Advances of experimental study on gas production from synthetic hydrate reservoir in China

China has entered the area of new normal economy which requires the harmonious development of energy consumption, environmental protection and economic development. Natural gas hydrate is a potential clean energy with tremendous reserve in China. The successful field test of marine hydrate exploitation in South China Sea created a new record of the longest continuous gas production from natural gas hydrate. However, the corresponding fundamental research is still urgently needed in order to narrow the gap between field test and commercial production. This paper reviewed the latest advances of experimental study on gas production from hydrate reservoir in China. The experimental apparatus for investigating the performance of hydrate dissociation in China has developed from one dimensional to two dimensional and three dimensional. In addition, well configuration developed from one tube to complicated multi-well networks to satisfy the demand of different production models. Besides, diverse testing methods have been established. The reviewed papers preliminary discussed the mechanical properties and the sediment deformation situation during the process of hydrate dissociation. However, most reported articles only consider the physical factor, the coupled mechanism of physical and chemical factor for the mechanical properties of the sediment and the sand production problem should be studied further.     

Reviews of gas hydrate inhibitors in gas-dominant pipelines and application of kinetic hydrate inhibitors in China

During the development and application of natural gas, hydrate plugging the pipelines is a very important issue to solve. Currently, adding thermodynamic hydrate inhibitors (THIs) and kinetic hydrate inhibitors (KHIs) in gas-dominated pipelines is a main way to prevent hydrate plugging of flow lines. This paper mainly reviews the efforts to develop THIs and KHIs in the past 20 years, compare the role of various THIs, such as methanol, ethylene glycol and electrolyte, and give the tips in using. The direction of KHIs is toward high efficiency, low toxicity, low pollution and low cost. More than a hundred inhibitors, including polymers, natural products and ionic liquids, have been synthesized in the past decade. Some of them have better performance than the current commercial KHIs. However, there are still few problems, such as the complex synthesis process, high cost and low solubility, impeding the commercialization of these inhibitors. The review also summarized some application of KHIs in China. Research of KHIs in China began late. There are no KHIs used in gas pipelines. Only a few field tests have been carried out. In the end of this paper, the field test of self-developed KHIs by China is summarized, and the guidance is given according to the application results.     

Unusual kinetic inhibitor effects on gas hydrate formation

Gas hydrate formation experiments were conducted with a methane-ethane mixture at 273.7 or 273.9 K and 5100 kPa and using water droplets or water contained in cylindrical glass columns. The effect of kinetic inhibitors and the water/solid interface on the induction time for hydrate crystallization and on the hydrate growth and decomposition characteristics was studied. It was found that inhibitors GHI 101 and Luvicap EG delayed the onset of hydrate nucleation. While this inhibition effects has been reported previously some unusual behaviour was observed and reported for the first time. In particular, the water droplet containing GHI 101 or Luvicap EG was found to collapse prior to nucleation and spread out on the Teflon surface. Subsequently, hydrate was formed as a layer on the surface. Catastrophic growth and spreading of the hydrate crystals was also observed during hydrate formation in the glass columns in the presence of the kinetic inhibitor. Finally, when polyethylene oxide (PEO) was added into the kinetic inhibitor solution the memory effect on the induction time decreased dramatically.     

Geomechanics involved in gas hydrate recovery

Gas hydrate is regarded as a promising energy owing to the large carbon reserve and high energy density. However, due to the particularity of the formation and the complexity of exploitation process, the commercial exploitation of gas hydrate has not been realized. This paper reviews the physical properties of gas hydrate-bearing sediments and focuses on the geomechanical response during the exploitation. The exploitation of gas hydrate is a strong thermal–hydrological–mechanical–chemical (THMC) coupling process: decomposition of hydrate into water and gas produces multi-physical processes including heat transfer, multi-fluid flow and deformation in the reservoir. These physical processes lead to a potential of geomechanical issues during the production process. Frequent occurrence of sand production is the major limitation of the commercial exploitation of gas hydrate. The potential landslide and subsidence will lead to the cessation of the production and even serious accidents. Preliminary researches have been conducted to investigate the geomechanical properties of gas hydrate-bearing sediments and to assess the wellbore integrity during the exploitation. The physical properties of hydrate have been fully studied, and some models have been established to describe the physical processes during the exploitation of gas hydrate. But the reproduction of actual conditions of hydrate reservoir in the laboratory is still a huge challenge, which will inevitably lead to a bias of experiment. In addition, because of the effect of microscopic mechanisms in porous media, the coupling mechanism of the existing models should be further investigated. Great efforts, however, are still required for a comprehensive understanding of this strong coupling process that is extremely different from the geomechanics involved in the conventional reservoirs.     

