Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 43

Search results for: hydrates

43 Analysis of the Black Sea Gas Hydrates

Authors: Sukru Merey, Caglar Sinayuc


Gas hydrate deposits which are found in deep ocean sediments and in permafrost regions are supposed to be a fossil fuel reserve for the future. The Black Sea is also considered rich in terms of gas hydrates. It abundantly contains gas hydrates as methane (CH4~80 to 99.9%) source. In this study, by using the literature, seismic and other data of the Black Sea such as salinity, porosity of the sediments, common gas type, temperature distribution and pressure gradient, the optimum gas production method for the Black Sea gas hydrates was selected as mainly depressurization method. Numerical simulations were run to analyze gas production from gas hydrate deposited in turbidites in the Black Sea by depressurization.

Keywords: CH4 hydrate, Black Sea hydrates, gas hydrate experiments, HydrateResSim

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42 Investigation of the Catalytic Role of Surfactants on Carbon Dioxide Hydrate Formation in Sediments

Authors: Ehsan Heidaryan


Gas hydrate sediments are ice like permafrost in deep see and oceans. Methane production in sequestration process and reducing atmospheric carbon dioxide, a main source of greenhouse gas, has been accentuated recently. One focus is capture, separation, and sequestration of industrial carbon dioxide. As a hydrate former, carbon dioxide forms hydrates at moderate temperatures and pressures. This phenomenon could be utilized to capture and separate carbon dioxide from flue gases, and also has the potential to sequester carbon dioxide in the deep seabeds. This research investigated the effect of synthetic surfactants on carbon dioxide hydrate formation, catalysis and consequently, methane production from hydrate permafrosts in sediments. It investigated the sequestration potential of carbon dioxide hydrates in ocean sediments. Also, the catalytic effect of biosurfactants in these processes was investigated.

Keywords: carbon dioxide, hydrate, sequestration, surfactant

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41 Onboard Heat, Pressure and Boil-Off Gas Treatment for Stacked NGH Tank Containers

Authors: Hee Jin Kang


Despite numerous studies on the reserves and availability of natural gas hydrates, the technology of transporting natural gas hydrates in large quantities to sea has not been put into practical use. Several natural gas hydrate transport technologies presented by the International Maritime Organization (IMO) are under preparation for commercialization. Among them, NGH tank container concept modularized transportation unit to prevent sintering effect during sea transportation. The natural gas hydrate can be vaporized in a certain part during the transportation. Unprocessed BOG increases the pressure inside the tank. Also, there is a risk of fire if you export the BOG out of the tank without proper handling. Therefore, in this study, we have studied the concept of technology to properly process BOG to modularize natural gas hydrate and to transport it to sea for long distance. The study is expected to contribute to the practical use of NGH tank container, which is a modular transport concept proposed to solve the sintering problem that occurs when transporting natural gas hydrate in the form of bulk cargo.

Keywords: Natural gas hydrate, tank container, marine transportation, boil-off gas

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40 Thermodynamic and Spectroscopic Investigation of Binary 2,2-Dimethyl-1-Propanol+ CO₂ Gas Hydrates

Authors: Seokyoon Moon, Yun-Ho Ahn, Heejoong Kim, Sujin Hong, Yunseok Lee, Youngjune Park


Gas hydrate is a non-stoichiometric crystalline compound consisting of host water-framework and low molecular weight guest molecules. Small gaseous molecules such as CH₄, CO₂, and N₂ can be captured in the host water framework lattices of the gas hydrate with specific temperature and pressure conditions. The three well-known crystal structures of structure I (sI), structure II (sII), and structure H (sH) are determined by the size and shape of guest molecules. In this study, we measured the phase equilibria of binary (2,2-dimethyl-1-propanol + CO₂, CH₄, N₂) hydrates to explore their fundamental thermodynamic characteristics. We identified the structure of the binary gas hydrate by employing synchrotron high-resolution powder diffraction (HRPD), and the guest distributions in the lattice of gas hydrate were investigated via dispersive Raman and ¹³C solid-state nuclear magnetic resonance (NMR) spectroscopies. The end-to-end distance of 2,2-dimethyl-1-propanol was calculated to be 7.76 Å, which seems difficult to be enclathrated in large cages of sI or sII. However, due to the flexibility of the host water framework, binary hydrates of sI or sII types can be formed with the help of small gas molecule. Also, the synchrotron HRPD patterns revealed that the binary hydrate structure highly depends on the type of help gases; a cubic Fd3m sII hydrate was formed with CH₄ or N₂, and a cubic Pm3n sI hydrate was formed with CO₂. Interestingly, dispersive Raman and ¹³C NMR spectra showed that the unique tuning phenomenon occurred in binary (2,2-dimethyl-1-propanol + CO₂) hydrate. By optimizing the composition of NPA, we can achieve both thermodynamic stability and high CO₂ storage capacity for the practical application to CO₂ capture.

Keywords: clathrate, gas hydrate, neopentyl alcohol, CO₂, tuning phenomenon

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39 Synthesis of Magnesium Borates from the Slurries of Magnesium Wastes by Microwave Energy

Authors: N. Tugrul, F. T. Senberber, A. S. Kipcak, E. Moroydor Derun, S. Piskin


In this research, it is aimed not only microwave synthesis of magnesium borates but also evaluation of magnesium wastes. Synthesis process can be described with the reaction of Mg wastes and boric acid using microwave energy. X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR) were applied to synthesized minerals. According to XRD results, magnesium borate hydrate mixtures were obtained as mcallisterite (pdf# = 01-070-1902, Mg2(B6O7(OH)6)2.9(H2O)) at higher crystallinity properties was achieved at the mole ratio raw material 1:1. Also, other kinds of magnesium borate hydrates were obtained at lower crystallinity such as admontite (pdf # = 01-076-0540, MgO(B2O3)3.7(H2O)), inderite (pdf # = 01-072-2308, 2MgO.3B2O3.15(H2O)) and magnesium borate hydrates (pdf # = 01-076-0539, MgO(B2O3)3.6(H2O)). FT-IR spectrums indicated that minor changes were seen at the band values of characteristic stretching in each experiment. At the end of experiments it is seen that using microwave energy may contribute positive effects to design of synthesis process such as reducing reaction time and products at higher crystallinity.

