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Papers - Ohmura, Ryo

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Continuous hydrate-based CO<inf>2</inf> separation from H<inf>2</inf> + CO<inf>2</inf> gas mixture using cyclopentane as co-guest

Misawa T., Ishikawa T., Takeya S., Alavi S., Ohmura R.

Journal of Industrial and Engineering Chemistry 121 228 - 234 2023.05

ISSN 1226086X

CO2 separation from H2 + CO2 gas mixture is a necessary technology for a stable supply of blue hydrogen. Among CO2 separation technology, hydrate-based CO2 separation is an environmentally and economically superior technology. Cyclopentane (CP) was selected as guest compound to enable hydrate-based CO2 separation under thermodynamic conditions closer to normal pressure and temperature. Hydrate-based continuous CO2 separation experiments are conducted in the H2 + CO2 + CP + H2O system at 284 K. The results of these experiments showed that mole fraction of H2 in the gas phase reached 0.9 at the steady state in the H2 + CO2 + CP + H2O system after the CO2 was extracted via hydrate formation. At the same time, more H2 was incorporated into the mixed hydrate during this process as the concentration of H2 in the gas phase increases post hydrate formation. Therefore, it was demonstrated that hydrate-based CO2 separation was successful in H2 + CO2 + CP + H2O system at 284 K but there is also increase of energy costs caused by H2 loss. The PXRD results identified H2 + CO2 + CP hydrate as structure II hydrate. Although H2 + CO2 + Tetrahydropyran (THP) hydrate also forms structure II hydrate, more H2 is encapsulated in the H2 + CO2 + CP mixed hydrate than in the H2 + CO2 + THP mixed hydrate. This difference may be caused by the difference in the lattice constants of CP and THP hydrates, which arises from the difference in molecular size of CP and THP, from the differences between the large guest–host interactions, and from differences arising from hydrogen bonding of THP with the host water framework which can decrease the H2 holding capacity. In this study, it was revealed that the molecular diameter of the guest molecules need also to be considered in addition to the phase equilibrium conditions of the hydrates when selecting guest compound of hydrates.

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Thermodynamic stability and characterization of double clathrate hydrate with carbon dioxide + cyclopentane + deuterium oxide

Maruyama M., Nagayama S., Misawa T., Takeya S., Ohmura R.

Journal of Chemical Thermodynamics 179 2023.04

ISSN 00219614

This paper reports characterization of clathrate hydrate formed in CO2 + cyclopentane + deuterium oxide (D2O) system with the phase equilibrium determination and the powder X-ray diffraction (PXRD) measurements towards the development of hydrate-based tritium separation technology. Four-phase (CO2 gas + liquid cyclopentane + liquid D2O + hydrate) equilibrium conditions were measured using the isochoric procedure in the pressure range from 0.279 MPa to 2.735 MPa and the temperature range from 285.35 K to 293.65 K. The equilibrium temperature of CO2 + cyclopentane + D2O system is always higher by 2.0 K to 2.4 K compared to that of CO2 + cyclopentane + H2O system. The detailed crystallographic properties of both CO2 + cyclopentane + D2O hydrate and CO2 + cyclopentane + H2O hydrate including the lattice constants, the radii and volumes of each cage and the cage occupancy were estimated by the PXRD analysis. Based on the obtained results, implications for the development and operation of D2O-hydrate-based process are discussed.

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Measurements of the Dissociation Heats of Tetrabutylammonium Acetate and Tetrabutylammonium Hydroxide Ionic Semiclathrate Hydrates

Iwai T., Takamura S., Hotta A., Ohmura R.

