Dependence of the formation kinetics of carbon dioxide hydrate on clay aging for solid carbon dioxide storage.

Clay-based marine sediments have great potential for safe and effective carbon dioxide (CO2) encapsulation by storing enormous amounts of CO2 in solid gas hydrate form. However, the aging of clay with time changes the surface properties of clay and complicates the CO2 hydrate formation behaviors in sediments. Due to the long clay aging period, it is difficult to identify the role of clay aging in the formation of CO2 hydrate in marine sediments. Here, we used ultrasonication and plasma treatment to simulate the breakage and oxidation of clay nanoflakes in aging and investigated the influence of clay aging on CO2 hydrate formation kinetics. We found that the breakage and oxidation of clay nanoflakes would disrupt the siloxane rings and graft hydroxyl on the clay nanoflakes. This decreased the negative charge density of clay nanoflakes and weakened the interfacial interaction of clay nanoflakes with the surrounding water. Therefore, the small clay nanoflakes enriched in hydroxyl would disrupt the surrounding tetrahedral water structure analogous to the CO2 hydrate, resulting in the prolongation of CO2 hydrate nucleation. These results revealed the influence of the structure-function relationship of clay nanoflakes with CO2 hydrate formation and are favorable for the development of hydrate-based CO2 storage.

A novel low-temperature evaporation wastewater treatment apparatus based on hydrate adsorption.

Heavy metal pollution is an urgent challenge worldwide due to the acceleration of industrialization. While adsorption desalination is regarded as an innovative method for wastewater treatment, the current technologies have been impeded by high costs and intensive energy consumption. In this work, a novel low-temperature evaporation wastewater treatment apparatus based on hydrate adsorption was proposed. The water vapor from wastewater evaporation reacted with CO2 to form hydrate under the pressure of 3.3 MPa, constantly promoting wastewater evaporation due to the consumption of water vapor. The effect of feeding concentration on treatment effect was analyzed in terms of removal efficiency, water yield, and enrichment factor. Remarkably, a maximum removal efficiency of 97.4% can be achieved by treating an artificial solution with a Cu2+ concentration of 500 mg/L. Furthermore, compared with the control group that only depended on evaporation and condensation without forming hydrate, the maximum water yield of purified water in the experimental group increased to 310%. This innovative design concept for a low-temperature wastewater treatment apparatus based on hydrate adsorption presents a promising solution for the green and energy-efficient treatment of heavy metal wastewater.

Heat Transport in Clathrate Hydrates Controlled by Guest Frequency and Host-Guest Interaction.

The underlying mechanism of common limited lattice thermal conductivity (κ) in energy-related host-guest crystalline compounds has been an ongoing topic in recent decades. Here, the guest-triggered intrinsic ultralow κ of the representative xenon clathrate hydrate was investigated using the time domain thermoreflectance technique and theoretical calculations. The localized guest modes were observed to hybridize with acoustic branches and severely limit the acoustic κ contribution. Besides, the strong mode coupling enables the reshaping of the overall lattice dynamics, especially for optical branches. More importantly, we identified that guest fillers prompt great phonon scattering in wide frequencies, which originates from both the guest-frequency-controlled enhancement of phase space and the host-guest-interaction-governed lattice anharmonicity. The extremely low guest frequency and strong host-guest interaction and coupling were thereby underlined to play vital but distinct roles in κ minimization. Our results unveil the dominant factors of guest reduction effects and facilitate the design of efficient thermoelectric or other thermal-related materials.

Clay nanoflakes and organic molecules synergistically promoting CO2 hydrate formation.