Keywords: magnesium wastes, boric acid, magnesium borate, microwave energy

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38 Understanding the Role of Gas Hydrate Morphology on the Producibility of a Hydrate-Bearing Reservoir

Authors: David Lall, Vikram Vishal, P. G. Ranjith


Numerical modeling of gas production from hydrate-bearing reservoirs requires the solution of various thermal, hydrological, chemical, and mechanical phenomena in a coupled manner. Among the various reservoir properties that influence gas production estimates, the distribution of permeability across the domain is one of the most crucial parameters since it determines both heat transfer and mass transfer. The aspect of permeability in hydrate-bearing reservoirs is particularly complex compared to conventional reservoirs since it depends on the saturation of gas hydrates and hence, is dynamic during production. The dependence of permeability on hydrate saturation is mathematically represented using permeability-reduction models, which are specific to the expected morphology of hydrate accumulations (such as grain-coating or pore-filling hydrates). In this study, we demonstrate the impact of various permeability-reduction models, and consequently, different morphologies of hydrate deposits on the estimates of gas production using depressurization at the reservoir scale. We observe significant differences in produced water volumes and cumulative mass of produced gas between the models, thereby highlighting the uncertainty in production behavior arising from the ambiguity in the prevalent gas hydrate morphology.

Keywords: gas hydrate morphology, multi-scale modeling, THMC, fluid flow in porous media

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37 Thermodynamic Phase Equilibria and Formation Kinetics of Cyclopentane, Cyclopentanone and Cyclopentanol Hydrates in the Presence of Gaseous Guest Molecules including Methane and Carbon Dioxide

Authors: Sujin Hong, Seokyoon Moon, Heejoong Kim, Yunseok Lee, Youngjune Park


Gas hydrate is an inclusion compound in which a low-molecular-weight gas or organic molecule is trapped inside a three-dimensional lattice structure created by water-molecule via intermolecular hydrogen bonding. It is generally formed at low temperature and high pressure, and exists as crystal structures of cubic systems − structure I, structure II, and hexagonal system − structure H. Many efforts have been made to apply them to various energy and environmental fields such as gas transportation and storage, CO₂ capture and separation, and desalination of seawater. Particularly, studies on the behavior of gas hydrates by new organic materials for CO₂ storage and various applications are underway. In this study, thermodynamic and spectroscopic analyses of the gas hydrate system were performed focusing on cyclopentanol, an organic molecule that forms gas hydrate at relatively low pressure. The thermodynamic equilibria of CH₄ and CO₂ hydrate systems including cyclopentanol were measured and spectroscopic analyses of XRD and Raman were performed. The differences in thermodynamic systems and formation kinetics of CO₂ added cyclopentane, cyclopentanol and cyclopentanone hydrate systems were compared. From the thermodynamic point of view, cyclopentanol was found to be a hydrate promotor. Spectroscopic analyses showed that cyclopentanol formed a hydrate crystal structure of cubic structure II in the presence of CH₄ and CO₂. It was found that the differences in the functional groups among the organic guest molecules significantly affected the rate of hydrate formation and the total amounts of CO₂ stored in the hydrate systems. The total amount of CO₂ stored in the cyclopentanone hydrate was found to be twice that of the amount of CO₂ stored in the cyclopentane and the cyclopentanol hydrates. The findings are expected to open up new opportunity to develop the gas hydrate based wastewater desalination technology.

Keywords: gas hydrate, CO₂, separation, desalination, formation kinetics, thermodynamic equilibria

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36 Microanalysis of a New Cementitious System Containing High Calcium Fly Ash and Waste Material by Scanning Electron Microscopy (SEM)

Authors: Anmar Dulaimi, Hassan Al Nageim, Felicite Ruddock, Linda Seton


Fast-curing cold bituminous emulsion mixture (CBEM) including active filler from high calcium fly ash (HCFA) and waste material (LJMU-A2) has been developed in this study. This will overcome the difficulties related with the use of hot mix asphalt such as greenhouse gases emissions and problems in keeping the temperature when transporting long distance. The aim of this study is to employ petrographic examinations using scanning electron microscopy (SEM) for characterizing the hydrates microstructure, in a new binary blended cement filler (BBCF) system. The new BBCF has been used as a replacement to traditional mineral filler in cold bituminous emulsion mixtures (CBEMs), comprises supplementary cementitious materials containing high calcium fly ash (HCFA) and a waste material (LJMU-A2). SEM analysis demonstrated the formation of hydrates after varying curing ages within the BBCF. The accelerated activation of HCFA by LJMU-A2 within the BBCF was revealed and as a consequence early and later stiffness was developed in novel CBEM.

