The Yen-Mullins model of asphaltenes has enabled the development of the industry's first asphaltene equation of state (EOS) for predicting asphaltene concentration gradients in oil reservoirs, the Flory-Huggins-Zuo (FHZ) EOS. The FHZ EOS is built on the existing the Flory-Huggins regular solution model, which has been widely used in modeling the phase behavior of asphaltene precipitation in the oil and gas industry. For crude oil in reservoirs with a low gas/oil ratio (GOR), the FHZ EOS reduces predominantly to a simple form—the gravity term only—and for mobile heavy oil, the gravity term is simply based on asphaltene clusters. The FHZ EOS has been applied to different crude oil columns from volatile oil to black oil to mobile heavy oil all over the world to address key reservoir issues such as reservoir connectivity/compartmentalization, tar mat formation, nonequilibrium with a late gas charge, and asphaltene destabilization by integrating downhole fluid analysis (DFA) measurements and the Yen-Mullins model of asphaltenes. Asphaltene or heavy-end concentration gradients in crude oils are treated using the FHZ EOS explicitly incorporating the size of resin molecules, asphaltene molecules, asphaltene nanoaggregates, or/and asphaltene clusters. Field case studies proved the value and simplicity of this asphaltene or heavy-end treatment. Heuristics can be developed from results corresponding to the estimation of asphaltene gradients. Perylene-like resins with the size of ∼1 nm are dispersed as molecules in high-GOR light oils (condensates) with high fluorescence intensity and without asphaltenes (0 wt% asphaltene). Heavy asphaltene-like resins with the size of ∼1.5 nm are molecularly dissolved in volatile oil at very low asphaltene content. Asphaltene nanoaggregates with the size of ∼2 nm are dispersed in stable crude oil at a bit higher asphaltene content. Asphaltene clusters are found in mobile heavy oil with the size of ∼5 nm at even higher asphaltene content (typically >8 wt% based on stock-tank oil). All these studies are in accord with the observations in the Yen-Mullins model within the FHZ EOS analysis.
Furthermore, the cubic EOS and FHZ EOS have been extended to a near critical fluid column with GOR changing from 2600 to 5600 scf/STB and API gravity changes from 34 to 41 °API. Data from the real-time third-generation of DFA were used to establish the early time EOS for advanced formation evaluation. The early-time EOS was updated after the laboratory PVT data were available. The results from the early-time EOS based on the new-generation DFA data were in accord with those from the updated one based on the pressure/volume/temperature (PVT) data. The large GOR gradient is well modeled by the cubic EOS assuming a small late gas charge from the crest to the base. The FHZ EOS with 1-nm diameter was employed to predict the fluorescence intensity gradient. This agrees that perylene-like resins with the size of ∼1 nm are dispersed as molecules in high-GOR light oil (rich gas condensate) with high fluorescence intensity and without asphaltenes (0 wt% asphaltene).