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Journal articles on the topic 'Methane. Carbon dioxide. Hydrates'

Author: Grafiati

Published: 4 June 2021

Last updated: 16 February 2022

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1

Horvat, Kristine, and Devinder Mahajan. "Carbon dioxide-induced liberation of methane from laboratory-formed methane hydrates." Canadian Journal of Chemistry 93, no. 9 (September 2015): 998–1006. http://dx.doi.org/10.1139/cjc-2014-0562.

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This paper reports a laboratory mimic study that focused on the extraction of methane (CH4) from hydrates coupled with sequestration of carbon dioxide (CO2) as hydrates, by taking advantage of preferential thermodynamic stability of hydrates of CO2 over CH4. Five hydrate formation-decomposition runs focused on CH4–CO2 exchange, two baselines and three with host sediments, were performed in a 200 mL high-pressure Jerguson cell fitted with two glass windows that allowed visualization of the time-resolved hydrate phenomenon. The baseline pure hydrates formed from artificial seawater (75 mL) under 6400–6600 kPa CH4 or 2800–3200 kPa CO2 (hydrate forming regime), when the bath temperature was maintained within 4–6 °C and the gas/liquid volumetric ratio was ∼1.7:1 in the water-excess systems. The data show that the induction time for hydrate appearance was largest at 96 h with CH4, while with CO2 the time shortened by a factor of four. However, when the secondary gas (CO2 or CH4) was injected into the system containing preformed hydrates, the entering gas formed the hydrate phase instantly (within minutes) and no lag was observed. In a system containing host Ottawa sand (104 g) and artificial seawater (38 mL), the induction period reduced to 24 h. In runs with multiple charges, the extent of hydrate formation reached 44% of the theoretical value in the water-excess system, whereas the value maximized at 23% in the gas-excess system. The CO2 hydrate formation in a system that already contained CH4 hydrates was facile and they remained stable, whereas CH4 hydrate formation in a system consisting of CO2 hydrates as hosts were initially stable, but CH4 gas in hydrates quickly exchanged with free CO2 gas to form more stable CO2 hydrates. In all five runs, even though the system was depressurized, left for over a week at room temperature, and flushed with nitrogen gas in between runs, hydrates exhibited the “memory effect”, irrespective of the gas used, a result in contradiction with that reported previously in the literature. The facile CH4–CO2 exchange observed under temperature and pressure conditions that mimic naturally occurring CH4 hydrates show promise to develop a commercial carbon sequestration system.

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2

Klapproth, A., E. Goreshnik, D. Staykova, H. Klein, and W. F. Kuhs. "Structural studies of gas hydrates." Canadian Journal of Physics 81, no. 1-2 (January 1, 2003): 503–18. http://dx.doi.org/10.1139/p03-024.

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An overview of recent structural work focusing on the gas hydrates of methane and carbon dioxide is given. Both the crystal structure and the microstructure are considered. We report on the pressure-dependent molecular structure of methane clathrate hydrate using laboratory-made hydrogenous and deuterated samples investigated by neutron and hard-X-ray synchrotron diffraction experiments. The isothermal compressibilities are determined for hydrogenated and deuterated CH4 hydrate, and isotopic differences between both compounds are established for the first time. The cage filling of carbon dioxide and methane hydrate is determined and compared with predictions from statistical thermodynamic theory. In the case of small cages in methane hydrate, experimental results and predictions do not agree. Field-emission scanning electron microscopy reveals the meso- to macro-porous nature of gas hydrates formed with an excess of free gas. Furthermore, in situ measurements of the formation kinetics of porous hydrates are reported in which differences between methane and carbon dioxide are established quantitatively and the transient existence of a type II carbon dioxide structure is found. PACS Nos.: 82.75-z, 61.10Nz, 61.12Ld, 68.37Hk

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3

Borodin, Stanislav L., and Denis S. Belskikh. "Mathematical modeling of the equilibrium complete replacement of methane by carbon dioxide in a gas hydrate reservoir at negative temperatures." Tyumen State University Herald. Physical and Mathematical Modeling. Oil, Gas, Energy 6, no. 2 (2020): 63–80. http://dx.doi.org/10.21684/2411-7978-2020-6-2-63-80.

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Gas hydrates, which contain the largest amount of methane on our planet, are a promising source of natural gas after the depletion of traditional gas fields, the reserves of which are estimated to last about 50 years. Therefore, it is necessary to study the methods for extracting gas from gas hydrates in order to select the best of them and make reasoned technological and engineering decisions in the future. One of these methods is the replacement of methane in its hydrate with carbon dioxide. This work studies the construction of a mathematical model to observe this method. The following process is considered in this article: on one side of a porous reservoir, initially saturated with methane and its hydrate, carbon dioxide is injected; on the opposite side of this reservoir, methane and/or carbon dioxide are extracted. In this case, both the decomposition of methane hydrate and the formation of carbon dioxide hydrate can occur. This problem is stated in a one-dimensional linear formulation for the case of negative temperatures and gaseous carbon dioxide, which means that methane, carbon dioxide, ice, methane, and carbon dioxide hydrates may be present in the reservoir. A mathematical model is built based on the following: the laws of conservation of masses of methane, carbon dioxide, and ice; Darcy’s law for the gas phase motion; equation of state of real gas; energy equation taking into account thermal conductivity, convection, adiabatic cooling, the Joule — Thomson effect, and the release or absorption of latent heat of hydrate formation. The modelling assumes that phase transitions occur in an equilibrium mode and that methane can be completely replaced by carbon dioxide. The results of numerical experiments are presented.

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Borodin, Stanislav L., and Denis S. Belskikh. "The Current State of Researches Related to the Extraction of Methane from a Porous Medium Containing Hydrate." Tyumen State University Herald. Physical and Mathematical Modeling. Oil, Gas, Energy 4, no. 4 (December 17, 2018): 131–47. http://dx.doi.org/10.21684/2411-7978-2018-4-4-131-147.