International Journal of Thermophysics 44 ( 3 ) 2023.03

ISSN 0195928X

Ionic semiclathrate hydrates mainly consist of water typically together with tetrabutylammonium and tetrabutylphosphonium salts. Since ionic semiclathrate hydrates have the large dissociation heat under ambient pressure and temperature conditions, various ionic semiclathrate hydrates have been studied as safety and eco-friendly phase change materials. In this study, tetrabutylammonium acetate hydrates and tetrabutylammonium hydroxide hydrates were proposed as thermal energy storage media for air conditioning and cooling lithium-ion batteries. The dissociation heat, which was a significant thermophysical property to design thermal energy storage systems, were measured at various mass fractions. The largest dissociation heats of tetrabutylammonium acetate hydrates and tetrabutylammonium hydroxide hydrates were 212.9 ± 0.9 kJ⋅kg−1 and 200.4 ± 2.2 kJ⋅kg−1. As a result of the comparison of the dissociation heats of tetrabutylammonium acetate hydrates and tetrabutylammonium hydroxide hydrates with those of other ionic semiclathrate hydrates, it was found that tetrabutylammonium acetate hydrates and tetrabutylammonium hydroxide hydrates had the promising thermophysical properties as thermal energy storage media for air conditioning and cooling lithium-ion batteries, respectively.

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Thermally Induced Phase Transition of Cubic Structure II Hydrate: Crystal Structures of Tetrahydropyran-CO<inf>2</inf> Binary Hydrate

Takeya S., Fujihisa H., Alavi S., Ohmura R.

Journal of Physical Chemistry Letters 14 ( 7 ) 1885 - 1891 2023.02

We report a thermally induced phase transition of cubic structure II hydrates of tetrahydropyran (THP) and CO2 below about 140 K. The phase transition was characterized by powder X-ray diffraction measurements at variable temperatures. A dynamical ordering of the CO2 guests in small pentagonal dodecahedral 512 host water cages, not previously observed in the simple CO2 hydrate, occurs simultaneously with the symmetry lowering transition from a cubic structure II (space group Fd-3m with cell dimensions a = 17.3202(7) Å at 153 K) to a tetragonal (space group I41/amd with cell dimensions a = 17.484(4) Å and c = 12.145(1) Å at 138 K) unit cell. The effect of guest molecules on the phase transition at low temperatures is discussed, which demonstrates that the clathrate hydrate structures and thermodynamic properties can be modified by adjusting the size and chemical structure of larger and smaller guest molecules.

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Equilibrium properties and crystal growth of D<inf>2</inf>O + cyclopentane hydrate for sustainable tritium separation

Maruyama M., Ohmura R.

Canadian Journal of Chemical Engineering 101 ( 2 ) 718 - 725 2023.02

ISSN 00084034

This study reports thermodynamic properties and crystal growth observations of D2O + cyclopentane hydrate toward the development of a hydrate-based tritium separation process. We employed D2O as a host of hydrate with respect to the investigation into the formation of D2O hydrate substrate, which is a core component of the tritium separation process. The hydrate phase equilibrium temperature in the liquid D2O + liquid cyclopentane system was 3.2°C higher than the corresponding H2O hydrate. Experiments on crystal growth were conducted at temperatures ranging from 5.1 to 8.5°C under atmospheric pressure. Under each thermodynamic condition, polygonal hydrate crystals appeared, growing along the D2O/cyclopentane interface. The geometric shape and size of the crystals varied depending on the temperature. The variation in crystal morphology was comparable to that of the H2O + cyclopentane hydrate. Implications based on the obtained results for the hydrate-based isotopic water separation process design are discussed.

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Thermophysical Properties of Ionic Semiclathrate Hydrate Formed with Tetrabutylphosphonium Malonate

Iwai T., Oguro S., Ota I., Hiraga K., Hotta A., Ohmura R.