An investigation into the laboratory method for the evaluation of the performance of kinetic hydrate inhibitors using superheated gas hydrates

Kinetic hydrate inhibitors (KHIs) are used to prevent gas hydrate formation in gas and oilfield operations. Recently, a new KHI test method was reported in which hydrates are formed and re-melted just above the equilibrium temperature, before the fluids are re-cooled and the performance of the chemical as a KHI is determined. The method, which we have called the superheated hydrate test method, is claimed to be more reliable for KHI ranking in small equipment, giving less scattering in the hold time data due to avoiding the stochastic nature of the first hydrate formation. We have independently investigated this superheated hydrate test method in steel and sapphire autoclave tests using a gas mixture forming Structure II hydrates and a liquid hydrocarbon phase, which was necessary for satisfactory results. Our results indicate that hold times are shorter than using non-superheated hydrate test methods, but they are more reproducible with less scattering. The reduced scattering occurs in isothermal or slow ramping experiments even when the hydrates are melted at more than 10 °C above the equilibrium temperature (T_eq). However, if a rapid cooling method is used, the improved reproducibility is retained when melting hydrate at 2.4 °C above T_eq but lost when warming to 8.4 °C above T_eq. Using the ramping test method, most, but not all the KHIs tested agreed with the same performance ranking obtained using traditional non-superheated hydrate test methods. This may be related to the variation in the dissociation temperature of gas hydrates with different KHIs and different KHI inhibition mechanisms. Results also varied between different size autoclave equipments.     

Surfactant effects on hydrate formation in an unstirred gas/liquid system: An experimental study using methane and sodium alkyl sulfates

This paper reports an experimental study on the effects of surfactant additives on the formation of a clathrate hydrate in a quiescent methane/liquid-water system, which was initially composed of a 300-cm³ aqueous phase and an ∼640-cm³ methane-gas phase, then successively provided with methane such that the system pressure was held constant. The surfactants used in the present study were three sodium alkyl sulfates appreciably different in the alkyl chain length—they were sodium dodecyl sulfate (abbreviated as SDS), sodium tetradecyl sulfate (abbreviated as STS) and sodium hexadecyl sulfate (abbreviated as SHS). For each surfactant added to water up to, at most, 1.82-3.75 times the solubility, we performed visual observations of hydrate formation simultaneously with the measurements of methane uptake due to the hydrate formation. The qualitative hydrate-formation behavior thus observed was almost the same irrespective of the species as well as the initial concentration of the surfactant used; i.e., thick, highly porous hydrate layers were formed and grew on the horizontal gas/liquid interface and also on the test-chamber wall above the level of the gas/liquid interface. In each experimental operation, hydrate formation continued for a limited time (from ∼6 to ) and then practically ceased, leaving only a small proportion (typically 15% or less) of the aqueous solution unconverted into hydrate crystals. The variations in the time-averaged rate of hydrate formation (as measured by the rate of methane uptake) and the final water-to-hydrate conversion ratio with the initial concentration of each surfactant were investigated. Moreover, we examined the promotion of hydrate formation with the aid of a water-cooled cold plate, a steel-made flat-plate-type heat sink, vertically dipped into the aqueous phase across the gas/liquid interface.     

Surfactant effects on hydrate formation in an unstirred gas/liquid system: Amendments to the previous study using HFC-32 and sodium dodecyl sulfate

This paper reports a set of experimental data of clathrate-hydrate formation from HFC-32 (difluoromethane) gas in contact with an aqueous solution of sodium dodecyl sulfate (SDS). This supersedes the corresponding data that we previously reported in this journal [Watanabe et al., 2005. Surfactant effects on hydrate formation in an unstirred gas/liquid system: an experimental study using HFC-32 and sodium dodecyl sulfate. Chemical Engineering Science 60, 4846-4857] with the new data reported herein, because of a suspicion of hydrate plugging occurring in the gas-feed line of our experimental system used to obtain the previous data. The new data show much higher levels in both the hydrate formation rate and the final water-to-hydrate conversion ratio as compared to the previous data. Neither the hydrate formation rate nor the water-to-hydrate conversion ratio exhibited a significant change with the SDS concentration in the aqueous phase over the range from 1000 to 4000 ppm.     