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In the next few decades due to a depletion of traditional gas deposits, a question of using alternative sources of natural gas, such as gas hydrates deposits, might arise. Besides, there is a problem of existing greenhouse effect, which is constantly aggravated by increasing carbon dioxide emissions into the atmosphere. At the same time, carbon dioxide can replace methane in gas hydrates and remain in its stable hydrate state in the reservoir. Therefore, available deposits of hydrates are not only potential sources of energy, but also allow a sequestration (“burial”) of carbon dioxide with simultaneous extraction of methane.<br> Several “classical” approaches to extract gas from its hydrate are discussed in the article: depressurization method (pressure reduction), thermal impact (temperature increase), and inhibitors’ use. Laboratory and practical experience of those approaches is reviewed, and their advantages and disadvantages are briefly described. Next, the most promising exchange method for simultaneous sequestration of the greenhouse gas and the production of energy is studied. The paper includes the results of this method’s use in the laboratory and the only practical application currently. The advantage of using a mixture of nitrogen and carbon dioxide for the exchange method was demonstrated, which significantly increases methane extraction degree from its hydrates, which was tested on the first well using this method. Comparing to previous studies reviewing this subject, additional studies related to methane exchange method in hydrates over the last two years were studied.<br> The exchange method is acknowledged the most effective since it ensures a successful extraction of methane from gas hydrate deposits and a “burial” of greenhouse carbon dioxide. In this case, the highest percentage of methane extraction is observed when a mixture of carbon dioxide and nitrogen is injected into the formation. An additional advantage is the exchange can be combined with depressurization and thermal impact. The most promising for research and further application is the combined method for obtaining energy and disposing of the resulting greenhouse carbon dioxide gas. First, a hot mixture of carbon dioxide and nitrogen from combustion of methane on a power plant is pumped into the reservoir through the first well. Then, decomposition/exchange of methane hydrates occurs in the formation. Methane and associated products of its decomposition/exchange are extracted through the second well by depressurization method, and then the methane is cleaned and fed to the power plant for further combustion.

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5

Gambelli, Alberto Maria, Beatrice Castellani, Mirko Filipponi, Andrea Nicolini, and Federico Rossi. "Experimental analysis of the CO2/CH4 Replacement Efficiency due to Sodium Chloride Presence in Natural Gas Hydrates Reservoirs." E3S Web of Conferences 197 (2020): 08008. http://dx.doi.org/10.1051/e3sconf/202019708008.

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Nowadays natural gas hydrates represent a promising opportunity for counteracting several crucial issues of the 21th century. They are a valid answer to the continuously increasing energy demand, moved by the global population growth; moreover, considering their conformation and the possibility of using them for carbon dioxide permanently storage, gas hydrates may become a carbon neutral energy source, where for each methane molecule recovered, another carbon dioxide molecule is entrapped in solid form. Considering that the combustion of one methane molecule for energy production leads to the formation of one CO2 molecule, the hydrates exploitation can be considered a clean process in terms of impact on the climate change. This work shows how the presence of sodium chloride affects the CO2/CH4 replacement process into a gas hydrates reservoir. Replacement experimental results carried out in pure demineralised water were compared with the same values performed in a mixture of water and salt, having a concentration of 37 g/l. Some parameters of interest were discussed, such us methane hydrates formed before the replacement process, total amount of hydrates (composed by both species) reached at the end of the whole process, CO2 moles that formed hydrate, quantity of hydrate present before the replacement process which were actually involved in the CO2/CH4 exchange and carbon dioxide amount which led to the formation of new hydrates structures.

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6

Nago, Annick, and Antonio Nieto. "Natural Gas Production from Methane Hydrate Deposits Using Clathrate Sequestration: State-of-the-Art Review and New Technical Approaches." Journal of Geological Research 2011 (August 28, 2011): 1–6. http://dx.doi.org/10.1155/2011/239397.

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This paper focuses on reviewing the currently available solutions for natural gas production from methane hydrate deposits using CO2 sequestration. Methane hydrates are ice-like materials, which form at low temperature and high pressure and are located in permafrost areas and oceanic environments. They represent a huge hydrocarbon resource, which could supply the entire world for centuries. Fossil-fuel-based energy is still a major source of carbon dioxide emissions which contribute greatly to the issue of global warming and climate change. Geological sequestration of carbon dioxide appears as the safest and most stable way to reduce such emissions for it involves the trapping of CO2 into hydrocarbon reservoirs and aquifers. Indeed, CO2 can also be sequestered as hydrates while helping dissociate the in situ methane hydrates. The studies presented here investigate the molecular exchange between CO2 and CH4 that occurs when methane hydrates are exposed to CO2, thus generating the release of natural gas and the trapping of carbon dioxide as gas clathrate. These projects include laboratory studies on the synthesis, thermodynamics, phase equilibrium, kinetics, cage occupancy, and the methane recovery potential of the mixed CO2–CH4 hydrate. An experimental and numerical evaluation of the effect of porous media on the gas exchange is described. Finally, a few field studies on the potential of this new gas hydrate recovery technique are presented.

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Klymenko, Vasyl, Yuriy Denysov, Oleksandr Skrypnyk, Skrypnyk Kononchuk, and Ruslan Teliuta. "Mining of methane from deposits subaquatic gas hydrates using OTEС." E3S Web of Conferences 230 (2021): 01009. http://dx.doi.org/10.1051/e3sconf/202123001009.

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The article proposes to using Ocean Thermal Energy Conversion (OTEC) to increase the energy efficiency mining of methane from deposits subaquatic gas hydrates on the gas hydrate cycle (GHET), that will allow not to spend 10-15% of the extracted methane for power supply of a gas-producing complex (GPC). The circuit-technological solution GPC is described, according to which carbon dioxide is introduced into the gas hydrate layer to extract methane from gas hydrates. To improve the kinetics of the process of replacement of methane with carbon dioxide in gas hydrates, it is proposed do recirculation part of CO2. The scheme and cycle of gas-hydrate energy-technological installation GHET are given, which operates using OTEC and generates together with electricity for GPC, fresh water and cold. Based on the method proposed in this paper, a comparative thermodynamic analysis of installations using OTEC for Black Sea conditions was performed. by GHET and Anderson cycles and it is shown that the specific useful work obtained in the GHET cycle, approximately 3 times more, and energetic efficiency 1.5 times more.