Keywords: cold bituminous emulsion mixtures, indirect tensile stiffness modulus, scanning electron microscopy (SEM), and high calcium fly ash

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35 Efficacy of Crystalline Admixtures in Self-Healing Capacity of Fibre Reinforced Concrete

Authors: Evangelia Tsampali, Evangelos Yfantidis, Andreas Ioakim, Maria Stefanidou


The purpose of this paper is the characterization of the effects of crystalline admixtures on concrete. Crystallites, aided by the presence of humidity, form idiomorphic crystals that block cracks and pores resulting in reduced porosity. In this project, two types of crystallines have been employed. The hydrophilic nature of crystalline admixtures helps the components to react with water and cement particles in the concrete to form calcium silicate hydrates and pore-blocking precipitates in the existing micro-cracks and capillaries. The underlying mechanism relies on the formation of calcium silicate hydrates and the resulting deposits of these crystals become integrally bound with the hydrated cement paste. The crystalline admixtures continue to activate throughout the life of the composite material when in the presence of moisture entering the concrete through hairline cracks, sealing additional gaps. The resulting concrete exhibits significantly increased resistance to water penetration under stress. Admixtures of calcium aluminates can also contribute to this healing mechanism in the same manner. However, this contribution is negligible compared to the calcium silicate hydrates due to the abundance of the latter. These crystalline deposits occur throughout the concrete volume and are a permanent part of the concrete mass. High-performance fibre reinforced cementitious composite (HPFRCC) were produced in the laboratory. The specimens were exposed in three healing conditions: water immersion until testing at 15 °C, sea water immersion until testing at 15 °C, and wet/dry cycles (immersion in tap water for 3 days and drying for 4 days). Specimens were pre-cracked at 28 days, and the achieved cracks width were in the range of 0.10–0.50 mm. Furthermore, microstructure observations and Ultrasonic Pulse Velocity tests have been conducted. Based on the outcomes, self-healing related indicators have also been defined. The results show almost perfect healing capability for specimens healed under seawater, better than for specimens healed in water while inadequate for the wet/dry exposure in both of the crystalline types.

Keywords: autogenous self-healing, concrete, crystalline admixtures, ultrasonic pulse velocity test

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34 Process Integration of Natural Gas Hydrate Production by CH₄-CO₂/H₂ Replacement Coupling Steam Methane Reforming

Authors: Mengying Wang, Xiaohui Wang, Chun Deng, Bei Liu, Changyu Sun, Guangjin Chen, Mahmoud El-Halwagi


Significant amounts of natural gas hydrates (NGHs) are considered potential new sustainable energy resources in the future. However, common used methods for methane gas recovery from hydrate sediments require high investment but with low gas production efficiency, and may cause potential environment and security problems. Therefore, there is a need for effective gas production from hydrates. The natural gas hydrate production method by CO₂/H₂ replacement coupling steam methane reforming can improve the replacement effect and reduce the cost of gas separation. This paper develops a simulation model of the gas production process integrated with steam reforming and membrane separation. The process parameters (i.e., reactor temperature, pressure, H₂O/CH₄ ratio) and the composition of CO₂ and H₂ in the feed gas are analyzed. Energy analysis is also conducted. Two design scenarios with different composition of CO₂ and H₂ in the feed gas are proposed and evaluated to assess the energy efficiency of the novel system. Results show that when the composition of CO₂ in the feed gas is between 43 % and 72 %, there is a certain composition that can meet the requirement that the flow rate of recycled gas is equal to that of feed gas, so as to ensure that the subsequent production process does not need to add feed gas or discharge recycled gas. The energy efficiency of the CO₂ in feed gas at 43 % and 72 % is greater than 1, and the energy efficiency is relatively higher when the CO₂ mole fraction in feed gas is 72 %.

Keywords: Gas production, hydrate, process integration, steam reforming

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33 Experimental Quantification and Modeling of Dissolved Gas during Hydrate Crystallization: CO₂ Hydrate Case

Authors: Amokrane Boufares, Elise Provost, Veronique Osswald, Pascal Clain, Anthony Delahaye, Laurence Fournaison, Didier Dalmazzone


Gas hydrates have long been considered as problematic for flow assurance in natural gas and oil transportation. On the other hand, they are now seen as future promising materials for various applications (i.e. desalination of seawater, natural gas and hydrogen storage, gas sequestration, gas combustion separation and cold storage and transport). Nonetheless, a better understanding of the crystallization mechanism of gas hydrate and of their formation kinetics is still needed for a better comprehension and control of the process. To that purpose, measuring the real-time evolution of the dissolved gas concentration in the aqueous phase during hydrate formation is required. In this work, CO₂ hydrates were formed in a stirred reactor equipped with an Attenuated Total Reflection (ATR) probe coupled to a Fourier Transform InfraRed (FTIR) spectroscopy analyzer. A method was first developed to continuously measure in-situ the CO₂ concentration in the liquid phase during solubilization, supersaturation, hydrate crystallization and dissociation steps. Thereafter, the measured concentration data were compared with those of equilibrium concentrations. It was observed that the equilibrium is instantly reached in the liquid phase due to the fast consumption of dissolved gas by the hydrate crystallization. Consequently, it was shown that hydrate crystallization kinetics is limited by the gas transfer at the gas-liquid interface. Finally, we noticed that the liquid-hydrate equilibrium during the hydrate crystallization is governed by the temperature of the experiment under the tested conditions.

