Diffusion-based modeling of film growth of hydrates on gas-liquid interfaces

Kar, Aritra; Bhati, Awan; Acharya, Palash V.; Mhadeshwar, Ashish B.; Venkataraman, Pradeep; Barckholtz, Timothy A.; Bahadur, Vaibhav

doi:10.1016/j.ces.2021.116456

Cited by 22 publications

(15 citation statements)

References 40 publications

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“…Silver iodide (AgI) is a strong promoter of ice nucleation; it has been observed that AgI particles nucleate ice at a much lower supercooling on direct contact with water drops (the presence of the air–water–AgI line) compared to the case of AgI particles immersed inside the water droplet. − Shaw et al reported that ice nuclei trigger faster nucleation of ice when placed on the water–air interface rather than being completely immersed. The benefits of three-phase nucleation have also been observed by the present group during nucleation of gas hydrates, − which are ice-like solids of gas and water and form at high pressures and temperatures close to 0 °C.…”

Section: Introductionsupporting

confidence: 59%

Faster Nucleation of Ice at the Three-Phase Contact Line: Influence of Interfacial Chemistry

et al. 2021

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Controlling the nucleation of ice is important in many areas including atmospheric sciences, cryopreservation, food science, and infrastructure protection. Presently, we conduct controlled experiments and analysis to uncover the influence of surface chemistry at the three-phase line on ice nucleation. We show that ice nucleation is faster upon replacing the air at the water−air interface with oils like silicone oil and almond oil. We show via statistically meaningful and carefully designed experiments that ice nucleation occurs at a higher temperature at an aluminum−water−silicone oil (or almond oil) interface as compared to an aluminum−water−air interface. We show that the location of ice nucleation can be controlled (in situations with multiple locations for ice nucleation) by controlling the interfacial chemistry at the three-phase line. We develop a model (which utilizes classical nucleation theory) to study the combined influence of two interfaces on a seed crystal of ice originating at the three-phase contact line. This model can evaluate the thermodynamic competition between nucleation at the three -phase line and heterogeneous nucleation at an interface. The model shows that three-phase contact lines usually result in a higher driving force than heterogeneous nucleation, which speeds up nucleation kinetics. Overall, our experiments and modeling uncover several useful insights into the influence of three-phase lines on nucleation during contact freezing.

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Section: Introductionsupporting

confidence: 59%

Faster Nucleation of Ice at the Three-Phase Contact Line: Influence of Interfacial Chemistry

et al. 2021

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“…Additional key challenges associated with hydrate formation involve slow growth rates and low gas-to-hydrate conversion. We note that the present group recently published a related article on the kinetics of film growth of hydrates …”

Section: Introductionmentioning

confidence: 97%

“…We note that the present group recently published a related article on the kinetics of film growth of hydrates. 11 There have been several advancements to address this wellknown issue of highly stochastic, long induction times. Surfactants, ionic liquids, and proteins are well-known kinetic promoters that accelerate the rate of hydrate nucleation.…”

Section: ■ Introductionmentioning

confidence: 99%

Magnesium-Promoted Rapid Nucleation of Carbon Dioxide Hydrates

Kar

Acharya

Bhati

et al. 2021

ACS Sustainable Chem. Eng.

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Gas hydrates offer solutions in areas like CO 2 sequestration and desalination. However, their formation is severely limited by long induction (wait) times for nucleation, which range from hours to days. Many existing nucleation promotion techniques involve chemical additives, which invite environmental and process-related concerns. Here, we report a simple, passive, and environmentally friendly technique to significantly promote the nucleation of CO 2 hydrates: magnesium (in pure and alloy forms) triggers nucleation almost instantaneously. We report induction times of less than 1 min, which is the fastest induction time reported for any gas hydrate under stagnant conditions. This translates to Mg-promoted nucleation rates being 3000 times higher than the baseline. Statistically meaningful measurements of nucleation kinetics (in milliliter and liter-scale reactors), direct visualization of nucleation, and X-ray photoelectron spectroscopy (XPS)/Fourier-transform infrared spectroscopy (FTIR) analysis uncover several chemistry-related insights associated with Mg-based promotion. Importantly, the three-phase line of magnesium−water−CO 2 gas is key to promotion. Porous oxide layers, generation of H 2 nanobubbles, and chemisorption of CO 2 on Mg surfaces are other factors responsible for accelerated nucleation. Interestingly, Mg alloys exhibit faster nucleation promotion than pure Mg, which is significant in salt water medium. Overall, our work opens up pathways for faster synthesis of hydrates, which is critical to realizing applications.

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“…They postulated that the science of film growth was better represented by a diffusion-limited kinetics rather than heat transfer-limited. This was backed up by the fact that water has a higher thermal effusivity when compared to gas, and hence the heat dissipation could be absorbed promptly by the water . Comprehensive reviews by Yin et al and Partoon et al describe the various available models depending on the controlling mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…This was backed up by the fact that water has a higher thermal effusivity when compared to gas, and hence the heat dissipation could be absorbed promptly by the water. 17 Comprehensive reviews by Yin et al and Partoon et al describe the various available models depending on the controlling mechanism. The various reactor configurations and solution methods adopted were also compiled.…”

Section: Introductionmentioning

confidence: 99%

Modeling Growth Kinetics of Methane Hydrate in Stirred Tank Batch Reactors

et al. 2021

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Hydrate formation could be looked upon as multicomponent and multiphase reaction which is heavily dependent on mass transfer and heat transfer limitations even under favorable thermodynamic conditions. Gas uptake measurement is one of the easiest ways to understand the kinetics of hydrate growth. In a typical gas uptake measurement, one could easily observe three phases of hydrate formation: in phase-I, hydrate forming gas dissolves in the liquid phase which leads to hydrate nucleation; in phase-II, fast hydrate growth is observed; and in phase-III, hydrate grows slowly for relatively longer time periods. In a batch reactor, a slow down in hydrate growth rate as seen in phase-III is either due to a drop in the pressure of the reactor during hydrate growth and/or reduced mass transfer due to hydrate accumulation at the interface. In this work, a model is developed to predict phase-II events. The model proposed is based on an earlier model available in the literature which captured the intrinsic kinetics of gas hydrate growth for a semibatch reactor. Model discussed in the current study works for batch and semibatch reactor, it captures the kinetics for different stirrer speeds, water to gas ratios and different thermodynamic conditions. Experimental validation was done in a batch reactor at 274 K and 6 MPa with methane as the hydrate forming gas. A batch reactor with two different stirrer arrangements, different water-to-gas ratios, and different stirrer speeds were considered, and the mass transfer limitations for both the reactor configurations were studied. Further, a comparison study with the existing model and the modified model (current study) showed that the current model can be extended to other reactor types.

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Diffusion-based modeling of film growth of hydrates on gas-liquid interfaces

Cited by 22 publications

References 40 publications

Faster Nucleation of Ice at the Three-Phase Contact Line: Influence of Interfacial Chemistry

Faster Nucleation of Ice at the Three-Phase Contact Line: Influence of Interfacial Chemistry

Magnesium-Promoted Rapid Nucleation of Carbon Dioxide Hydrates

Modeling Growth Kinetics of Methane Hydrate in Stirred Tank Batch Reactors

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