Farshid Mostowfi

Measurement of Asphaltenes Using Optical Spectroscopy on a Microfluidic Platform

We present a microfluidic apparatus and method for the measurement of asphaltene content in crude-oil samples. The measurement is based on an optical absorption technique, where it was established that asphaltene coloration correlated linearly with asphaltene weight content. The initial absorbance of the oil is measured, and asphaltenes are removed from the oil by the addition of n-alkane, leading to flocculation and subsequent filtration. The absorbance of the deasphalted oil (maltenes) is then measured, and the initial asphaltene content is revealed by the change in absorbance. The asphaltene optical densities correlated linearly with conventional weight measurement results (e.g., ASTM D6560) for 38 crude-oil samples from around the world. Sample measurement repeatability was shown to be within ±2% over several months. Other aspects influencing performance of the system were evaluated, including plug dispersion, flocculation kinetics, membrane degradation, and channel clogging. The microfluidic approach described here permits asphaltene content measurement in less than 30 min as opposed to days required with traditional gravimetric techniques. This many-fold reduction in measurement time will enable more frequent characterization of crude oil samples.

Pressure drop of slug flow in microchannels with increasing void fraction: experiment and modeling

Pressure drop in a gas-liquid slug flow through a long microchannel of rectangular cross-section was investigated. Pressure measurements in a lengthy (∼0.8 m) microchannel determined the pressure gradient to be constant in a flow where gas bubbles progressively expanded and the flow velocity increased due to a significant pressure drop. Most of the earlier studies of slug flow in microchannels considered systems where the expansion of the gas bubbles was negligible in the channel. In contrast, we investigated systems where the volume of the gas phase increased significantly due to a large pressure drop (up to 1811 kPa) along the channel. This expansion of the gas phase led to a significant increase in the void fraction, causing considerable flow acceleration. The pressure drop in the microchannel was studied for three gas-liquid systems; water-nitrogen, dodecane-nitrogen, and pentadecane-nitrogen. Inside the microchannel, local pressure was measured using a series of embedded membranes acting as pressure sensors. Our investigation of the pressure drop showed a linear trend over a wide range of void fractions and flow conditions in the two-phase flow. The lengths and the velocities of the liquid slugs and the gas bubbles were also studied along the microchannel by employing a video imaging technique. Furthermore, a model describing the gas-liquid slug flow in a long microchannel was developed to calculate the pressure drop under conditions similar to the experiments. An excellent agreement between the developed model and the experimental data was obtained.

Condensation in One-Dimensional Dead-End Nanochannels

Phase change at the nanoscale is at the heart of many biological and geological phenomena. The recent emergence and global implications of unconventional oil and gas production from nanoporous shale further necessitate a higher understanding of phase behavior at these scales. Here, we directly observe condensation and condensate growth of a light hydrocarbon (propane) in discrete sub-100 nm (∼70 nm) channels. Two different condensation mechanisms at this nanoscale are distinguished, continuous growth and discontinuous growth due to liquid bridging ahead of the meniscus, both leading to similar net growth rates. The growth rates agree well with those predicted by a suitably defined thermofluid resistance model. In contrast to phase change at larger scales (∼220 and ∼1000 nm cases), the rate of liquid condensate growth in channels of sub-100 nm size is found to be limited mainly by vapor flow resistance (∼70% of the total resistance here), with interface resistance making up the difference. The condensation-induced vapor flow is in the transitional flow regime (Knudsen flow accounting for up to 13% of total resistance here). Collectively, these results demonstrate that with confinement at sub-100 nm scales, such as is commonly found in porous shale and other applications, condensation conditions deviate from the microscale and larger bulk conditions chiefly due to vapor flow and interface resistances.

Determination of boron in produced water using the carminic acid assay

Using the carminic acid assay, we determined the concentration of boron in oilfield waters. We investigated the effect of high concentrations of salts and dissolved metals on the assay performance. The influence of temperature, development time, reagent concentration, and water volume was studied. Ten produced and flowback water samples of different origins were measured, and the method was successfully validated against ICP-MS measurements. In water-stressed regions, produced water is a potential source of fresh water for irrigation, industrial applications, or consumption. Therefore, boron concentration must be determined and controlled to match the envisaged waste water reuse. Fast, precise, and onsite measurements are needed to minimize errors introduced by sample transportation to laboratories. We found that the optimum conditions for our application were a 5:1 mixing volume ratio (reagent to sample), a 1 g L(-1) carminic acid concentration in 99.99% sulfuric acid, and a 30 min reaction time at ambient temperature (20 °C to 23 °C). Absorption values were best measured at 610 nm and 630 nm and baseline corrected at 865 nm. Under these conditions, the sensitivity of the assay to boron was maximized while its cross-sensitivity to dissolved titanium, iron, barium and zirconium was minimized, alleviating the need for masking agents and extraction methods.

Condensation in Nanoporous Packed Beds

In materials with tiny, nanometer-scale pores, liquid condensation is shifted from the bulk saturation pressure observed at larger scales. This effect is called capillary condensation and can block pores, which has major consequences in hydrocarbon production, as well as in fuel cells, catalysis, and powder adhesion. In this study, high pressure nanofluidic condensation studies are performed using propane and carbon dioxide in a colloidal crystal packed bed. Direct visualization allows the extent of condensation to be observed, as well as inference of the pore geometry from Bragg diffraction. We show experimentally that capillary condensation depends on pore geometry and wettability because these factors determine the shape of the menisci that coalesce when pore filling occurs, contrary to the typical assumption that all pore structures can be modeled as cylindrical and perfectly wetting. We also observe capillary condensation at higher pressures than has been done previously, which is important because many applications involving this phenomenon occur well above atmospheric pressure, and there is little, if any, experimental validation of capillary condensation at such pressures, particularly with direct visualization.