Keywords: gas hydrate, dissolved gas, crystallization, infrared spectroscopy

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32 Modeling of Gas Extraction from a Partially Gas-Saturated Porous Gas Hydrate Reservoir with Respect to Thermal Interactions with Surrounding Rocks

Authors: Angelina Chiglintseva, Vladislav Shagapov


We know from the geological data that quite sufficient gas reserves are concentrated in hydrates that occur on the Earth and on the ocean floor. Therefore, the development of these sources of energy and the storage of large reserves of gas hydrates is an acute global problem. An advanced technology for utilizing gas is to store it in a gas-hydrate state. Under natural conditions, storage facilities can be established, e.g., in underground reservoirs, where quite large volumes of gas can be conserved compared with reservoirs of pure gas. An analysis of the available experimental data of the kinetics and the mechanism of the gas-hydrate formation process shows the self-conservation effect that allows gas to be stored at negative temperatures and low values of pressures of up to several atmospheres. A theoretical model has been constructed for the gas-hydrate reservoir that represents a unique natural chemical reactor, and the principal possibility of the full extraction of gas from a hydrate due to the thermal reserves of the reservoirs themselves and the surrounding rocks has been analyzed. The influence exerted on the evolution of a gas hydrate reservoir by the reservoir thicknesses and the parameters that determine its initial state (a temperature, pressure, hydrate saturation) has been studied. It has been established that the shortest time of exploitation required by the reservoirs with a thickness of a few meters for the total hydrate decomposition is recorded in the cyclic regime when gas extraction alternated with the subsequent conservation of the gas hydrate deposit. The study was performed by a grant from the Russian Science Foundation (project No.15-11-20022).

Keywords: conservation, equilibrium state, gas hydrate reservoir, rocks

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31 Avoiding Gas Hydrate Problems in Qatar Oil and Gas Industry: Environmentally Friendly Solvents for Gas Hydrate Inhibition

Authors: Nabila Mohamed, Santiago Aparicio, Bahman Tohidi, Mert Atilhan


Qatar's one of the biggest problem in processing its natural resource, which is natural gas, is the often occurring blockage in the pipelines caused due to uncontrolled gas hydrate formation in the pipelines. Several millions of dollars are being spent at the process site to dehydrate the blockage safely by using chemical inhibitors. We aim to establish national database, which addresses the physical conditions that promotes Qatari natural gas to form gas hydrates in the pipelines. Moreover, we aim to design and test novel hydrate inhibitors that are suitable for Qatari natural gas and its processing facilities. From these perspectives we are aiming to provide more effective and sustainable reservoir utilization and processing of Qatari natural gas. In this work, we present the initial findings of a QNRF funded project, which deals with the natural gas hydrate formation characteristics of Qatari type gas in both experimental (PVTx) and computational (molecular simulations) methods. We present the data from the two fully automated apparatus: a gas hydrate autoclave and a rocking cell. Hydrate equilibrium curves including growth/dissociation conditions for multi-component systems for several gas mixtures that represent Qatari type natural gas with and without the presence of well known kinetic and thermodynamic hydrate inhibitors. Ionic liquids were designed and used for testing their inhibition performance and their DFT and molecular modeling simulation results were also obtained and compared with the experimental results. Results showed significant performance of ionic liquids with up to 0.5 % in volume with up to 2 to 4 0C inhibition at high pressures.

Keywords: gas hydrates, natural gas, ionic liquids, inhibition, thermodynamic inhibitors, kinetic inhibitors

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30 Predicting Long-Term Performance of Concrete under Sulfate Attack

Authors: Elakneswaran Yogarajah, Toyoharu Nawa, Eiji Owaki


Cement-based materials have been using in various reinforced concrete structural components as well as in nuclear waste repositories. The sulfate attack has been an environmental issue for cement-based materials exposed to sulfate bearing groundwater or soils, and it plays an important role in the durability of concrete structures. The reaction between penetrating sulfate ions and cement hydrates can result in swelling, spalling and cracking of cement matrix in concrete. These processes induce a reduction of mechanical properties and a decrease of service life of an affected structure. It has been identified that the precipitation of secondary sulfate bearing phases such as ettringite, gypsum, and thaumasite can cause the damage. Furthermore, crystallization of soluble salts such as sodium sulfate crystals induces degradation due to formation and phase changes. Crystallization of mirabilite (Na₂SO₄:10H₂O) and thenardite (Na₂SO₄) or their phase changes (mirabilite to thenardite or vice versa) due to temperature or sodium sulfate concentration do not involve any chemical interaction with cement hydrates. Over the past couple of decades, an intensive work has been carried out on sulfate attack in cement-based materials. However, there are several uncertainties still exist regarding the mechanism for the damage of concrete in sulfate environments. In this study, modelling work has been conducted to investigate the chemical degradation of cementitious materials in various sulfate environments. Both internal and external sulfate attack are considered for the simulation. In the internal sulfate attack, hydrate assemblage and pore solution chemistry of co-hydrating Portland cement (PC) and slag mixing with sodium sulfate solution are calculated to determine the degradation of the PC and slag-blended cementitious materials. Pitzer interactions coefficients were used to calculate the activity coefficients of solution chemistry at high ionic strength. The deterioration mechanism of co-hydrating cementitious materials with 25% of Na₂SO₄ by weight is the formation of mirabilite crystals and ettringite. Their formation strongly depends on sodium sulfate concentration and temperature. For the external sulfate attack, the deterioration of various types of cementitious materials under external sulfate ingress is simulated through reactive transport model. The reactive transport model is verified with experimental data in terms of phase assemblage of various cementitious materials with spatial distribution for different sulfate solution. Finally, the reactive transport model is used to predict the long-term performance of cementitious materials exposed to 10% of Na₂SO₄ for 1000 years. The dissolution of cement hydrates and secondary formation of sulfate-bearing products mainly ettringite are the dominant degradation mechanisms, but not the sodium sulfate crystallization.

