Revisiting the flocculation kinetics of destabilized asphaltenes.

A comprehensive review of the recently published work on asphaltene destabilization and flocculation kinetics is presented. Four different experimental techniques were used to study asphaltenes undergoing flocculation process in crude oils and model oils. The asphaltenes were destabilized by different n-alkanes and a geometric population balance with the Smoluchowski collision kernel was used to model the asphaltene aggregation process. Additionally, by postulating a relation between the aggregation collision efficiency and the solubility parameter of asphaltenes and the solution, a unified model of asphaltene aggregation model was developed. When the aggregation model is applied to the experimental data obtained from several different crude oil and model oils, the detection time curves collapsed onto a universal single line, indicating that the model successfully captures the underlying physics of the observed process.

Multiscale scattering investigations of asphaltene cluster breakup, nanoaggregate dissociation, and molecular ordering.

Small-angle X-ray and neutron scattering (SAXS/SANS) by asphaltenes in various solvents (toluene, tetrahydrofuran, and 1-methylnaphthalene) at dilute concentrations of asphaltenes are presented and discussed. As asphaltenes are diluted, it was found that the cluster size decreases and follows a fractal scaling law. This observation reveals that asphaltene clusters persist to dilute concentrations and maintain fractal characteristics, regardless of concentration. For the first time, the fraction of asphaltenes that exist in nanoaggregates compared to those molecularly dispersed was estimated from the scattering intensity. Significant dissociation was detected at concentrations similar to the previously reported critical nanoaggregate concentration (CNAC); however, the dissociation was observed to occur gradually as the asphaltene concentration was lowered. Complete dissociation was not detected, and aggregates persisted down to asphaltene concentrations as low as 15 mg/L (0.00125 vol. %). A simplified thermodynamic aggregation model was applied to the measurements, and the free energy change of association per asphaltene-asphaltene interaction was calculated to be approximately -31 kJ/mol. Finally, novel solvent-corrected WAXS results of asphaltene in a liquid environment are presented and reveal three distinct separation distances, in contrast to the two separation distances observed in diffraction studies of solid phase asphaltenes. Significant differences in the WAXS peak positions and shapes between aromatic and nonaromatic solvents suggests that there may be large differences between the solvation shell or conformation of the asphaltene alkyl shell depending on the surrounding liquid environment.

The fractal aggregation of asphaltenes.

This paper discusses time-resolved small-angle neutron scattering results that were used to investigate asphaltene structure and stability with and without a precipitant added in both crude oil and model oil. A novel approach was used to isolate the scattering from asphaltenes that are insoluble and in the process of aggregating from those that are soluble. It was found that both soluble and insoluble asphaltenes form fractal clusters in crude oil and the fractal dimension of the insoluble asphaltene clusters is higher than that of the soluble clusters. Adding heptane also increases the size of soluble asphaltene clusters without modifying the fractal dimension. Understanding the process of insoluble asphaltenes forming fractals with higher fractal dimensions will potentially reveal the microscopic asphaltene destabilization mechanism (i.e., how a precipitant modifies asphaltene-asphaltene interactions). It was concluded that because of the polydisperse nature of asphaltenes, no well-defined asphaltene phase stability envelope exists and small amounts of asphaltenes precipitated even at dilute precipitant concentrations. Asphaltenes that are stable in a crude oil-precipitant mixture are dispersed on the nanometer length scale. An asphaltene precipitation mechanism is proposed that is consistent with the experimental findings. Additionally, it was found that the heptane-insoluble asphaltene fraction is the dominant source of small-angle scattering in crude oil and the previously unobtainable asphaltene solubility at low heptane concentrations was measured.

Silica precipitation in acidic solutions: mechanism, pH effect, and salt effect.

This study is the first to show that silica precipitation under very acidic conditions ([HCl] = 2-8 M) proceeds through two distinct steps. First, the monomeric form of silica is quickly depleted from solution as it polymerizes to form primary particles approximately 5 nm in diameter. Second, the primary particles formed then flocculate. A modified Smoluchowski equation that incorporates a geometric population balance accurately describes the exponential growth of silica flocs. Variation of the HCl concentration between 2 and 8 M further showed that polymerization to form primary particles and subsequent particle flocculation become exponentially faster with increasing acid concentration. The effect of salt was also studied by adding 1 M chloride salts to the solutions; it was found that salts accelerated both particle formation and growth rates in the order: AlCl(3) > CaCl(2) > MgCl(2) > NaCl > CsCl > no salt. It was also found that ionic strength, over cation identity, determines silica polymerization and particle flocculation rates. This research reveals that precipitation of silica products from acid dissolution of minerals can be studied apart from the mineral dissolution process. Thus, silica product precipitation from mineral acidization follows a two-step process--formation of 5 nm primary particles followed by particle flocculation--which becomes exponentially faster with increasing HCl concentration and with salts accelerating the process in the above order. This result has implications for any study of acid dissolution of aluminosilicate or silicate material. In particular, the findings are applicable to the process of acidizing oil-containing rock formations, a common practice of the petroleum industry where silica dissolution products encounter a low-pH, salty environment within the oil well.