Determination of boron concentration in oilfield water with a microfluidic ion exchange resin instrument.

We developed and validated a microfluidic instrument for interference-free determination of boron in produced water. The instrument uses a boron-specific chelating resin to separate the analyte from its complex matrix. Ten produced water samples were analyzed with the instrument and the results were successfully validated against ICP-MS measurements. Removing interference effects enables precise boron measurement for wastewater even with high total dissolved solid (TDS) levels. 1,4-Piperazinediethanesulfonic acid conditions the resin and maintains the optimum pH for boron adsorption from the sample. Boron is then eluted from the resin using a 10% sulfuric acid solution and its concentration measured with the colorimetric carminic acid assay in 95% sulfuric acid. The use of a microfluidic mixer greatly enhances the sensitivity and kinetics of the carminic acid assay, by factors of 2 and 7.5, respectively, when compared against the same assay performed manually. A maximum sensitivity of 2.5mg(-1)L, a precision of 4.2% over the 0-40.0mgL(-1) measuring range, a 0.3mgL(-1) limit of detection, and a sampling rate of up to four samples per hour were achieved. Automation and microfluidics reduce the operator workload and fluid manipulation errors, translating into safer and higher-quality measurements in the field.

Microfluidic technique for measuring wax appearance temperature of reservoir fluids

A microfluidic technique for measuring wax appearance temperature (WAT) of reservoir fluids is presented. The technique is based on continuous monitoring of pressure across a microchannel as wax particles are deposited and gradually clog the channel. A rapid pressure increase was observed as the temperature was systematically decreased to wax appearance temperature. The relationship between pressure change rate and sample temperature is explored as the working principle in the proposed WAT measurement technique. This technique yields results which are comparable to measurements obtained from a cross-polar microscopy technique (CPM); the current industry-standard for WAT measurement. The method is validated by systematically investigating phase transition of pure hydrocarbons, binary mixtures, and real crude oils. The new technique has two distinct advantages over the existing industry standard methods in that its experimental setup is much simpler and it can be adapted to field applications. The microchannel can be easily cleaned and reused to test different samples.

Capillary Condensation in 8 nm Deep Channels

Condensation on the nanoscale is essential to understand many natural and synthetic systems relevant to water, air, and energy. Despite its importance, the underlying physics of condensation initiation and propagation remain largely unknown at sub-10 nm, mainly due to the challenges of controlling and probing such small systems. Here we study the condensation of n-propane down to 8 nm confinement in a nanofluidic system, distinct from previous studies at ∼100 nm. The condensation initiates significantly earlier in the 8 nm channels, and it initiates from the entrance, in contrast to channels just 10 times larger. The condensate propagation is observed to be governed by two liquid-vapor interfaces with an interplay between film and bridging effects. We model the experimental results using classical theories and find good agreement, demonstrating that this 8 nm nonpolar fluid system can be treated as a continuum from a thermodynamic perspective, despite having only 10-20 molecular layers.

Pressure Drop of Accelerating Slug Flow in Microchannels: Modeling and Experiment

An investigation on the pressure drop of a gas-liquid slug flow through a long microchannel of rectangular cross-section is presented. A constant pressure gradient in the microchannel was observed in a flow where gas bubbles progressively expanded and the flow velocity increased due to significant pressure drop. In contrast to majority of the earlier studies of slug flow in microchannels, where void fraction was nearly constant throughout the channel, we investigated systems where the volume of the gas phase increased significantly due to large pressure drop (up to 2000 kPa) along the lengthy (∼1 m) channel. This expansion of the gas phase led to a significant increase in the void fraction, causing considerable increase in flow velocity. Local pressure was measured along the channel using a series of embedded membranes acting as pressure sensors. The axial pressure profile for a gas-liquid system, namely, Dodecane/Nitrogen was studied. Our investigation on pressure gradient showed linear trend over a wide range of void fractions (30–90%) and flow conditions in the two-phase flow. The lengths and the velocities of the liquid slugs and the gas bubbles were also studied along the microchannel by employing video imaging technique. Furthermore, a model describing the gas-liquid slug flow in long microchannels was developed. Excellent agreement between the developed model and the experimental data was obtained.Copyright

Nanoscale Phase Measurement for the Shale Challenge: Multicomponent Fluids in Multiscale Volumes

Hydrocarbon recovery from shale reservoirs provides an increasing share of world energy. These resources are multicomponent fluid mixtures within multiscale geometries, and understanding their associated phase-change thermodynamics presents an array of challenges for experimentalists, theorists, operators, and policy makers. Here, we quantify hydrocarbon mixture phase behavior via direct imaging of connected channels spanning 4 orders of magnitude (10 nm to 10 μm) with supporting density functional theory. The methane/propane mixture dew point shifts, with early condensation of heavy components in nanopores because of a combination of capillarity and competitive surface adsorption. The bubble point in nanoconfinement is found to be deeply suppressed (∼3-fold), to below the bulk dew point of the original mixture, because of the exchange of mixture components with larger connected volumes. The trapping of the heaviest components of hydrocarbon mixtures within the smallest connected pores has implications for shale operations, reserve estimation, and ultimately energy security.