International Journal of Thermophysics 44 ( 2 ) 2023.02

ISSN 0195928X

Ionic semiclathrate hydrate is a crystalline compound mainly composed of water, which can dissociate at ordinary pressure and temperature. Ionic semiclathrate hydrates have been widely studied to develop prospective green and safety phase change materials utilized in a thermal energy storage system to cool batteries, in air conditioning, and in a cold chain system. The thermophysical properties, such as equilibrium temperature and dissociation heat, and the mass fraction dependence of such properties need to be carefully investigated to design such systems. In this study, the equilibrium temperature and the dissociation heat of tetrabutylphosphonium malonate ionic semiclathrate hydrates were experimentally determined at various mass fractions through an established method: the maximum value of the dissociation heat was 179.70 kJ·kg−1 at w = 0.357 and the equilibrium temperature was 8.9 °C at w = 0.357. By comparing tetrabutylphosphonium malonate ionic semiclathrate hydrates with other media in terms of the measured equilibrium temperature and the dissociation heat, the usability of the hydrates as thermal energy storage media for general air conditioning was discussed.

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Zero emissions, low-energy water production system using clathrate hydrate: Engineering design and techno-economic assessment

Maruyama M., Tomura S., Yasuda K., Ohmura R.

Journal of Cleaner Production 383 2023.01

ISSN 09596526

Seawater desalination via the crystallization using clathrate hydrate is a promising technology for displacing conventional desalination processes, yet the technology immaturity and poor cost performance are the issues to be resolved. In this study, conceptual designs of hydrate-based dual functional plant (desalination and salt production) utilizing the eutectic crystallization of hydrate and NaCl dihydrate have been presented on an industrial scale with the capacity of 24 m3/day. The conceptual design proposed in this study focuses on detailed and executive aspects, including the size of individual reactors, the selection of pumps, and the setting of operating temperature and pressure conditions. The process designs help meet these present demands on hydrate-based desalination and conform to the global standards of minimizing energy requirement and the disposal of environmental pollutants. Hydrate-based plant was designed as a novel Zero Liquid Discharge (ZLD) process to produce potable water and salt simultaneously, with the recovery ratio of pure water from seawater achieving 95%. The design-based cost estimation showed that the annual operating cost is estimated US$2.29/m3 for cyclopentane-hydrate-based plant and US$3.64/m3 for CO2-hydrate-based plant. The results suggest that the hydrate-based plants will bring gross profit comparable to the reported ZLD plants; that is, the gross profit will achieve US$20 per 1 m3 of water production. In addition to these two improvements over the existing plants, the hydrate-based process designs also exhibit favorable energy requirement compared to the eutectic system of ice. This design-based study may contribute to the promotion of additional construction of hydrate-based process unit to the existing reverse osmosis plant or even the new construction of hydrate-based desalination plant worldwide.

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Phase equilibrium conditions in cyclopentane hydrate forming systems coexisting with sodium chloride aqueous solution under atmospheric pressure and vacuum condition

Kamochi K., Tripathi A., Taoka M., Ohmura R., Yasuda K.

Journal of Chemical Thermodynamics 175 2022.12

ISSN 00219614

The equilibrium condition measurements were performed in the cyclopentane clathrate hydrate forming systems coexisting with sodium chloride as a technological basis for the development of seawater desalination technology using clathrate hydrates. The experiments were performed in the system under vacuum condition in addition to the system under atmospheric pressure. The equilibrium conditions in the system under the vacuum condition are essential to accurately construct the phase diagram in the cyclopentane clathrate hydrate forming system without the effects of the surrounding air. The equilibrated phases were sodium chloride aqueous solution + cyclopentane clathrate hydrate + liquid cyclopentane + vapor cyclopentane in the system under the vacuum condition. The concentration of sodium chloride investigated in this study, wNaCl, was 0 ≤ wNaCl ≤ 0.210 in mass fraction. The equilibrium temperature in both systems decreased with increasing wNaCl. The equilibrium temperature at a fixed concentration of sodium chloride under the vacuum condition was lower than that under the atmospheric pressure. It was attributed to the compression by the atmospheric pressure in addition to the incorporation of molecules constituting the atmospheric air.

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Synthesis and thermophysical properties of Tetrabutylammonium picolinate hydrate as an energy storage phase change material for cold chain

Yamamoto K., Iwai T., Hiraga K., Miyamoto T., Hotta A., Ohmura R.