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8

Janicki, Georg, Stefan Schlüter, Torsten Hennig, Hildegard Lyko, and Görge Deerberg. "Simulation of Methane Recovery from Gas Hydrates Combined with Storing Carbon Dioxide as Hydrates." Journal of Geological Research 2011 (October 18, 2011): 1–15. http://dx.doi.org/10.1155/2011/462156.

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In the medium term, gas hydrate reservoirs in the subsea sediment are intended as deposits for carbon dioxide (CO2) from fossil fuel consumption. This idea is supported by the thermodynamics of CO2 and methane (CH4) hydrates and the fact that CO2 hydrates are more stable than CH4 hydrates in a certain P-T range. The potential of producing methane by depressurization and/or by injecting CO2 is numerically studied in the frame of the SUGAR project. Simulations are performed with the commercial code STARS from CMG and the newly developed code HyReS (hydrate reservoir simulator) especially designed for hydrate processing in the subsea sediment. HyReS is a nonisothermal multiphase Darcy flow model combined with thermodynamics and rate kinetics suitable for gas hydrate calculations. Two scenarios are considered: the depressurization of an area 1,000 m in diameter and a one/two-well scenario with CO2 injection. Realistic rates for injection and production are estimated, and limitations of these processes are discussed.

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9

Khasanov, M. K., and G. R. Rafikova. "Analysis of methane production intensity during its displacement from a gas hydrate formation by carbon dioxide." Multiphase Systems 14, no. 3 (2019): 149–56. http://dx.doi.org/10.21662/mfs2019.3.021.

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The theoretical model is considered in the one-dimensional approximations and numerical solutions are obtained for the process of replacing methane with carbon dioxide from a hydrate in a formation saturated with methane and its hydrate when carbon dioxide is injected into the formation. The process is considered under thermobaric conditions corresponding to the stability region of methane gas and carbon dioxide and the region of existence of CO2 in the form of a gaseous phase. The case is considered when the rate of carbon dioxide hydrate formation is limited by diffusion of carbon dioxide through the formed hydrate layer between the gas mixture stream and methane hydrate. It is accepted that the hydration substitution process occurs without the release of water from the hydrate. To describe the mathematical model, the main equations are the mass conservation equations for methane, carbon dioxide and their hydrates, Darcy’s law for filtration, Fick’s law for diffusive mixing of the gas mixture, state equations for the gas phase, Dalton’s law, energy equation, diffusion equation for transport CO2 through the hydration layer at the pore microchannel scale. The dynamics of the mass flow rates of the outgoing carbon dioxide and methane recovered has been investigated. The influence of the diffusion coefficient, the absolute permeability and the length of the formation on the intensity of the methane produced as a result of the gas substitution process is analyzed. Three main stages of the process were identified: displacement of free methane from the reservoir; extraction of free methane obtained as a result of the beginning of hydrate substitution in the formation; complete conversion of methane hydrate to carbon dioxide hydrate and complete extraction of methane from the formation. It is determined how the two main factors relate to each other in terms of the degree of influence on the replacement rate: heat and mass transfer in the reservoir and the kinetics of the replacement process.

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10

Adisasmito, Sanggono, Robert J. Frank, and E. Dendy Sloan. "Hydrates of carbon dioxide and methane mixtures." Journal of Chemical & Engineering Data 36, no. 1 (January 1991): 68–71. http://dx.doi.org/10.1021/je00001a020.

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11

Kvamme, Bjørn. "Environmentally Friendly Production of Methane from Natural Gas Hydrate Using Carbon Dioxide." Sustainability 11, no. 7 (April 2, 2019): 1964. http://dx.doi.org/10.3390/su11071964.

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Huge amounts of natural gas hydrate are trapped in an ice-like structure (hydrate). Most of these hydrates have been formed from biogenic degradation of organic waste in the upper crust and are almost pure methane hydrates. With up to 14 mol% methane, concentrated inside a water phase, this is an attractive energy source. Unlike conventional hydrocarbons, these hydrates are widely distributed around the world, and might in total amount to more than twice the energy in all known sources of conventional fossil fuels. A variety of methods for producing methane from hydrate-filled sediments have been proposed and developed through laboratory scale experiments, pilot scale experiments, and theoretical considerations. Thermal stimulation (steam, hot water) and pressure reduction has by far been the dominating technology platforms during the latest three decades. Thermal stimulation as the primary method is too expensive. There are many challenges related to pressure reduction as a method. Conditions of pressure can be changed to outside the hydrate stability zone, but dissociation energy still needs to be supplied. Pressure release will set up a temperature gradient and heat can be transferred from the surrounding formation, but it has never been proven that the capacity and transport ability will ever be enough to sustain a commercial production rate. On the contrary, some recent pilot tests have been terminated due to freezing down. Other problems include sand production and water production. A more novel approach of injecting CO2 into natural gas hydrate-filled sediments have also been investigated in various laboratories around the world with varying success. In this work, we focus on some frequent misunderstandings related to this concept. The only feasible mechanism for the use of CO2 goes though the formation of a new CO2 hydrate from free water in the pores and the incoming CO2. As demonstrated in this work, the nucleation of a CO2 hydrate film rapidly forms a mass transport barrier that slows down any further growth of the CO2 hydrate. Addition of small amounts of surfactants can break these hydrate films. We also demonstrate that the free energy of the CO2 hydrate is roughly 2 kJ/mol lower than the free energy of the CH4 hydrate. In addition to heat release from the formation of the new CO2 hydrate, the increase in ion content of the remaining water will dissociate CH4 hydrate before the CO2 hydrate due to the difference in free energy.