Keywords: thermodynamic calculations, reactive transport, radioactive waste disposal, PHREEQC

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29 Study of Nucleation and Growth Processes of Ettringite in Supersaturated Diluted Solutions

Authors: E. Poupelloz, S. Gauffinet


Ettringite Ca₆Al₂(SO₄)₃(OH)₁₂26H₂O is one of the major hydrates formed during cement hydration. Ettringite forms in Portland cement from the reaction between tricalcium aluminate Ca₃Al₂O₆ and calcium sulfate. Ettringite is also present in calcium sulfoaluminate cement in which it is the major hydrate, formed by the reaction between yeelimite Ca₄(AlO₂)₆SO₄ and calcium sulfate. About the formation of ettringite, numerous results are available in the literature even if some issues are still under discussion. However, almost all published work about ettringite was done on cementitious systems. Yet in cement, hydration reactions are very complex, the result of dissolution-precipitation processes and are submitted to various interactions. Understanding the formation process of a phase alone, here ettringite, is the first step to later understand the much more complex reactions happening in cement. This study is crucial for the comprehension of early cement hydration and physical behavior. Indeed formation of hydrates, in particular, ettringite, will have an influence on the rheological properties of the cement paste and on the need for admixtures. To make progress toward the understanding of existing phenomena, a specific study of nucleation and growth processes of ettringite was conducted. First ettringite nucleation was studied in ionic aqueous solutions, with controlled but different experimental conditions, as different supersaturation degrees (β), different pH or presence of exogenous ions. Through induction time measurements, interfacial ettringite crystals solution energies (γ) were determined. Growth of ettringite in supersaturated solutions was also studied through chain crystallization reactions. Specific BET surface area measurements and Scanning Electron Microscopy observations seemed to prove that growth process is favored over the nucleation process when ettringite crystals are initially present in a solution with a low supersaturation degree. The influence of stirring on ettringite formation was also investigated. Observation was made that intensity and nature of stirring have a high influence on the size of ettringite needles formed. Needle sizes vary from less than 10µm long depending on the stirring to almost 100µm long without any stirring. During all previously mentioned experiments, initially present ions are consumed to form ettringite in such a way that the supersaturation degree with regard to ettringite is decreasing over time. To avoid this phenomenon a device compensating the drop of ion concentrations by adding some more solutions, and therefore always have constant ionic concentrations, was used. This constant β recreates the conditions of the beginning of cement paste hydration, when the dissolution of solid reagents compensates the consumption of ions to form hydrates. This device allowed the determination of the ettringite precipitation rate as a function of the supersaturation degree β. Taking samples at different time during ettringite precipitation and doing BET measurements allowed the determination of the interfacial growth rate of ettringite in m²/s. This work will lead to a better understanding and control of ettringite formation alone and thus during cements hydration. This study will also ultimately define the impact of ettringite formation process on the rheology of cement pastes at early age, which is a crucial parameter from a practical point of view.

Keywords: cement hydration, ettringite, morphology of crystals, nucleation-growth process

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28 Optical Properties of Tetrahydrofuran Clathrate Hydrates at Terahertz Frequencies

Authors: Hyery Kang, Dong-Yeun Koh, Yun-Ho Ahn, Huen Lee


Terahertz time-domain spectroscopy (THz-TDS) was used to observe the THF clathrate hydrate system with dosage of polyvinylpyrrolidone (PVP) with three different average molecular weights (10,000 g/mol, 40,000 g/mol, 360,000 g/mol). Distinct footprints of phase transition in the THz region (0.4 - 2.2 THz) were analyzed and absorption coefficients and complex refractive indices are obtained and compared in the temperature range of 253 K to 288 K. Along with the optical properties, ring breathing and stretching modes for different molecular weights of PVP in THF hydrate are analyzed by Raman spectroscopy.

Keywords: clathrate hydrate, terahertz, polyvinylpyrrolidone (PVP), THz-TDS, inhibitor

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27 Numerical Analysis of CO₂ Storage as Clathrates in Depleted Natural Gas Hydrate Formation

Authors: Sheraz Ahmad, Li Yiming, Li XiangFang, Xia Wei, Zeen Chen


Holding CO₂ at massive scale in the enclathrated solid matter called hydrate can be perceived as one of the most reliable methods for CO₂ sequestration to take greenhouse gases emission control measures and global warming preventive actions. In this study, a dynamically coupled mass and heat transfer mathematical model is developed which elaborates the unsteady behavior of CO₂ flowing into a porous medium and converting itself into hydrates. The combined numerical model solution by implicit finite difference method is explained and through coupling the mass, momentum and heat conservation relations, an integrated model can be established to analyze the CO₂ hydrate growth within P-T equilibrium conditions. CO₂ phase transition, effect of hydrate nucleation by exothermic heat release and variations of thermo-physical properties has been studied during hydrate nucleation. The results illustrate that formation pressure distribution becomes stable at the early stage of hydrate nucleation process and always remains stable afterward, but formation temperature is unable to keep stable and varies during CO₂ injection and hydrate nucleation process. Initially, the temperature drops due to cold high-pressure CO₂ injection since when the massive hydrate growth triggers and temperature increases under the influence of exothermic heat evolution. Intermittently, it surpasses the initial formation temperature before CO₂ injection initiates. The hydrate growth rate increases by increasing injection pressure in the long formation and it also expands overall hydrate covered length in the same induction period. The results also show that the injection pressure conditions and hydrate growth rate affect other parameters like CO₂ velocity, CO₂ permeability, CO₂ density, CO₂ and H₂O saturation inside the porous medium. In order to enhance the hydrate growth rate and expand hydrate covered length, the injection temperature is reduced, but it did not give satisfactory outcomes. Hence, CO₂ injection in vacated natural gas hydrate porous sediment may form hydrate under low temperature and high-pressure conditions, but it seems very challenging on a huge scale in lengthy formations.