Journal of Energy Storage 55 2022.11

Ionic semiclathrate hydrates, the water-based phase change materials (PCMs) have potential for thermal energy storage media. There are a number of hydrates, reported in the literature, which are suitable as PCMs for air conditioning system of the required temperature range 10–15 °C. In this study, Tetrabutylammonium picolinate hydrate (TBAPi hydrate) was newly synthesized as a PCM for the cold chain, which has a lower phase equilibrium temperature than the previously reported hydrates. Thermophysical properties of TBAPi hydrate were experimentally measured. The hydrate dissociation heat was determined using a differential scanning calorimeter (DSC). The phase equilibrium temperature was measured by visually observing system with a CMOS camera and microscope. Also, the cycling test was conducted to confirm the long-term stability of thermophysical properties. The largest dissociation heat was 157.7 ± 4.9 kJ・kg−1 at a mass fraction of TBAPi aqueous solution, wTBAPi of 0.37. The highest phase equilibrium temperature of TBAPi hydrate was 5.5 °C at 0.34 ≤ wTBAPi ≤ 0.36. These thermophysical properties did not change even after 200 cycles of hydrate formation and dissociation. Based on the experimental results, TBAPi hydrate can be applied to the transport and storage of vaccines, blood packs, and perishable foods.

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Measurements of phase equilibrium temperature and dissociation heat of tetrabutylphosphonium glutarate ionic semiclathrate hydrate

Iwai T., Ohta I., Hiraga K., Kashima K., Hotta A., Ohmura R.

Fluid Phase Equilibria 562 2022.11

ISSN 03783812

Thermophysical properties such as phase equilibrium temperature and dissociation heat are important to determine the performance of phase change materials targeting thermal energy storage. The phase equilibrium temperature and dissociation heat of tetrabutylphosphoniumglutarate ionic semiclathrate hydrate were measured in this study. The highest phase equilibrium temperature of tetrabutylphosphoniumglutarate hydrate was experimentally determined 287.4 K at the mass fraction 0.347 and 0.357. The largest dissociation heat was 193.3 ± 1.6 kJ/kg at the mass fraction 0.357. The measurement results in this work show that the dissociation heat can be utilized in the suitable temperature range targeting general air conditioning and data center.

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Molecular dynamics simulations of interfacial structure, dynamics, and interfacial tension of tetrabutylammonium bromide aqueous solution in the presence of methane and carbon dioxide

Naeiji P., Woo T.K., Ohmura R., Alavi S.

Journal of Chemical Physics 157 ( 15 ) 2022.10

ISSN 00219606

The interfacial behavior of tetrabutylammonium bromide (TBAB) aqueous solutions in the absence of gas and the presence of methane and carbon dioxide gases is studied by molecular dynamics simulations. The aqueous TBAB phase, at concentrations similar to the solid semiclathrate hydrate (1:38 mol ratio), has a smaller interfacial tension and an increase in the gas molecules adsorbed at the interface compared to that in pure water. Both these factors may contribute to facilitating the uptake of the gases into the solid phase during the process of semiclathrate hydrate formation. At similar gas pressures, CO2 is adsorbed preferentially compared to CH4, giving it a higher surface density, due to the stronger intermolecular interactions of CO2 molecules of the solution at the interface. The increase in relative adsorption of CH4 at the solution surface compared to that in pure water surface is due to the hydrophobic interactions between the n-alkyl chains of the TBA+ cation and methane gas.

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Development of dual functional methodology for seawater desalination and salt manufacture by carbon dioxide hydrate formation

Gibo A., Nakao S., Shiraishi S., Takeya S., Tomura S., Ohmura R., Yasuda K.