Carbon dioxide (CO2) reduction is an urgent challenge worldwide due to the dramatically increased CO2 concentration and concomitant environmental problems. Geological CO2 storage in gas hydrate in marine sediment is a promising and attractive way to mitigate CO2 emissions owning to its huge storage capability and safety. However, the sluggish kinetics and unclear enhancing mechanisms of CO2 hydrate formation limit the practical application of hydrate-based CO2 storage technologies. Here, we used vermiculite nanoflakes (VMNs) and methionine (Met) to investigate the synergistic promotion of natural clay surface and organic matter on CO2 hydrate formation kinetics. Induction time and t90 in VMNs dispersion with Met were shorter by one to two orders of magnitude than Met solution and VMNs dispersion. Besides, CO2 hydrate formation kinetics showed significant concentration-dependence on both Met and VMNs. The side chains of Met can promote CO2 hydrate formation by inducing water molecules to form a clathrate-like structure. However, when Met concentration exceeded 3.0 mg/mL, the critical amount of ammonium ions from dissociated Met distorted the ordered structure of water molecules, inhibiting CO2 hydrate formation. Negatively charged VMNs can attenuate this inhibition by adsorbing ammonium ions in VMNs dispersion. This work sheds light on the formation mechanism of CO2 hydrate in the presence of clay and organic matter which are the indispensable constituents of marine sediments, also contributes to the practical application of hydrate-based CO2 storage technologies.

Magnetically Recyclable -SO3--Coated Nanoparticles Promote Gas Storage via Forming Hydrates.

Efficient gas enrichment approaches are of great importance for the storage and transportation of clean energy and the sequestration of carbon dioxide. Of special interest is the regulated gas hydrate-based method; however, its operation requires adequate additives to overcome the low-storage capacity issue. Thus, this method is not economically feasible or environmentally friendly. In this work, a novel recyclable hydrate promoter of copolystyrene-sodium styrenesulfonate@Fe3O4 (PNS) nanoparticles with an integrated core-shell structure was synthesized through emulsion polymerization. This was found to effectively reduce the induction time of methane hydrate formation by one-third compared with the widely used sodium dodecyl sulfate (SDS); the corresponding gas storage capacity was also comparable, up to 155 v/v. In addition, the PNS nanoparticles showed a good performance in foam inhibition upon hydrate decomposition, which frequently occurred with the use of SDS and other surfactant-based promoters. In particular, the new promoters contributed to a more than 30% increase in CO2 storage capacity, coacting with the fine sediments that mimic a marine environment. This provided further possibilities of sequestering CO2 in the form a gas hydrate under the seafloor. The underlying mechanism was proposed to involve anchored surfactants on the surface and tiny channels between the nanoparticles that lead to rapid hydrate nucleation and controlled growth. The results showed that the integrated magnetically recovering nanoparticles developed in this study could improve the efficiency of gas storage by forming gas hydrates; the excellent recycling performance paved the way for solving the economic and environmental problems encountered in additive usage.

Kinetic process of upward gas hydrate growth and water migration on the solid surface.

Gas hydrates have gained great interest in the energy and environmental field as a medium for gas storage and transport, gas separation, and carbon dioxide sequestration. The presence of small doses of surfactants in the aqueous phase has been reported to enhance hydrate formation; however, the underlying mechanisms remain poorly understood. Thus, in situ high-resolution X-ray computed tomography measurements were performed to monitor the upward water migration and the resulting hydrate nucleation and growth. It was found that the presence of hydrate crystals at the gas-liquid-solid contact line triggered the enhanced growth of hydrates on the reactor wall. A time delay was observed between the disappearance of the bulk water reservoir and its transformation into hydrate. The lower interfacial tension between the hydrate surface and the solution facilitated its adsorption onto the reactor wall once a thin film of hydrate nucleated on the solid wall surface. These hydrate layers present on the reactor wall were found to be porous, wherein the porosity decreased with increased subcooling. These fundamental results will be of value in understanding the mechanism of hydrate growth in the presence of surfactants and its potential application in hydrate-based technologies.

Molecular behavior of hybrid gas hydrate nucleation: separation of soluble H2S from mixed gas.