Keywords: CO₂ hydrates, CO₂ injection, CO₂ Phase transition, CO₂ sequestration

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26 Influence of Variable Calcium Content on Mechanical Properties of Geopolymer Synthesized at Different Temperature and Moisture Conditions

Authors: Suraj D. Khadka, Priyantha W. Jayawickrama


In search of a sustainable construction material, geopolymer has been investigated for past decades to evaluate its advantage over conventional products. Synthesis of geopolymer requires a source of aluminosilicate mixed with sodium hydroxide and sodium silicate at different proportions to maintain a Si/Al molar ratio of 1-3 and Na/Al molar ratio of unity. A comprehensive geopolymer study was performed with Metakaolin and Class C Fly ash as primary aluminosilicate sources. Synthesized geopolymer was analyzed for time-dependent viscosity, setting period and strength at varying initial moisture content, curing temperature and humidity. Different concentration of Ca(OH)₂ and CaSO₄.2H₂O were added to vary the amount of calcium contained in synthesized geopolymer. Influence of calcium content in unconfined compressive strength behavior of geopolymer were analyzed. Finally, Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS) was performed to investigate the hardened product. It was observed that fly ash based geopolymer had shortened setting time and faster increase in viscosity as compared to geopolymer synthesized from metakaolin. This was primarily attributed to higher calcium content resulting in formation of calcium silicate hydrates (CSH). SEM-EDS was performed to verify the presence of CSH phases. Spectral analysis of geopolymer prepared by addition of Ca(OH)₂ and CaSO₄.2H₂O indicated higher CSH phases at higher concentration. It was observed that lower concentration of added calcium favored strength gain in geopolymer. However, at higher calcium concentration, decrease in strength was observed. Strength variation was also observed with humidity at initial curing condition. At 100% humidity, geopolymer with added calcium presented higher strength compared to samples cured at ambient humidity condition (40%). Reduction in strength in these samples at lower humidity was primarily attributed to reduction in moisture content in specimen due to the formation of CSH phases and loss of moisture through evaporation. For low calcium content geopolymers, with increase in temperature, gain in strength was observed with maximum strength observed at 200 ˚C. However, samples with higher calcium content demonstrated severe cracking resulting in low strength at elevated temperatures.

Keywords: calcium silicate hydrates, geopolymer, humidity, Scanning Electron Microscopy-Energy Dispersive Spectroscopy, unconfined compressive strength

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25 Production of Natural Gas Hydrate by Using Air and Carbon Dioxide

Authors: Yun-Ho Ahn, Hyery Kang, Dong-Yeun Koh, Huen Lee


In this study, we demonstrate the production of natural gas hydrates from permeable marine sediments with simultaneous mechanisms for methane recovery and methane-air or methane-air/carbon dioxide replacement. The simultaneous melting happens until the chemical potentials become equal in both phases as natural gas hydrate depletion continues and self-regulated methane-air replacement occurs over an arbitrary point. We observed certain point between dissociation and replacement mechanisms in the natural gas hydrate reservoir, and we call this boundary as critical methane concentration. By the way, when carbon dioxide was added, the process of chemical exchange of methane by air/carbon dioxide was observed in the natural gas hydrate. The suggested process will operate well for most global natural gas hydrate reservoirs, regardless of the operating conditions or geometrical constraints.

Keywords: air injection, carbon dioxide sequestration, hydrate production, natural gas hydrate

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24 Nondestructive Natural Gas Hydrate Production by Using Air and Carbon Dioxide

Authors: Ahn Yun-Ho, Hyery Kang, Koh Dong-Yeun, Huen Lee


In this study, we demonstrate the production of natural gas hydrates from permeable marine sediments with simultaneous mechanisms for methane recovery and methane-air or methane-air/carbon dioxide replacement. The simultaneous melting happens until the chemical potentials become equal in both phases as natural gas hydrate depletion continues and self-regulated methane-air replacement occurs over an arbitrary point. We observed certain point between dissociation and replacement mechanisms in the natural gas hydrate reservoir, and we call this boundary as critical methane concentration. By the way, when carbon dioxide was added, the process of chemical exchange of methane by air/carbon dioxide was observed in the natural gas hydrate. The suggested process will operate well for most global natural gas hydrate reservoirs, regardless of the operating conditions or geometrical constraints.

Keywords: air injection, carbon dioxide sequestration, hydrate production, natural gas hydrate

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23 Investigate the Effects of Anionic Surfactant on THF Hydrate

Authors: Salah A. Al-Garyani, Yousef Swesi


Gas hydrates can be hazardous to upstream operations. On the other hand, the high gas storage capacity of hydrate may be utilized for natural gas storage and transport. Research on the promotion of hydrate formation, as related to natural gas storage and transport, has received relatively little attention. The primary objective of this study is to gain a better understanding of the effects of ionic surfactants, particularly their molecular structures and concentration, on the formation of tetrahydrofuran (THF) hydrate, which is often used as a model hydrate former for screening hydrate promoters or inhibitors. The surfactants studied were sodium n-dodecyl sulfate (SDS), sodium n-hexadecyl sulfate (SHS). Our results show that, at concentrations below the solubility limit, the induction time decreases with increasing surfactant concentration. At concentrations near or above the solubility, however, the surfactant concentration no longer has any effect on the induction time. These observations suggest that the effect of surfactant on THF hydrate formation is associated with surfactant monomers, not the formation of micelle as previously reported. The lowest induction time (141.25 ± 21 s, n = 4) was observed in a solution containing 7.5 mM SDS. The induction time decreases by a factor of three at concentrations near or above the solubility, compared to that without surfactant.