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12

Gambelli, Alberto Maria, Beatrice Castellani, Andrea Nicolini, and Federico Rossi. "Water Salinity as Potential Aid for Improving the Carbon Dioxide Replacement Process’ Effectiveness in Natural Gas Hydrate Reservoirs." Processes 8, no. 10 (October 16, 2020): 1298. http://dx.doi.org/10.3390/pr8101298.

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Natural gas hydrates represent a valid opportunity to counteract two of the most serious issues that are affecting humanity this century: climate change and the need for new energy sources, due to the fast and constant increase in the population worldwide. The energy that might be produced with methane contained in hydrates is greater than any amount of energy producible with known conventional energy sources; being widespread in all oceans, they would greatly reduce problems and conflicts associated with the monopoly of energy sources. The possibility of extracting methane and simultaneously performing the permanent storage of carbon dioxide makes hydrate an almost carbon-neutral energy source. The main topic of scientific research is to improve the recovery of technologies and guest species replacement strategies in order to make the use of gas hydrates economically advantageous. In the present paper, an experimental study on how salt can alter the formation process of both methane and carbon dioxide hydrate was carried out. The pressure–temperature conditions existing between the two respective equilibrium curves are directly proportional to the effectiveness of the replacement process and thus its feasibility. Eighteen formation tests were realized at three different salinity values: 0, 30 and 37 g/L. Results show that, as the salinity degree increases, the space between CO2 and CH4 formation curves grows. A further aspect highlighted by the tests is how the carbon dioxide formation process tends to assume a very similar trend in all experiments, while curves obtained during methane tests show a similar trend but with some significant differences. Moreover, this tendency became more pronounced with the increase in the salinity degree.

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13

Khan, Muhammad Saad, Cornelius Borecho Bavoh, Khor Siak Foo, Azmi Mohd Shariff, Zamzila Kassim, Nurzatil Aqmar Bt Othman, Bhajan Lal, Iqbal Ahmed, Mohammad Azizur Rahman, and Sina Rezaei Gomari. "Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates." Molecules 26, no. 2 (January 7, 2021): 275. http://dx.doi.org/10.3390/molecules26020275.

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This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH4 + CO2 hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH4 + CO2 hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.

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14

Khan, Muhammad Saad, Cornelius Borecho Bavoh, Khor Siak Foo, Azmi Mohd Shariff, Zamzila Kassim, Nurzatil Aqmar Bt Othman, Bhajan Lal, Iqbal Ahmed, Mohammad Azizur Rahman, and Sina Rezaei Gomari. "Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates." Molecules 26, no. 2 (January 7, 2021): 275. http://dx.doi.org/10.3390/molecules26020275.

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This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH4 + CO2 hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH4 + CO2 hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.

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15

Ghosh, Jyotirmoy, Rabin Rajan J. Methikkalam, Radha Gobinda Bhuin, Gopi Ragupathy, Nilesh Choudhary, Rajnish Kumar, and Thalappil Pradeep. "Clathrate hydrates in interstellar environment." Proceedings of the National Academy of Sciences 116, no. 5 (January 10, 2019): 1526–31. http://dx.doi.org/10.1073/pnas.1814293116.

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Clathrate hydrates (CHs) are ubiquitous in earth under high-pressure conditions, but their existence in the interstellar medium (ISM) remains unknown. Here, we report experimental observations of the formation of methane and carbon dioxide hydrates in an environment analogous to ISM. Thermal treatment of solid methane and carbon dioxide–water mixture in ultrahigh vacuum of the order of 10−10 mbar for extended periods led to the formation of CHs at 30 and 10 K, respectively. High molecular mobility and H bonding play important roles in the entrapment of gases in the in situ formed 512 CH cages. This finding implies that CHs can exist in extreme low-pressure environments present in the ISM. These hydrates in ISM, subjected to various chemical processes, may act as sources for relevant prebiotic molecules.

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16

Vidal-Vidal, Ángel, Martín Pérez-Rodríguez, Jean-Philippe Torré, and Manuel M. Piñeiro. "DFT calculation of the potential energy landscape topology and Raman spectra of type I CH4and CO2hydrates." Physical Chemistry Chemical Physics 17, no. 10 (2015): 6963–75. http://dx.doi.org/10.1039/c4cp04962d.

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17

Abbasov, Abbas, Sukru Merey, and Mahmut Parlaktuna. "Experimental investigation of carbon dioxide injection effects on methane-propane-carbon dioxide mixture hydrates." Journal of Natural Gas Science and Engineering 34 (August 2016): 1148–58. http://dx.doi.org/10.1016/j.jngse.2016.07.065.

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18

Yu, Shuman, and Shun Uchida. "Geomechanical effects of carbon sequestration as CO2 hydrates and CO2-N2 hydrates on host submarine sediments." E3S Web of Conferences 205 (2020): 11003. http://dx.doi.org/10.1051/e3sconf/202020511003.

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Over the past 10 years, more than 300 trillion kg of carbon dioxide (CO2) have been emitted into the atmosphere, deemed responsible for climate change. The capture and storage of CO2 has been therefore attracting research interests globally. CO2 injection in submarine sediments can provide a way of CO2 sequestration as solid hydrates in sediments by reacting with pore water. However, CO2 hydrate formation may occur relatively fast, resulting decreasing CO2 injectivity. In response, nitrogen (N2) addition has been suggested to prevent potential blockage through slower CO2-N2 hydrate formation process. Although there have been studies to explore this technique in methane hydrate recovery, little attention is paid to CO2 storage efficiency and geomechanical responses of host marine sediments. To better understand carbon sequestration efficiency via hydrate formation and related sediment geomechanical behaviour, this study presents numerical simulations for single well injection of pure CO2 and CO2-N2 mixture into submarine sediments. The results show that CO2-N2 mixture injection improves the efficiency of CO2 storage while maintaining relatively small deformation, which highlights the importance of injectivity and hydrate formation rate for CO2 storage as solid hydrates in submarine sediments.