Soluble H2S widely exists in natural gas or oil potentially corroding oil/gas pipelines. Furthermore, it can affect the hydrate formation condition, resulting in pipeline blockage; the nucleation mechanism from mixed gas including H2S is still largely unclear. Molecular dynamics simulations were performed to reveal the effects of different initial mixed H2S/CH4 compositions on the hydrate nucleation and growth process. The geometric details of the nanobubbles and gas composition in the nanobubbles were analyzed; the size of the nanobubbles was found to decrease from 3.4 nm to 1.4 nm. With the increase in the initial H2S proportion, the diameter of the nanobubbles decreased; more guest molecules were dissolved in the water, which improved the initial concentration of guest molecules in the water. A multi-site nucleation process was observed, and separate hydrate clusters could grow independently until the simulation box limited their growth due to high local H2S concentration as a potential nucleation location. When the initial proportion of mixed gas approaches, H2S preferred to occupy and stabilize the incipient cage. Moreover, 512, 4151062, and 51262 cages accounted for approximately 95% of the first hydrate cage. Nucleation rates were shown to increase from 4.62 × 1024 to 9.438 × 1026 nuclei cm-3 s-1. The present high subcooling and H2S concentration provided a high driving force to promote mixed hydrate nucleation and growth. The proportion of cages occupied by H2S increased with increasing initial H2S proportion, but the largest enrichment factor of 1.38 occurred at 10% initial H2S/CH4 mixed gas.

A novel apparatus for measuring gas solubility in aqueous solution under multiphase conditions by isobaric method.

With the increasing energy shortage and global warming, the oil/gas development and CO2 sequestration are moving toward the deep sea, and such a geological environment is conducive to gas hydrate formation. At present, for the gas solubility of a hydrate solution system, only Duan's simulation data are widely accepted, and a systematic experimental study is absent. The conventional measurement instruments for solubility of dissolved gas lack control of hydrate phase change, detailed regulation of temperature and pressure, and liquid-solid separation of sampling analysis. This paper describes the working principle, design, and use of a novel apparatus that can measure gas solubility in the solution system in the presence of hydrate. The application of constant pressure equipment avoids disturbing the phase equilibrium and dissolution equilibrium of the system in the sampling process. The apparatus is attractive for the continuous measurement of gas solubility and the guarantee of high accuracy. In addition, an isobaric method is proposed for gas solubility measurement, which promotes the measurement system to reach the target equilibrium state quickly and obtains highly regular data of gas solubility under environmental conditions. The experimental data obtained by this work are highly consistent with the Duan model, and the relative errors of measurements are within 2%. Gas solubility data from this apparatus will provide theoretical support for estimation of the marine CO2 sequestration capacity and prevention of hydrate blockage in oil/gas transportation.

Organics-Coated Nanoclays Further Promote Hydrate Formation Kinetics.

A deeper understanding of the kinetics of CO2 hydrate formation in the complicated natural environment is required for its enhanced sequestration. Here we found that the organics-coated nanoclays enriched in the natural sediments could contribute to a 92% decline of the induction time of hydrate formation. This can be ascribed to the negative charges carried by the organics and the resulting ordered arrangement of the surrounding water molecules. It was, for the first time, proposed that the abundant functional groups from the coating organics could function as a protecting crust enabling the system more resistant to the acidification potentially upon the CO2 sequestration; besides, the negative charges could help prevent the deposition of the nanoclays via interparticle repulsive forces. These would consequently secure their sustainable promoting effect on hydrate formation. The findings suggest the deposits of gas hydrate a kinetically promising geological setting for the CO2 sequestration via forming hydrates.

Behaviors of CO2 Hydrate Formation in the Presence of Acid-Dissolvable Organic Matters.