Desalination 539 2022.10

ISSN 00119164

Clathrate-hydrate-based seawater desalination is a novel technology that is performed by reaction between seawater and guest compounds to obtain fresh water. This study proposed a dual functional methodology for seawater desalination and salt manufacture by using carbon dioxide clathrate hydrate. In this methodology, the clathrate hydrate formation continues until the concentration of electrolytes in unreacted brine reaches the saturated solubility for the salt precipitation. The visual observation of the clathrate hydrate formation and the salt precipitation coupled with the analysis utilizing the powder X-ray diffraction (PXRD) technique was implemented to demonstrate the methodology. The carbon dioxide clathrate hydrate formation was first performed with sodium chloride aqueous solution. The carbon dioxide clathrate hydrate crystals floated on high salinity water. This experiment was followed by the occurrence of the sodium chloride dihydrate precipitation upon the carbon dioxide clathrate hydrate formation. The formed compounds, carbon dioxide clathrate hydrate and sodium chloride dihydrate, were identified by PXRD analysis. The mass fraction of the compounds was also determined by PXRD.

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Continuous CO<inf>2</inf>Separation from a N<inf>2</inf>+ CO<inf>2</inf>Gas Mixture Using Clathrate Hydrate: Insights into Sustainable Post-combustion Carbon Capture

Maruyama M., Kao S., Kiyokawa H., Takeya S., Ohmura R.

Energy and Fuels 36 ( 18 ) 10601 - 10609 2022.09

ISSN 08870624

Clathrate-hydrate-based CO2 capture from a post-combustion N2 + CO2 gas mixture has been experimentally investigated for decarbonization. In this study, we performed hydrate-based continuous CO2 separation experiments for N2 + CO2 + tetrahydropyran (THP) + water system. The experimental conditions were set at 280.1 K under 3.0 MPa with THP mass fractions wTHP of 0.22 and 0.11. For each experimental run, the time-dependent changes in compositions in the gas phase and the hydrate slurry were recorded hourly until the system reached a steady state. The cage occupancies of N2 and CO2 in the structure II 512 small cages were determined to be 43 and 24%, respectively, with the powder X-ray diffraction analysis. The obtained results showed that the continuous carbon capture is a practicable scheme, yet the CO2 concentration rate and CO2 recovery ratio are comparable to or lower than those of the pre-combustion systems reported in previous studies. Still, our investigation revealed that the development of an efficient hydrate formation method, such as the improvement of the geometry of mixing impellers, could enhance the CO2 recovery ratio for the continuous operation.

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Synthesis and evaluation of green phase change materials for efficient air conditioning by tetrabutylphosphonium phosphate ionic semiclathrate hydrate

Iwai T., Miyamoto T., Kurokawa N., Hotta A., Ohmura R.

Journal of Energy Storage (Journal of Energy Storage) 52 2022.08

A tetrabutylammonium bromide (TBAB) hydrate is the only ionic semiclathrate hydrate that has been commercialized as a medium for efficient thermal energy storage targeting general air conditioning. However, TBAB is an environmental pollutant, while liquid water and ice that have been widely used as conventional media, also have difficulty in increasing the thermal energy storage density as well as the coefficient of performance (COP) of a refrigerator to form solid. In this study, a tetrabutylphosphonium phosphate ((TBP)3PO4) hydrate was proposed as an alternative green medium. The dissociation heat and the phase equilibrium temperature, which were both crucial factors to evaluate the thermal energy storage density, and COP was experimentally determined. It was found that the maximum dissociation heat was 154.1 ± 2.0 kJ・kg−1 at the mass fraction of 0.309. The highest phase equilibrium temperature was 10.0 °C at the mass fractions of 0.290, 0.299, and 0.309. The thermal energy storage density of (TBP)3PO4 hydrates was 3.7 times larger than that of water. (TBP)3PO4 hydrates increased the COP of a refrigerator to form solid by 42% as compared with ice, indicating the potential size-reduction of conventional devices with the decrease in the power consumption of a refrigerator. The effective balance between environmental protection and the system performance through (TBP)3PO4 hydrates was also discussed.

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Pinacol hydrate as a novel thermal energy storage medium for electric vehicles

Kiyokawa H., Kondo Y., Koyama R., Kurokawa N., Atsushi H., Alavi S., Ota I., Ohmura R.