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Voronov, V. P., E. E. Gorodetskii, A. R. Muratov, and S. S. Safonov. "Experimental studies of methane replacement by carbon dioxide in hydrates." Doklady Earth Sciences 429, no. 1 (November 2009): 1411–13. http://dx.doi.org/10.1134/s1028334x09080388.

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20

Babu, Ponnivalavan, She Hern Bryan Yang, Somik Dasgupta, and Praveen Linga. "Methane Production from Natural Gas Hydrates via Carbon Dioxide Fixation." Energy Procedia 61 (2014): 1776–79. http://dx.doi.org/10.1016/j.egypro.2014.12.210.

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21

Kvamme, Bjørn. "Feasibility of simultaneous CO2 storage and CH4 production from natural gas hydrate using mixtures of CO2 and N2." Canadian Journal of Chemistry 93, no. 8 (August 2015): 897–905. http://dx.doi.org/10.1139/cjc-2014-0501.

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Production of natural gas from hydrate using carbon dioxide allows for a win-win situation in which carbon dioxide can be safely stored in hydrate form while releasing natural gas from in situ hydrate. This concept has been verified experimentally and theoretically in different laboratories worldwide, and lately also in a pilot plant in Alaska. The use of carbon dioxide mixed with nitrogen has the advantage of higher gas permeability. Blocking of flow channels due to formation of new hydrate from injected gas will also be less compared to injection of pure carbon dioxide. The fastest mechanism for conversion involves the formation of a new hydrate from free pore water and the injected gas. As a consequence of the first and second laws of thermodynamics, the most stable hydrate will form first in a dynamic situation, in which carbon dioxide will dominate the first hydrates formed from water and carbon dioxide / nitrogen mixtures. This selective formation process is further enhanced by favorable selective adsorption of carbon dioxide onto mineral surfaces as well as onto liquid water surfaces, which facilitates efficient heterogeneous hydrate nucleation. In this work we examine limitations of hydrate stability as function of gradually decreasing content of carbon dioxide. It is argued that if the flux of gas through the reservoir is high enough to prevent the gas from being depleted for carbon dioxide prior to subsequent supply of new gas, then the combined carbon dioxide storage and natural gas production is still feasible. Otherwise the residual gas dominated by nitrogen will still dissociate the methane hydrate, if the released in situ CH4 from hydrate does not mix in with the gas but escapes through separate flow channels by buoyancy. The ratio of nitrogen to carbon dioxide in such mixtures is therefore a sensitive balance between flow rates and formation rates of new carbon dioxide dominated hydrate. Hydrate instability due to undersaturations of hydrate formers have not been discussed in this work but might add additional instability aspects.

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Sizova, A. A., S. A. Grintsevich, M. A. Kochurin, V. V. Sizov, and E. N. Brodskaya. "Molecular Simulations of CO2/CH4, CO2/N2 and N2/CH4 Binary Mixed Hydrates." Colloid Journal 83, no. 3 (May 2021): 372–78. http://dx.doi.org/10.1134/s1061933x21030145.

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Abstract Grand canonical Monte Carlo simulations were performed to study the occupancy of structure I multicomponent gas hydrates by CO2/CH4, CO2/N2, and N2/CH4 binary gas mixtures with various compositions at a temperature of 270 K and pressures up to 70 atm. The presence of nitrogen in the gas mixture allows for an increase of both the hydrate framework selectivity to CO2 and the amount of carbon dioxide encapsulated in hydrate cages, as compared to the CO2/CH4 hydrate. Despite the selectivity to CH4 molecules demonstrated by N2/CH4 hydrate, nitrogen can compete with methane if the gas mixture contains at least 70% of N2.

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23

Abbasi, A., and F. Mohd Hashim. "Evaluating Pressure in Deepwater Gas Pipeline for the Prediction of Natural Gas Hydrate Formation." Engineering, Technology & Applied Science Research 9, no. 6 (December 1, 2019): 5033–36. http://dx.doi.org/10.48084/etasr.3174.

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This paper proposes the prediction of hydrate formation pressure in deepwater pipeline with an approach of intelligent optimization. The proposed novel correlation of hydrate formation is using the function of ordinary differential equation. The developed optimization prediction model was founded on the constant coefficients which were examined by a multiple set of experimental data of methane (CH4), ethane (C2H6), propane (C3H8), iso-butane (iC4), nitrogen (N), Carbon Dioxide (CO2) and hydrogen sulfide (H2S) hydrates. The consequences of this research are highly optimistic for the natural gas production industry.

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24

Loveday, J., C. Bull, A. Frantzana, C. Wilson, D. Amos, and R. Nelmes. "Gas hydrates at high pressure." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C900. http://dx.doi.org/10.1107/s2053273314090998.

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The behaviour of gas hydrates at high pressure is of wide interest and importance. Gas hydrates are stablised by water-gas repulsive interactions. Information on the effect of changing density on these water-gas interactions provides fundamental insight into the nature of the water potential. Gas hydrates are also widely found in nature and systems like the ammonia-water and methane-water systems form the basis of 'mineralogy' of planetary bodies like Saturn's moon Titan. Finally, gas hydrates offer the possibility of cheap environmentally inert transportation and storage for gases like carbon dioxide and hydrogen. We have been carrying out investigations of a range of gas hydrates at high pressure using neutron and x-ray diffraction as well as other techniques. Results from these studies including; the phase diagram of the ammonia water system, the occupancies of hexgonal clathrate structures, and new structures in the carbon dioxide water system, will be presented.

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25

Nakano, S., K. Yamamoto, and K. Ohgaki. "Natural gas exploitation by carbon dioxide from gas hydrate fields—high-pressure phase equilibrium for an ethane hydrate system." Proceedings of the Institution of Mechanical Engineers, Part A: Journal of Power and Energy 212, no. 3 (May 1, 1998): 159–63. http://dx.doi.org/10.1243/0957650981536826.