Elimination mechanism of micropores on bonding interface during solid-state crystal growth method

A pure yttrium aluminum garnet (YAG) ceramic/YAG single crystal composite material is prepared using the optimized solid-state crystal growth (SSCG) method. The micropores on the bonding interface of the composite sample are eliminated for the first time during the SSCG process and the transmittance is very close to the theoretical value, which reached 83.14% at 1064 nm. Meanwhile, the mechanism of elimination and migration of the pores under high temperature is studied. Additionally, the single crystal growth rate has significantly improved and the time of composite sample preparation has also significantly reduced proving that the SSCG method is an effective method for producing high quality composite material.     

Al2O3-Ce:GdYAG composite ceramic phosphors for high-power white light-emitting-diode applications

In order to meet the increasing demand of high-power light-emitting-diode (LED) lighting, state-of-the-art white light-emitting diode technology needs phosphors with high thermal conductivity and high luminous efficacy as color converters. In this work, translucent Al₂O₃-Ce:GdYAG composite phosphors were prepared by solid-state reactive sintering. The microstructure shows that the Al₂O₃ particles are uniformly dispersed in the Ce:GdYAG matrix. These particles can not only improve the thermal conductivity of the ceramics, but also promote the extraction efficacy. The luminous characteristics of the Ce:GdYAG and Al₂O₃-Ce:GdYAG ceramics were analyzed after being packaged with blue LED. When the molar ratio of Al₂O₃/Ce:GdYAG is 0.8, a high luminous efficacy value of 112.6 lm/W is achieved by the Al₂O₃-Ce:GdYAG composite ceramic phosphor with the thickness of 0.4 mm, as well as the highest CRI valve of 71.4. The appropriate photoelectric properties of this kind of ceramic phosphor make it a promising candidate for high-power LED device.     

Influence of LiBO2 addition on the microstructure and lithium-ion conductivity of Li1+xAlxTi2−x(PO4)3(x = 0.3) ceramic electrolyte

Concerning the safety problems of conventional Li-ion batteries with liquid electrolytes, it is crucial to develop reliable solid-state electrolytes with high ionic conductivity. Li_1+xAl_xTi_2?x(PO₄)₃ (LATP, x = 0.3) is regarded as one of the most promising solid electrolytes due to its high ionic conductivity and excellent chemical stability to humidity.Herein, a new strategy is proposed for improving the sintering behavior and enhancing the ionic conductivity of LATP by using LiBO₂ as the sintering aid via liquid phase sintering. The as-prepared sample LATP with homogeneous microstructure and high relative density of 97.1% was successfully synthesized, yielding high total ionic conductivity of 3.5 × 10^?4 S cm^?1 and low activation energy of 0.39 eV at room temperature. It was found that the addition of LiBO₂ could effectively enhance the densification and increase the ionic conductivity of LATP electrolyte, proving an effective way to synthesis LATP ceramics by a simple and reliable route.     

Precipitating spinel into precursor glass and its assistance in crystallization

The crystallization phenomena of spinel in CaO-MgO-Al₂O₃-SiO₂-Fe₂O₃ glass have received much attention due to the particular role in preparation of glass-ceramic materials, which represent an effective option to manage hazardous waste. In this study, both preliminary spinel and secondary spinel were precipitated in the precursor glass. The formation of these spinel was meticulously assessed by a combination of X-ray diffractometry and scanning electron microscopy. The structure of the microenvironment in the precursor glass was characterized by Raman spectrums. These advanced techniques highlight the potential for one-step crystallization of the glass. The investigation, which focused on one-step crystallization, demonstrated the growth of pyroxene on spinel accompanying a migration of chromium. The results also show the microstructure of the obtained glass-ceramic was very dependent on the heat-treat temperature. This study not only unambiguously reveals the precipitation mechanisms of spinel but also provides more documentation for one-step crystallization in the glass-ceramics field.     