Journal of Energy Storage (Journal of Energy Storage) 51 2022.07

Movement towards the gradual replacement of gasoline combustion vehicles to electrical vehicles is occurring on a global scale. Heat management of lithium-ion batteries (LIB) is necessary for long-term operation and safety of the power sources of electrical vehicles. This research suggests pinacol hydrate as a phase change material (PCM) for use as an alternative cooling media for LIB. The pinacol hydrate crystallizes under atmospheric pressure and temperatures around 45 °C, which are compatible with LIB operating conditions. Its dissociation enthalpy can control the excessive heating of the battery. The equilibrium phase transition temperature of pinacol hydrate was reported about a decade ago, but its thermal storage capacity has not been reported yet and updated quantitative measurements are required. Hence, in this study the equilibrium temperatures and dissociation enthalpies are experimentally measured for pinacol aqueous solutions prepared with mass fractions between 0.40 and 0.85. The maximum thermal storage capacity is measured by differential scanning calorimetry to be 301.9 kJ/kg for mass fraction of 0.50 which is compatible with operating conditions of up to 45.6 °C. A minimization of reservoir tank mass by 35% of that needed for conventional technologies may be possible by using pinacol hydrate.

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Investigation of crystal growth of CO<inf>2</inf> hydrate in aqueous fructose solution for the potential application in carbonated solid foods

Shigehara S., Ohmura R.

Food Chemistry (Food Chemistry) 371 2022.03

ISSN 03088146

CO2 hydrate is applicable to solid carbonated foods. The hydrate crystal morphology, which represents the crystal size and shape, is an important characteristic that changes the texture of foods. We report an observational study of the crystal growth of CO2 hydrate in aqueous fructose solution. The difference between the phase equilibrium temperature and the experimental temperature, ΔTsub, is applied as an index of the driving force. Experiments were performed at ΔTsub range of 0.9 K to 5.4 K. At all ΔTsub, initial crystal formed at the gas-solution interface and grew along the interface. After covering the interface, the crystals grew in the liquid phase The individual crystals were identified as polyhedral with facets (ΔTsub = 0.9 K), skeletal crystals (ΔTsub = 2.0 K) and dendrites (ΔTsub = 3.0 K and 5.4 K). Based on these results, the potential effect of gas hydrate morphology on texture of foods has been discussed.

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Synthesis and thermophysical property evaluation of ionic semiclathrate hydrate formed with tetrabutylphosphonium glycine as a chilling temperature phase change material

Miyamoto T., Kurokawa N., Ota I., Hotta A., Ohmura R.

Journal of Energy Storage (Journal of Energy Storage) 45 2022.01

Ionic semiclathrate hydrate, which is formed under atmospheric pressure with sustainably safe properties, has a potential for solid-liquid phase change materials(PCMs). In this study, the thermophysical property of tetrabutylphosphonium glycine(TBPGly) hydrate containing no halogen guest compound, glycine (aminoacetic acid), was investigated to evaluate the availability as an eco-efficient thermal energy storage medium. The phase equilibrium temperature was obtained through visual observation method. The heat flow rate curve behavior and dissociation heat were measured via differential scanning calorimetry(DSC). In the dissociation process, a single hydrate dissociation peak emerged, indicating TBPGly hydrate has one type of crystallographic structure. The concentration dependency of the TBPGly aqueous solution on the equilibrium temperature and the dissociation heat was confirmed. The highest equilibrium temperature of 5.8 °C was confirmed at the fraction range wTBPGly =0.368 or xTBPGly =0.0306, and the largest dissociation heat was 177.7 kJ·kg−1 at the fraction range wTBPGly =0.377or xTBPGly =0.0318. The estimated hydration number in the congruent composition was found to be in 31.2 to 32.5. In addition, based on the measured physical property, the optimum operating temperature and volume fraction of TBPGly hydrate was evaluated to determine the concentration for the practical cooling system. These data revealed TBPGly hydrate is available as a solid or slurry PCM under the operating temperature range 2 °C to 5.8 °C. The experimental data as well as the illustrative calculations contribute to accelerate the expansion in the application range, and provide the prospect in selecting the suitable composition toward the actual hydrate-based cooling system.