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Natural gas hydrate fields, which have a large amount of methane and ethane deposits in the subterranean Arctic and in the bottom of the sea at various places in the world, have become the object of public attention as a potential natural gas resource. Here the idea of natural gas exploitation from natural gas hydrate fields combined with CO2 isolation using CO2 hydrate has been presented. As a fundamental study, high-pressure phase behaviour for the ethane hydrate system was investigated in a high-pressure cell up to a maximum pressure of 100 MPa, following a previous study of CO2 and methane hydrates. Consequently, the phase equilibrium relationship of an ethane hydrate—water—liquid ethane mixture was obtained in the temperature range from 290.4 to 298.4 K and over a pressure range of 19.48 to 83.75 MPa. The observed phase boundary corresponds to the three-phase coexisting line with a non-variant quadruple point of ethane hydrate—water—liquid ethane—gaseous ethane at 288.8 K and 3.50 MPa, similar to the CO2 hydrate—water—liquid CO2 system.

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26

Shagapov, V. Sh, M. K. Khasanov, and R. S. Bayramgulova. "The theory of injection of liquid carbon dioxide in formation, saturated system “hydrate of methane–methane” in the mode of formation of the intermediate melt zone." Proceedings of the Mavlyutov Institute of Mechanics 11, no. 2 (2016): 171–80. http://dx.doi.org/10.21662/uim2016.2.025.

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The scheme and the corresponding theoretical model of process of methane replacement by liquid carbon dioxide at his injection in a gas hydrate layer are offered. The flat one-dimensional automodel solution corresponding to injection of carbon dioxide in semi-infinite layer through flat border is constructed. It is fixed that such solution can contain three characteristic zones in general case: the far zone, where there is a methane filtration in the porous medium which is partially saturated by methane hydrate in the absence of phase transitions; the melted zone of products of decomposition of methane hydrate (water and methane) can be formed in the intermediate zone (this zone is formed because of heating owing to injection of warm carbon dioxide); the near zone where there is a filtration of liquid carbon dioxide in the layer which is partially saturated by hydrate of carbon dioxide. The analysis of influence of parameters of layer, his initial state (temperature, pressure and hydrate saturation) and the parameters of the injected dioxide of carbon on the various modes of filtration is conducted.

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27

Servio, Phillip, and Peter Englezos. "Morphology of methane and carbon dioxide hydrates formed from water droplets." AIChE Journal 49, no. 1 (January 2003): 269–76. http://dx.doi.org/10.1002/aic.690490125.

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28

Khan, Muhammad Saad, Sana Yaqub, Naathiya Manner, Nur Ani Karthwathi, Ali Qasim, Nurhayati Binti Mellon, and Bhajan Lal. "Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates." IOP Conference Series: Materials Science and Engineering 344 (April 2018): 012025. http://dx.doi.org/10.1088/1757-899x/344/1/012025.

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29

Smith, Duane H., Kal Seshadri, Tsutoma Uchida, and Joseph W. Wilder. "Thermodynamics of methane, propane, and carbon dioxide hydrates in porous glass." AIChE Journal 50, no. 7 (2004): 1589–98. http://dx.doi.org/10.1002/aic.10141.

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30

Shepelkevich, O. F. "The replacement of methane hydrate in the reservoir by injection into the liquid carbon dioxide." Proceedings of the Mavlyutov Institute of Mechanics 12, no. 2 (2017): 206–13. http://dx.doi.org/10.21662/uim2017.2.031.

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The paper deals with the process of injecting liquid carbon dioxide into a hydrate reservoir. It is shown that the process of methane replacement in a hydrate reservoir by injecting liquid carbon dioxide into it can consist of the following steps: piston displacement of free gas from the pores; replacement of methane with liquid carbon dioxide, its dissolution and leaching from the formation; completion of hydrate formation and leaching of the remaining methane gas from the hydrate reservoir. We have presented the distributions of pressure, density, hydrate saturation and temperature at different times.

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31

Uchida, Tsutomu, Hiroshi Miyoshi, Kenji Yamazaki, and Kazutoshi Gohara. "Promoting Effect of Ultra-Fine Bubbles on CO2 Hydrate Formation." Energies 14, no. 12 (June 8, 2021): 3386. http://dx.doi.org/10.3390/en14123386.

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When gas hydrates dissociate into gas and liquid water, many gas bubbles form in the water. The large bubbles disappear after several minutes due to their buoyancy, while a large number of small bubbles (particularly sub-micron-order bubbles known as ultra-fine bubbles (UFBs)) remain in the water for a long time. In our previous studies, we demonstrated that the existence of UFBs is a major factor promoting gas hydrate formation. We then extended our research on this issue to carbon dioxide (CO2) as it forms structure-I hydrates, similar to methane and ethane hydrates explored in previous studies; however, CO2 saturated solutions present severe conditions for the survival of UFBs. The distribution measurements of CO2 UFBs revealed that their average size was larger and number density was smaller than those of other hydrocarbon UFBs. Despite these conditions, the CO2 hydrate formation tests confirmed that CO2 UFBs played important roles in the expression of the promoting effect. The analysis showed that different UFB preparation processes resulted in different promoting effects. These findings can aid in better understanding the mechanism of the promoting (or memory) effect of gas hydrate formation.

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32

Xu, Chun-Gang, Jing Cai, Yi-Song Yu, Ke-Feng Yan, and Xiao-Sen Li. "Effect of pressure on methane recovery from natural gas hydrates by methane-carbon dioxide replacement." Applied Energy 217 (May 2018): 527–36. http://dx.doi.org/10.1016/j.apenergy.2018.02.109.

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33

Sergeeva, Daria, Vladimir Istomin, Evgeny Chuvilin, Boris Bukhanov, and Natalia Sokolova. "Influence of Hydrate-Forming Gas Pressure on Equilibrium Pore Water Content in Soils." Energies 14, no. 7 (March 26, 2021): 1841. http://dx.doi.org/10.3390/en14071841.