Keywords: tetrahydrofuran, hydrate, surfactant, induction time, monomers, micelle

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22 Comparison of the Hydration Products of Commercial and Experimental Calcium Silicate Cement: The Preliminary Observational Study

Authors: Seok Woo Chang


Aim: The objective of this study was to compare and evaluate the hydration products of commercial and experimental calcium silicate cement. Materials and Methods: The commercial calcium silicate cement (ProRoot MTA, Dentsply) and experimental calcium silicate cement (n=10) were mixed with distilled water (water/powder ratio = 20 w/w) and stirred at room temperature for 10 hours. These mixtures were dispersed on wafer and dried for 12 hours at room temperature. Thereafter, the dried specimens were examined with Scanning Electron Microscope (SEM). Electron Dispersive Spectrometry (EDS) was also carried out. Results: The commercial calcium silicate cement (ProRoot MTA) and experimental calcium silicate cement both showed precipitation of rod-like and globule-like crystals. Based on EDS analysis, these precipitates were supposed to be calcium hydroxide or calcium silicate hydrates. The degree of formation of these precipitates was higher in commercial MTA. Conclusions: Based on the results, both commercial and experimental calcium silicate cement had ability to produce calcium hydroxide or calcium silicate hydrate precipitates.

Keywords: calcium silicate cement, ProRoot MTA, precipitation, calcium hydroxide, calcium silicate hydrate

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21 Characterization of Cement Mortar Based on Fine Quartz

Authors: K. Arroudj, M. Lanez, M. N. Oudjit


The introduction of siliceous mineral additions in cement production allows, in addition to the ecological and economic gain, improvement of concrete performance. This improvement is mainly due to the fixing of Portlandite, released during the hydration of cement, by fine siliceous, forming denser calcium silicate hydrates and therefore a more compact cementitious matrix. This research is part of the valuation of the Dune Sand (DS) in the cement industry in Algeria. The high silica content of DS motivated us to study its effect, at ground state, on the properties of mortars in fresh and hardened state. For this purpose, cement pastes and mortars based on ground dune sand (fine quartz) has been analyzed with a replacement to cement of 15%, 20% and 25%. This substitution has reduced the amount of heat of hydration and avoids any risk of initial cracking. In addition, the grinding of the dune sand provides amorphous thin populations adsorbed at the surface of the crystal particles of quartz. Which gives to ground quartz pozzolanic character. This character results an improvement of mechanical strength of mortar (66 MPa in the presence of 25% of ground quartz).

Keywords: mineralogical structure, pozzolanic reactivity, Quartz, mechanical strength

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20 Damage in Cementitious Materials Exposed to Sodium Chloride Solution and Thermal Cycling: The Effect of Using Supplementary Cementitious Materials

Authors: Fadi Althoey, Yaghoob Farnam


Sodium chloride (NaCl) can interact with the tricalcium aluminate (C3A) and its hydrates in concrete matrix. This interaction can result in formation of a harmful chemical phase as the temperature changes. It is thought that this chemical phase is embroiled in the premature concrete deterioration in the cold regions. This work examines the potential formation of the harmful chemical phase in various pastes prepared by using different types of ordinary portland cement (OPC) and supplementary cementitious materials (SCMs). The quantification of the chemical phase was done by using a low temperature differential scanning calorimetry. The results showed that the chemical phase formation can be reduced by using Type V cement (low content of C3A). The use of SCMs showed different behaviors on the formation of the chemical phase. Slag and Class F fly ash can reduce the chemical phase by the dilution of cement whereas silica fume can reduce the amount of the chemical phase by dilution and pozzolanic activates. Interestingly, the use of Class C fly ash has a negative effect on concrete exposed to NaCl through increasing the formation of the chemical phase.

Keywords: concrete, damage, chemcial phase, NaCl, SCMs

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19 Influence of Silica Fume on the Hydration of Cement Pastes Studied by Simultaneous TG-DSC Analysis

Authors: Anton Trník, Lenka Scheinherrová, Robert Černý


Silica fume is a by-product of the ferro-silicon and silicon metal industries. It is mainly in the form of amorphous silica. Silica fume belongs to pozzolanic active materials which can be used in concrete to improve its final properties. In this paper, the influence of silica fume on hydration of cement pastes is studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) at various curing times (2, 7, 28, and 90 days) in the temperature range from 25 to 1000 °C in an argon atmosphere. Samples are prepared from Portland cement CEM I 42.5 R which is partially replaced with the silica fume of 4, 8, and 12 wt.%. The water/binder ratio is chosen as 0.5. It is identified and described the liberation of physically bound water, calcium–silicate–hydrates dehydration, portlandite and calcite decomposition in studied samples. Also, it is found out that an exothermic peak at 950 °C is observed without a significant mass change for samples with 12 wt.% of silica fume after two days of hydration. This peak is probably caused by the pozzolanic reaction between silica fume and Portland cement. Its size corresponds to the degree of crystallization between Ca and Si. The portlandite content is lower for the samples with a higher amount of silica fume.

Keywords: differential scanning calorimetry, hydration, silica fume, thermogravimetry

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18 Carbonation and Mechanical Performance of Reactive Magnesia Based Formulations

Authors: Cise Unluer


Reactive MgO hydrates to form brucite (Mg(OH)2, magnesium hydroxide), which can then react with CO2 and additional water to form a range of strength providing hydrated magnesium carbonates (HMCs) within cement-based formulations. The presented work focuses on the use of reactive MgO in a range of concrete mixes, where it carbonates by absorbing CO2 and gains strength accordingly. The main goal involves maximizing the amount of CO2 absorbed within construction products, thereby reducing the overall environmental impact of the designed formulations. Microstructural analyses including scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermogravimetry/differential thermal analysis (TG/DTA) are used in addition to porosity, permeability and unconfined compressive strength (UCS) testing to understand the performance mechanisms. XRD Reference Intensity Ratio (RIR), acid digestion and TG/DTA are utilized to quantify the amount of CO2 sequestered, with the goal of achieving 100% carbonation through careful mix design, leading to a range of carbon neutral products with high strengths. As a result, samples stronger than those containing Portland cement (PC) were produced, revealing the link between the mechanical performance and microstructural development of the developed formulations with the amount of CO2 sequestered.