New insights into linear electrical properties of pressureless sintered SiC-MoSi2-AlN composites

Highly conductive SiC-MoSi₂-AlN composites were fabricated by β-SiC, AlN and MoSi₂ powders with Y₂O₃ additive via pressureless sintering. The effect of MoSi₂ content on the microstructure, mechanical and electrical properties of SiC-MoSi₂-AlN composites was systematically investigated. A finer microstructure was obtained and electrical conductivity was enhanced with increasing MoSi₂ content. The impedance spectroscopy and potential-current measurements were implemented to figure out the electrical conduction mechanism. The introduction of MoSi₂ effectively reduced the Schottky barrier height at the grain boundary, and subsequently the U-I curves changed from nonlinear to linear electrical characteristics. The notable decrease in electrical resistivity was owing to the breakdown of grain boundaries and the formation of percolation paths. The percolation threshold was in the range of 0–5.44 vol% MoSi₂, much lower than the reference value. The composites with 10 wt% MoSi₂ exhibited an electrical resistivity of about 60 Ω cm, suitable for infrared source element applications.     

Investigation on the effect of oxalic acid,succinic acid and aspartic acid on the gas hydrate formation kinetics

Gas hydrate reserves are potential source of clean energy having low molecular weight hydrocarbons trapped in water cages. In this work, we report how organic compounds of different chain lengths and hydrophilicities when used in small concentration may modify hydrate growth and either act as hydrate inhibitors or promoters. Hydrate promoters foster the hydrate growth kinetics and are used in novel applications such as methane storage as solidified natural gas, desalination of sea water and gas separation. On the other hand, gas hydrate inhibitors are used in oil and gas pipelines to alter the rate at which gas hydrate nucleates and grows. Inhibitors such as methanol and ethanol which form strong hydrogen bond with water have been traditionally used as hydrate inhibitors. However, due to relatively high volatility a significant portion of these inhibitors ends up in gas stream and brings further complexity to the safe transportation of natural gas. In this study, organic additives such as oxalic acid, succinic acid and L-aspartic acid (all three) having—COOH group(s) with aspartic acid having an additional—NH₂ group, are investigated for gas hydrate promotion/inhibition behavior. These compounds are polar in nature and thus have significant solubility in liquid water; the presence of weak acidic and water loving (carboxylic/amine groups) moieties makes these organic acids an excellent candidate for further study. This study would pave ways to identify a novel(read better) promoter/inhibitor for gas hydrate formation. Suitable thermodynamic conditions were generated in a stirred tank reactor coupled with cooling system; comparison of gas hydrate formation kinetics with and without additives were carried out to identify the effect of these acids on the formation and growth of hydrates. The possible mechanisms by which these additives inhibit or promote the hydrate growth are also discussed.     

Highly transparent yttrium titanate (Y2Ti2O7) ceramics from co-precipitated powders

Highly transparent yttrium titanate (Y₂Ti₂O₇) ceramics were fabricated by vacuum sintering using co-precipitated powders for the first time. The effects of the powder calcination temperature on the phase composition, morphology of the calcined powders, and on the microstructure and transmittance of the Y₂Ti₂O₇ ceramics were investigated. When the calcination temperature was above 850 °C, pure phase Y₂Ti₂O₇ nanopowders with high sintering activity were obtained. Transparent Y₂Ti₂O₇ ceramics were obtained after vacuum sintered at 1600 °C for 6 h and annealed at 1100 °C for 5 h in air. The highest transmittance reached 73% at 1000 nm when the calcination temperature was 1150 °C. The measured refractive index of Y₂Ti₂O₇ ceramics was higher than 2.24 at the wavelength range of 350–1000 nm, making it a promising candidate for optical devices.     

The effect of A-site nonstoichiometry on the microstructure,electric properties,and phase stability of NaNbO3 polycrystalline ceramics

The impact of A-site nonstoichiometry on the microstructure, electric properties, and phase stability of sodium niobate ceramics (Na_1+xNbO₃, x = ?2 to 1 mol %) was investigated. All the components maintained an orthorhombic antiferroelectric (AFE) structure. The grain size increased from 3.9 to 14.3 μm with the variation in x from ?2 to 1. The AFE–FE phase transition electric field dramatically increased from 100 kV cm^?1 at x = 0 to 170 kV cm^?1 at x = ?2, confirming the enlarged energy barrier between AFE Pbma and FE Pmc2₁ phase under external field in A-site deficient components. This is attributed to the lattice compressive stress generated by introducing proper A-site vacancies. Combined results of transmission electron microscopy and Raman spectroscopy indicated that the AFE distortion of Pbma phase was significantly enhanced in A-site deficient components, which jointly contributed to the stability of AFE phase in A-site deficient NaNbO₃ material.     