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Natural gas hydrates (primarily methane hydrates) are considered to be an important and promising unconventional source of hydrocarbons. Most natural gas hydrate accumulations exist in pore space and are associated with reservoir rocks. Therefore, gas hydrate studies in porous media are of particular interest, as well as, the phase equilibria of pore hydrates, including the determination of equilibrium pore water content (nonclathrated water). Nonclathrated water is analogous to unfrozen water in permafrost soils and has a significant effect on the properties of hydrate-bearing reservoirs. Nonclathrated water content in hydrate-saturated porous media will depend on many factors: pressure, temperature, gas composition, the mineralization of pore water, etc. In this paper, the study is mostly focused on the effect of hydrate-forming gas pressure on nonclathrated water content in hydrate-bearing soils. To solve this problem, simple thermodynamic equations were proposed which require data on pore water activity (or unfrozen water content). Additionally, it is possible to recalculate the nonclathrated water content data from one hydrate-forming gas to another using the proposed thermodynamic equations. The comparison showed a sufficiently good agreement between the calculated nonclathrated water content and its direct measurements for investigated soils. The discrepancy was ~0.15 wt% and was comparable to the accuracy of direct measurements. It was established that the effect of gas pressure on nonclathrated water content is highly nonlinear. For example, the most pronounced effect of gas pressure on nonclathrated water content is observed in the range from equilibrium pressure to 6.0 MPa. The developed thermodynamic technique can be used for different hydrate-forming gases such as methane, ethane, propane, nitrogen, carbon dioxide, various gas mixtures, and natural gases.

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34

Dornan, Peter, Saman Alavi, and T. K. Woo. "Free energies of carbon dioxide sequestration and methane recovery in clathrate hydrates." Journal of Chemical Physics 127, no. 12 (September 28, 2007): 124510. http://dx.doi.org/10.1063/1.2769634.

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35

Kwon, Tae-Hyuk, Timothy J. Kneafsey, and Emily V. L. Rees. "Thermal Dissociation Behavior and Dissociation Enthalpies of Methane–Carbon Dioxide Mixed Hydrates." Journal of Physical Chemistry B 115, no. 25 (June 30, 2011): 8169–75. http://dx.doi.org/10.1021/jp111490w.

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36

Park, Youngjune, Jaehyoung Lee, Kyuchul Shin, Jiwoong Seol, Kyung-Min Lee, Dae-Gee Huh, Keun-Pil Park, and Huen Lee. "Phase and kinetic behavior of the mixed methane and carbon dioxide hydrates." Korean Journal of Chemical Engineering 23, no. 2 (March 2006): 283–87. http://dx.doi.org/10.1007/bf02705728.

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37

Lee, Huen, Yongwon Seo, Yu-Taek Seo, Igor L. Moudrakovski, and John A. Ripmeester. "Recovering Methane from Solid Methane Hydrate with Carbon Dioxide." Angewandte Chemie 115, no. 41 (October 27, 2003): 5202–5. http://dx.doi.org/10.1002/ange.200351489.

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38

Lee, Huen, Yongwon Seo, Yu-Taek Seo, Igor L. Moudrakovski, and John A. Ripmeester. "Recovering Methane from Solid Methane Hydrate with Carbon Dioxide." Angewandte Chemie International Edition 42, no. 41 (October 27, 2003): 5048–51. http://dx.doi.org/10.1002/anie.200351489.

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39

Khasanov, Marat K., Nail G. Musakaev, Maxim V. Stolpovsky, and Svetlana R. Kildibaeva. "Mathematical Model of Decomposition of Methane Hydrate during the Injection of Liquid Carbon Dioxide into a Reservoir Saturated with Methane and Its Hydrate." Mathematics 8, no. 9 (September 2, 2020): 1482. http://dx.doi.org/10.3390/math8091482.

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The article describes a mathematical model of pumping of heated liquid carbon dioxide into a reservoir of finite extent, the pores of which in the initial state contain methane and methane gas hydrate. This model takes into account the existence in the reservoir of three characteristic regions. We call the first region “near”, the second “intermediate”, and the third “far”. According to the problem statement, the first region contains liquid CO2 and hydrate, the second region is saturated with methane and water, the third contains methane and hydrate. The main features of mathematical models that provide a consistent description of the considered processes are investigated. It was found that at sufficiently high injection pressures and low pressures at the right reservoir boundary, the boundary of carbon dioxide hydrate formation can come up with the boundary of methane gas hydrate decomposition. It is also shown that at sufficiently low values of pressure of injection of carbon dioxide and pressure at the right boundary of the reservoir, the pressure at the boundary of hydrate formation of carbon dioxide drops below the boiling pressure of carbon dioxide. In this case, for a consistent description of the considered processes, it is necessary to correct the mathematical model in order to take into account the boiling of carbon dioxide. Maps of possible solutions have been built, which show in what ranges of parameters one or another mathematical model is consistent.

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40

Ohgaki, Kazunari, Kiyoteru Takano, Hiroyuki Sangawa, Takuya Matsubara, and Shinya Nakano. "Methane exploitation by carbon dioxide from gas hydrates. Phase equilibria for CO2-CH4 mixed hydrate system." JOURNAL OF CHEMICAL ENGINEERING OF JAPAN 29, no. 3 (1996): 478–83. http://dx.doi.org/10.1252/jcej.29.478.

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41

Khan, Muhammad Saad, Cornelius Borecho Bavoh, Mohammad Azizur Rahman, Bhajan Lal, Ato Kwamena Quainoo, and Abdulhalim Shah Maulud. "Assessing the Alkyl Chain Effect of Ammonium Hydroxides Ionic Liquids on the Kinetics of Pure Methane and Carbon Dioxide Hydrates." Energies 13, no. 12 (June 24, 2020): 3272. http://dx.doi.org/10.3390/en13123272.