Keywords: carbonation, compressive strength, reactive MgO cement, sustainability

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17 Compatibility of Copolymer-Based Grinding Aids and Sulfonated Acetone-Formaldehyde Superplasticizer

Authors: Zhang Tailong


Compatibility between sulfonated acetone-formalehyde superplasticizer (SAF) and copolymer-based grinding aids (GA) were studied by fluidity, Zeta potential, setting time of cement pasts, initial slump and slump flow of concrete and compressive strength of concrete. ESEM, MIP, and XRD were used to investigate the changing of microstructure of interior concrete. The results indicated that GA could noticeably enhance the dispersion ability of SAF. It was found that better fluidity and slump-keeping ability of cement paste were obtained in the case of GA. In addition, GA and SAF together had a certain retardation effect on hydration of cement paste. With increasing of the GA dosage, the dispersion ability and retardation effect of admixture increased. The compressive strength of the sample made with SAF and GA after 28 days was higher than that of the control sample made only with SAF. The initial slump and slump flow of concrete increased by 10.0% and 22.9%, respectively, while 0.09 wt.% GA was used. XRD examination indicated that new products were not found in the case of GA. In addition, more dense arrangement of hydrates and lower porosity of the specimen were observed by ESEM and MIP, which contributed to higher compressive strength.

Keywords: copolymer-based grinding aids, superplasiticizer, compatibility, microstructure, cement, concrete

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16 Assessment of the Performance of Fly Ash Based Geo-Polymer Concrete under Sulphate and Acid Attack

Authors: Talakokula Visalakshi


Concrete is the most commonly used construction material across the globe, its usage is second only to water. It is prepared using ordinary Portland cement whose production contributes to 5-8% of total carbon emission in the world. On the other hand the fly ash by product from the power plants is produced in huge quantities is termed as waste and disposed in landfills. In order to address the above issues mentioned, it is essential that other forms of binding material must be developed in place of cement to make concrete. The geo polymer concrete is one such alternative developed by Davidovits in 1980’s. Geopolymer do not form calcium-silicate hydrates for matrix formation and strength but undergo polycondensation of silica and alumina precursors to attain structural strength. Its setting mechanism depends upon polymerization rather than hydration. As a result it is able to achieve its strength in 3-5 days whereas concrete requires about a month to do the same. The objective of this research is to assess the performance of geopolymer concrete under sulphate and acid attack. The assessment is done based on the experiments conducted on geopolymer concrete. The expected outcomes include that if geopolymer concrete is more durable than normal concrete, then it could be a competitive replacement option of concrete and can lead to significant reduction of carbon foot print and have a positive impact on the environment. Fly ash based geopolymer concrete offers an opportunity to completely remove the cement content from concrete thereby making the concrete a greener and future construction material.

Keywords: fly ash, geo polymer, geopolymer concrete, construction material

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15 Unbranched, Saturated, Carboxylic Esters as Phase-Change Materials

Authors: Anastasia Stamatiou, Melissa Obermeyer, Ludger J. Fischer, Philipp Schuetz, Jörg Worlitschek


This study evaluates unbranched, saturated carboxylic esters with respect to their suitability to be used as storage media for latent heat storage applications. Important thermophysical properties are gathered both by means of literature research as well as by experimental measurements. Additionally, esters are critically evaluated against other common phase-change materials in terms of their environmental impact and their economic potential. The experimental investigations are performed for eleven selected ester samples with a focus on the determination of their melting temperature and their enthalpy of fusion using differential scanning calorimetry. Transient Hot Bridge was used to determine the thermal conductivity of the liquid samples while thermogravimetric analysis was employed for the evaluation of the 5% weight loss temperature as well as of the decomposition temperature of the non-volatile samples. Both experimental results and literature data reveal the high potential of esters as phase-change materials. Their good thermal and environmental properties as well as the possibility for production from natural sources (e.g. vegetable oils) render esters as very promising for future storage applications. A particularly high short term application potential of esters could lie in low temperature storage applications where the main alternative is using salt hydrates as phase-change material.

Keywords: esters, phase-change materials, thermal properties, latent heat storage

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14 High Resolution Solid State NMR Structural Study of a Ternary Hydraulic Mixture

Authors: Rym Sassi, Franck Fayon, Mohend Chaouche, Emmanuel Veron, Valerie Montouillout


The chemical phenomena occurring during cement hydration are complex and interdependent, and even after almost two centuries of studies, they are still difficult to solve for complex mixtures combining different hydraulic binders. Powder-XRD has been widely used for characterizing the crystalline phases in both anhydrous and hydrated cement, but only limited information is obtained in the case of strongly disordered and amorphous phases. In contrast, local spectroscopies like solid-state NMR can provide a quantitative description of noncrystalline phases. In this work, the structural modifications occurring during hydration of a fast-setting ternary binder based on white Portland cement, white calcium aluminate cement, and calcium sulfate were investigated using advanced solid-state NMR methods. We particularly focused on the early stage of the hydration up to 28 days, working with samples whose hydration was controlled and stopped. ²⁷Al MQ-MAS as well as {¹H}-²⁷Al and {¹H}-²⁹Si Cross- Polarization MAS NMR techniques were combined to distinguish all of the aluminum and silicon species formed during the hydration. The NMR quantification of the different phases was conducted in parallel with the XRD analyses. The consumption of initial products, as well as the precipitation of hydraulic phases (ettringite, monosulfate, strätlingite, CSH, and CASH), were unambiguously quantified. Finally, the drawing of the consumption and formation of phases was correlated with mechanical strength measurements.

Keywords: cement, hydration, hydrates structure, mechanical strength, NMR

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