Understanding the dissolution of zeolites.

Scientific knowledge of how zeolites, a unique classification of microporous aluminosilicates, undergo dissolution in aqueous hydrochloric acid solutions is limited. Understanding the dissolution of zeolites is fundamental to a number of processes occurring in nature and throughout industry. To better understand the dissolution process, experiments were carried out establishing that the Si-to-Al ratio controls zeolite framework dissolution, by which the selective removal of aluminum constrains the removal of silicon. Stoichiometric dissolution is observed for Type 4A zeolite in HCl where the Si-to-Al ratio is equal to 1.0. Framework silicon dissolves completely during Type 4A dissolution and is followed by silicate precipitation. However, for the zeolite analcime which has a Si-to-Al ratio of 2.0 dissolves non-stoichiometrically as the selective removal of aluminum results in partially dissolved silicate particles followed by silicate precipitation. In Type Y zeolite, exhibiting a Si-to-Al ratio of 3.0, there is insufficient aluminum to weaken the structure and cause silicon to dissolve in HCl. Thus, little or no precipitation is observed, and amorphous undissolvable silicate particles remain intact. The initial dissolution rates of Type Y and 4A zeolites demonstrate that dissolution is constrained by the number of available reaction sites, and a selective removal rate parameter is applied to delineate the mechanism of particle dissolution by demonstrating the kinetic influence of the Si-to-Al ratio. Zeolite framework models are constructed and used to undergird the basic dissolution mechanism. The framework models, scanning electron micrographs of partially dissolved crystals, and experimentally measured dissolution rates all demonstrate that a zeolite's Si-to-Al framework ratio plays a universal role in the dissolution mechanism, independent of framework type. Consequently, the unique mechanism of zeolite dissolution has general implications on how petroleum reservoir stimulation treatments should be designed.

The unique mechanism of analcime dissolution by hydrogen ion attack.

Acidization is the process of injecting acid into porous oil bearing formations to dissolve minerals in the pore space and is a common technique to increase oil production. Analcime is a zeolite which is one of the minerals found in oil reservoirs in the Gulf of Mexico. This mineral is particularly troublesome during the injection of hydrochloric acid during stimulation of the well reservoir because of the precipitation of silicate and analcime dissolution products. To better understand the dissolution/precipitation process, a fundamental investigation of dissolution of analcime was carried out. Experiments establish that silicate precipitates completely from solution during analcime dissolution in hydrochloric acid and that the precipitation does not influence the dissolution kinetics. Comparison of Si and Al initial dissolution rates demonstrates that Al is selectively removed from the zeolite. The selective removal rate parameter is defined as the ratio of the measured Si dissolution rate to the stoichiometric Si dissolution rate. A new concept is introduced of using the selective removal rate parameter to delineate the mechanism of particle dissolution by demonstrating the influence of the Si-to-Al ratio. The mechanism comprises the removal of Si facilitated by the selective removal of Al, leading to the formation of undissolvable silicate particles. Consequently, the unique mechanism of analcime dissolution has general implications pertaining to how microporous materials dissolve.

A physiologically based model for ethanol and acetaldehyde metabolism in human beings.

Pharmacokinetic models for ethanol metabolism have contributed to the understanding of ethanol clearance in human beings. However, these models fail to account for ethanol's toxic metabolite, acetaldehyde. Acetaldehyde accumulation leads to signs and symptoms, such as cardiac arrhythmias, nausea, anxiety, and facial flushing. Nevertheless, it is difficult to determine the levels of acetaldehyde in the blood or other tissues because of artifactual formation and other technical issues. Therefore, we have constructed a promising physiologically based pharmacokinetic (PBPK) model, which is an excellent match for existing ethanol and acetaldehyde concentration-time data. The model consists of five compartments that exchange material: stomach, gastrointestinal tract, liver, central fluid, and muscle. All compartments except the liver are modeled as stirred reactors. The liver is modeled as a tubular flow reactor. We derived average enzymatic rate laws for alcohol dehydrogenase (ADH) and acetaldehyde dehydrogenase (ALDH), determined kinetic parameters from the literature, and found best-fit parameters by minimizing the squared error between our profiles and the experimental data. The model's transient output correlates strongly with the experimentally observed results for healthy individuals and for those with reduced ALDH activity caused by a genetic deficiency of the primary acetaldehyde-metabolizing enzyme ALDH2. Furthermore, the model shows that the reverse reaction of acetaldehyde back into ethanol is essential and keeps acetaldehyde levels approximately 10-fold lower than if the reaction were irreversible.