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In this study, four ammonium hydroxide ionic liquids (AHILs) with varying alkyl chains were evaluated for their kinetic hydrate inhibition (KHI) impact on pure carbon dioxide (CO2) and methane (CH4) gas hydrate systems. The constant cooling technique was used to determine the induction time, the initial rate of hydrate formation, and the amount of gas uptake for CH4-AHILs and CO2-AHILs systems at 8.0 and 3.50 MPa, respectively, at 1 wt.% aqueous AHILs solutions. In addition, the effect of hydrate formation sub-cooling temperature on the performance of the AHILs was conducted at experimental temperatures 274.0 and 277.0 K. The tested AHILs kinetically inhibited both CH4 and CO2 hydrates at the studied sub-cooling temperatures by delaying the hydrate induction time and reducing the initial rate of hydrate formation and gas uptake. The hydrate inhibition performance of AHILs increases with increasing alkyl chain length, due to the better surface adsorption on the hydrate crystal surface with alkyl chain length enhancement. TPrAOH efficiently inhibited the induction time of both CH4 and CO2 hydrate with an average inhibition percentage of 50% and 84%, respectively. Tetramethylammonium Hydroxide (TMAOH) and Tetrabutylammonium Hydroxide (TBAOH) best reduced CH4 and CO2 total uptake on average, with TMAOH and Tetraethylammonium Hydroxide (TEAOH) suitably reducing the average initial rate of CH4 and CO2 hydrate formation, respectively. The findings in this study could provide a roadmap for the potential use of AHILs as KHI inhibitors, especially in offshore environs.

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42

Tung, Yen-Tien, Li-Jen Chen, Yan-Ping Chen, and Shiang-Tai Lin. "In Situ Methane Recovery and Carbon Dioxide Sequestration in Methane Hydrates: A Molecular Dynamics Simulation Study." Journal of Physical Chemistry B 115, no. 51 (December 29, 2011): 15295–302. http://dx.doi.org/10.1021/jp2088675.

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43

Waage, Magnus H., Thijs J. H. Vlugt, and Signe Kjelstrup. "Phase Diagram of Methane and Carbon Dioxide Hydrates Computed by Monte Carlo Simulations." Journal of Physical Chemistry B 121, no. 30 (July 24, 2017): 7336–50. http://dx.doi.org/10.1021/acs.jpcb.7b03071.

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44

Voronov, V. P., E. E. Gorodetskii, and A. R. Muratov. "Study of methane replacement in hydrates by carbon dioxide in a cyclic process." Journal of Natural Gas Science and Engineering 21 (November 2014): 1107–12. http://dx.doi.org/10.1016/j.jngse.2014.11.003.

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45

Kang, Seong-Pil, Moon-Kyoon Chun, and Huen Lee. "Phase equilibria of methane and carbon dioxide hydrates in the aqueous MgCl2 solutions." Fluid Phase Equilibria 147, no. 1-2 (June 1998): 229–38. http://dx.doi.org/10.1016/s0378-3812(98)00233-7.

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46

Shagapov, V. Sh, G. R. Rafikova, and M. K. Khasanov. "The Theory of the Replacement of Methane by Carbon Dioxide in Gas Hydrates." Theoretical Foundations of Chemical Engineering 53, no. 1 (January 2019): 64–74. http://dx.doi.org/10.1134/s0040579518060118.

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47

Khan, Muhammad Saad, Bhajan Lal, Lau Kok Keong, and Iqbal Ahmed. "Tetramethyl ammonium chloride as dual functional inhibitor for methane and carbon dioxide hydrates." Fuel 236 (January 2019): 251–63. http://dx.doi.org/10.1016/j.fuel.2018.09.001.

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48

Partoon, Behzad, Khalik M. Sabil, Hariz Roslan, Bhajan Lal, and Lau Kok Keong. "Impact of acetone on phase boundary of methane and carbon dioxide mixed hydrates." Fluid Phase Equilibria 412 (March 2016): 51–56. http://dx.doi.org/10.1016/j.fluid.2015.12.027.

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49

Cannone, Salvatore F., Andrea Lanzini, and Massimo Santarelli. "A Review on CO2 Capture Technologies with Focus on CO2-Enhanced Methane Recovery from Hydrates." Energies 14, no. 2 (January 12, 2021): 387. http://dx.doi.org/10.3390/en14020387.

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Natural gas is considered a helpful transition fuel in order to reduce the greenhouse gas emissions of other conventional power plants burning coal or liquid fossil fuels. Natural Gas Hydrates (NGHs) constitute the largest reservoir of natural gas in the world. Methane contained within the crystalline structure can be replaced by carbon dioxide to enhance gas recovery from hydrates. This technical review presents a techno-economic analysis of the full pathway, which begins with the capture of CO2 from power and process industries and ends with its transportation to a geological sequestration site consisting of clathrate hydrates. Since extracted methane is still rich in CO2, on-site separation is required. Focus is thus placed on membrane-based gas separation technologies widely used for gas purification and CO2 removal from raw natural gas and exhaust gas. Nevertheless, the other carbon capture processes (i.e., oxy-fuel combustion, pre-combustion and post-combustion) are briefly discussed and their carbon capture costs are compared with membrane separation technology. Since a large-scale Carbon Capture and Storage (CCS) facility requires CO2 transportation and storage infrastructure, a technical, cost and safety assessment of CO2 transportation over long distances is carried out. Finally, this paper provides an overview of the storage solutions developed around the world, principally studying the geological NGH formation for CO2 sinks.

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Segtovich, Iuri Soter Viana, Amaro Gomes Barreto Jr., and Frederico Wanderley Tavares. "Phase diagrams for hydrates beyond incipient condition — Complex behavior in methane/propane and carbon dioxide/iso-butane hydrates." Fluid Phase Equilibria 426 (October 2016): 75–82. http://dx.doi.org/10.1016/j.fluid.2016.02.002.

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