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Investigation of the thermodynamic properties of hydrates as cooling phase change materials for their implementation in electric vehicles

Kiyokawa H., Miyamoto T., Takeya S., Ota I., Iwai T., Hotta A., Ohmura R.

New Journal of Chemistry (New Journal of Chemistry) 46 ( 19 ) 9214 - 9221 2022

ISSN 11440546

Electric vehicles (EVs) play key roles in realizing a sustainable society. Lithium-ion batteries (LIBs) implemented in EVs deteriorate due to significant temperature changes. To maintain LIBs in an appropriate temperature range, a competitive thermal energy storage (TES) medium is needed. Phase change materials (PCMs) that can utilize their latent heat have great potential. In this study, we focused on piperazine hexahydrate as a promising candidate for a PCM and investigated its thermodynamic properties that are essential for practical design. The equilibrium temperature and dissociation enthalpy were determined in the mass fraction range of 0.250 to 0.550. The results showed that piperazine hexahydrate had a maximum equilibrium temperature of 42.9 °C and a maximum dissociation enthalpy of 250.0 ± 3.7 kJ kg−1 at a mass fraction of 0.443, which is the congruent point of piperazine hexahydrate. Piperazine hexahydrate can be utilized as a PCM in the temperature range of 34.4 °C to 42.9 °C. By utilizing piperazine hexahydrate instead of a conventional water-cooling system, the volume of the TES tank may be reduced by 31% approximately. The crystal system of the piperazine hexahydrate prepared in the present study was determined to be pseudomonoclinic by powder X-ray diffraction (PXRD) measurements, which is the same as that reported in the literature.

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Thermophysical Properties of a Promising Material for Thermal Energy Storage Synthesized by Tetrabutylphosphonium Malonate and Water

Iwai T., Oguro S., Ohta I., Hotta A., Ohmura R.

Proceedings of IEEE Asia-Pacific Conference on Computer Science and Data Engineering, CSDE 2022 2022

Thermal energy storage for air conditioning is increasingly becoming important because the fluctuating output of renewable energy and the growing cooling demand will need to be addressed. In this study, we proposed tetrabutylphosphonium malonate hydrate as an environment friendly thermal energy storage medium for air conditioning. Equilibrium temperature and dissociation heat, which were significant thermophysical properties for commercialization, were experimentally determined at three mass fractions of tetrabutylphosphonium malonate aqueous solution. The maximum value of equilibrium temperature was determined to be 8.9 °C. The largest dissociation heat was measured to be 148.1 kJ/kg. These results indicate that tetrabutylphosphonium malonate hydrate has appropriate thermophysical properties for a thermal energy storage medium.

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Phase Equilibrium for Clathrate Hydrate Formed in Deuterium Oxide + CO<inf>2</inf>+ Cyclopentane System: Application to Low-Concentration Tritium Separation

Maruyama M., Misawa T., Ohmura R.

Proceedings of IEEE Asia-Pacific Conference on Computer Science and Data Engineering, CSDE 2022 2022

This paper reports pressure-temperature conditions for liquid + hydrate + vapor phase equilibrium of hydrate formed with deuterium oxide (D2O), CO2 and cyclopentane. The aim of this study is to obtain the equilibrium properties of the formed hydrate for the application to hydrate-based tritium separation process. Measurements with batch isochoric method were performed. The pressure and temperature ranges of measurement were from 1.63 MPa to 2.46 MPa and from 290.6 K to 293.4 K. The obtained results indicate that D2O + CO2+ cyclopentane hydrate is formed in milder conditions than H2O + CO2+ cyclopentane hydrate by 2.1 K at the given pressure conditions.

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