Carbon storage in the form of solid hydrate under seafloor has been considered to be promising for greenhouse gas control. Yet, open issues still remain on the role of the organic matters abundant in marine environments in the kinetics of hydrate formation; of particular interest is the involvement of the acid-dissolvable organic matters accompanying the acidification upon CO2 injection. In this work, the CO2 hydrate formation in the presence of the organic matters was in-situ monitored through the low-field nuclear magnetic resonance technique. It was found that the organic matters could kinetically promote the formation of CO2 hydrate; this effect was further enhanced by the sulfur-containing acid-dissolvable organic matters. Water in the large pores was preferentially consumed; the following water conversion facilitated by the organic matters would result in a fragmentation of the large pores into separated small pores isolated by the hydrate clusters. Consequently, a further enhancement of the gas-water contact is suggested as the existence of substantial hydrate patches could act as a mass transfer barrier. Our findings expand our understandings on the kinetics of CO2 hydrate formation in the presence of the organic matters and indicate the stability zone of gas hydrate a kinetically favorable geological setting for CO2 sequestration.

In-situ observation for natural gas hydrate in porous medium: Water performance and formation characteristic.

Extensive efforts have been made regarding gas hydrate sample reconstruction in the laboratory for a better understanding and development of natural gas resources. Magnetic resonance imaging (MRI) is a useful method for directly observing the reconstruction of methane hydrate, yet relevant studies remain limited. In this study, a 9.4-T 400-MHz MRI instrument was employed to investigate CH4 hydrate formation in porous media involving various initial water saturation levels and sand diameters. Pressure histories and MRI signal variations were monitored to discuss the process of CH4 hydrate growth, and the three main formation stages of induction, rapid growth, and slow formation were determined. Furthermore, the liquid water performance in MRI micro-images was analyzed to predict the characteristics of CH4 hydrate formation. The results indicated that CH4 hydrate formed in a spatially and temporally random manner and that pore plugging occurred owing to the residual water encased in grown hydrate. Additionally, phase saturations, water conversion percentages, and formation rates were defined to evaluate the effect of sand diameter and initial water saturation on CH4 hydrate formation. With the reduction in the diameter of quartz glass beads from 400 µm to 100 µm, the average hydrate formation rate increased from 0.0010 min-1 to 0.0034 min-1, respectively. When the initial water saturation decreased to the optimized value (0.22 in this study), the water conversion percentage and hydrate saturation increased.

Analyzing spatially and temporally visualized formation behavior of methane hydrate in unconsolidated porous media.

An understanding of the nucleation and growth mechanism of methane hydrate in porous space is essential for exploitation and application of hydrates, but the mechanism is yet to be clarified. Magnetic resonance imaging (MRI) was employed to visually analyze the spatial and temporal formation behavior of methane hydrate in a porous media. Detailed information about the water distribution, initial nucleation sites, and hydrate growth was obtained, in addition to MRI images. The results demonstrated that the water molecules distributed in the vertical direction preferred the middle slice of a porous medium sample, and the decrease in the number of molecules in the middle slice and on both sides of the slice was similar during hydrate formation. The formation process are quite different in selected horizontal slices, which were contributed to the various distribution of water and gas in pore spaces and the randomness of methane hydrate formation. The extension of these predicted results could have important implications for optimizing the formation processes of gas hydrate in hydrate-based technologies.

Effects of carbon-nitrogen ratio on nitrogen removal in a sequencing batch reactor enhanced with low-intensity ultrasound.

A sequencing batch reactor (SBR) enhanced with low-intensity ultrasound was designed to study the removal of nitrogen under different carbon-nitrogen (C/N) ratios. The results showed that the removal efficiencies of CODCr and nitrogen were inversely proportional to C/N ratios. The CODCr of the effluent in the control reactor (CR) and the low-intensity ultrasound-enhanced reactor (UER) were lower than 40 mg L(-1). With a decrease in C/N ratio, the NH4(+)-N removal load of the CR showed little change, while the NH4(+)-N removal load of UER increased from 21.2 to 56.1mg NH4(+)-N/g mixed liquid suspended solids per day. To further understand effects of low-intensity ultrasound, the denaturing gel gradient electrophoresis (DGGE) analysis showed that the similar coefficients of the community structures in the UER and CR were 86%, 52% and 29% when the C/N ratios were 15:1, 10:1, 5:1, respectively.