Scale inhibition study by turbidity measurement.

The concept of a critical supersaturation ratio (CSSR) has been used to characterize the effectiveness of different types of scale inhibitors, inhibitor concentration, and precipitating solution pH in order to prevent the formation of barium sulfate scale. The scale inhibitors used in this work were aminotrimethylene phosphonic acid (ATMP), diethylenetriaminepentamethylene phosphonic acid (DTPMP), and phosphinopolycarboxylic acid polymer (PPCA). The CSSR at which barium sulfate precipitates was obtained as a function of time for different precipitation conditions and was used as an index to evaluate the effect of the precipitation conditions. The results showed that the CSSRs decrease with increasing elapsed time after mixing the precipitating solutions, but increases with increasing scale inhibitor concentration and solution pH. The CSSR varies linearly with the log of the scale inhibitor concentration and with the precipitating solution pH. A SEM analysis showed that the higher the scale inhibitor concentration and solution pH, the smaller and more spherical the BaSO4 precipitates. Analysis of the particle size distribution revealed that increasing the elapsed time, the scale inhibitor concentration, and precipitating solution pH, all produce a broader particle size distribution and a smaller mean diameter of the BaSO4 precipitates. DTPMP and PPCA were the most effective BaSO4 scale inhibitors per ionizable proton and the most effective on a concentration basis, respectively.

Growth of Leuconostoc mesenteroides NRRL-B523 in an alkaline medium: suboptimal pH growth inhibition of a lactic acid bacterium.

Bacterial profile modification (BPM), a form of tertiary oil recovery, diverts water from the water-flooded high-permeability zone into the oil-bearing low-permeability zone. During field use, exopolymer-producing bacteria plug the high-permeability zone only in the immediate vicinity of the injection point (the near-well bore region). For effective BPM the plug must penetrate far into the formation. Slowing the specific growth rate, lengthening the lag phase, and slowing the polymerization rate are techniques that can prolong the onset of biopolymer gelation and extend the depth of the biological plug. In batch experiments, the growth of Leuconostoc mesenteroides NRRL-B523 was inhibited by the synergistic effects of high substrate loading and an alkaline pH. Exponential growth was delayed up to 190 h. It was observed that cell division was significantly retarded until the medium pH, reduced by the acid byproducts of fermentation, reached a critical value of 6.79 +/- 0.06. A mathematical model was developed to describe the relationship between specific growth rate, lag time, and medium pH.

Characterization of fractionated asphaltenes by UV-vis and NMR self-diffusion spectroscopy.

Asphaltenes have been fractionated by liquid/liquid extraction, yielding four subfractions. The characteristics of fractionated asphaltenes were studied with respect to solubility, aromaticity, heteroatom content, and diffusion behavior. It was observed that asphaltenes from the four subfractions showed variations in their tendency to flocculate and also distinct differences in aromaticity. Furthermore, NMR self-diffusion studies showed that the average diffusion coefficients varied for asphaltenes from the different subfractions. The results suggest a variation in average size and stability between asphaltenes, depending on what subfraction they belong to. The subfraction that consisted of asphaltenes with the largest average size and the highest aromaticity was also found to contain the asphaltenes that had the strongest tendency to flocculate.

Study of Ca-ATMP precipitation in the presence of magnesium ion.

ATMP (aminotri(methylenephosphonic acid)), a phosphonate scale inhibitor used in the petroleum industry, was used as a model scale inhibitor in this study. One of the goals of this work was to determine the range of conditions under which Mg ions, which are formed in reservoir formations containing dolomite, modulate the formation of Ca-ATMP precipitate as a scale inhibitor. The results revealed that the amount of ATMP precipitated decreased with addition of Mg ions in solution at all values of the solution pH. Furthermore, an increase in both the solution pH and the concentration of the divalent cations in solution resulted in a change of the molar ratio of (Ca + Mg) to ATMP in the precipitates. At a low solution pH (pH 1.5), Mg ions had little effect on the composition of the Ca-ATMP precipitate. However, at higher values of the solution pH (pH 4 and 7), the Ca to ATMP molar ratio in the precipitates decreased with increasing concentration of the Mg. Here it was found that Mg ions replaced Ca ions on available reactive sites of ATMP molecules. These results determined the limits of the Mg ion concentration, which affects the precipitation of Ca-ATMP, Mg-ATMP, and (Ca + Mg)-ATMP. The dissolution of the scale inhibitors was studied using a rotating disk reactor. These experiments showed that the total divalent cation molar ratio (Ca + Mg) to ATMP in the precipitates is the primary factor that controls the rate of dissolution (release) of the phosphonate precipitates. The phosphonate precipitate dissolution rates decreased as the molar ratio of divalent cations to ATMP in the precipitates increased.