for longer times, and at moderately elevated pressures, reduces yields but improves product quality relative to surface retort methods. The composition of the produced oil is generally uniform over the course of artificial maturation. It has a high H/C ratio and is predominantly composed of saturates and light aromatics, which are desirable for refinery operations. The oil has little sulfur, which is mostly in thiophene-containing moieties. Extracted bitumen has a high polar content, and its H/C ratio decreases as a result of oil and gas generation during maturation. Produced gas is rich in natural gas liquids.