Enhanced gas sensing properties to NO2 of SnO2/rGO nanocomposites synthesized by microwave-assisted gas-liquid interfacial method

The detection of nitrogen dioxide (NO₂) is essential for the environment and human health. Tin dioxide (SnO₂) based sensors have demonstrated capabilities to detect NO₂, while their response, response/recover speed and selectivity are not good enough for their practical applications. To address these issues, the SnO₂ nanoparticles doped with reduced graphene oxides (rGO) have been synthesized by using a facile microwave-assisted gas-liquid interfacial solvothermal method in this work. The NO₂ sensing performances have been greatly enhanced after the doping of rGO due to the improved electronic conductivity and the formation of the p-n junction in the as-synthesized SnO₂/rGO nanocomposites. Moreover, our results demonstrate that the sensors based on the SnO₂/(0.3%)rGO nanocomposites (with an average diameter about 10–15 nm) exhibit the best overall performance with the high response of 247.8 to 10 ppm NO₂, fast response/recovery speed (39 s/15 s) and the excellent selectivity at the working temperature of 200 ℃. Remarkably, the SnO₂/(0.3%)rGO sensors still exhibit a good gas sensing performance to NO₂ even at room temperature.     

Methodology for dependence-based integrated constitutive modelling: An illustrative application to SiCp/Al composites

In industrial forming and machining process, the large plastic deformation of material takes place in wide loading ranges of strain-rate and forming temperature. A satisfactory modelling of quasi-static and dynamic material behaviors is of great importance for understanding physical process and processes optimization. A dependence-based integrated methodology, together with an improved weighted multi-objective parameter identification strategy is presented for the development of phenomenological constitutive model and the parameter identification using experimental data from quasi-static and dynamic tests with instantaneous strain rate variations and plastic strain-related temperature changes. The improved multi-objective parameter identification model is reformulated by introducing three weighting factors for valuing different measure errors and fit standard errors in individual objective function corresponding to each test, considering the sampling point number and active material parameter number under different loading conditions, and balancing optimization opportunity of quasi-static and dynamic sub-objective functions. The methodology is verified for feasibility through illustrative constitutive identification for SiC_p/Al composites. This may provide a methodology of constitutive modelling for predicting material behaviors in quasi-static and dynamic modes equally well.     

Enhanced piezoelectric properties and temperature stability of Bi4Ti3O12-based Aurivillius ceramics via W/Nb substitution

Bi₄Ti₃O₁₂ (BIT), a typical Aurivillius ceramics with high Curie temperature (T_c ? 675 °C), has great potential for high temperature applications. This work provides an effective method of inducing structure distortion, relieving the tetragonal strain of the TiO₆ octahedron and decreasing the concentration of oxygen vacancies to improve the piezoelectricity and temperature stability of BIT ceramics. Bi₄Ti_2.98W_0.01Nb_0.01O₁₂ possesses an optimum piezoelectric coefficient (d₃₃) of 32 pC/N, a high T_c of 655 °C and a large resistivity of 3 × 10⁶ Ω·cm at 500 °C. The maximum d₃₃ reported here is approximately quadruple than that of pure BIT (?7 pC/N). Moreover, the d₃₃ of W/Nb co-doped BIT and the in-situ temperature stability of the compression-mode sensor present a highly stable characteristic in the range of 25–600 °C. These results imply that W/Nb-modified BIT ceramics is a promising candidate for application at high temperatures of up to 600 °C.     

The potential of pervaporation for biofuel recovery from fermentation:An energy consumption point of view

Recovering alcohols from dilute fermentation broth is an emergent task in bio-fuel production process. Since they are primary planned for fuels, energy required to separate these alcohols should be considered in evaluating the potential of a separation technology. A membrane-based process, pervaporation, is of special interest because of its environmental friendliness and easy integrating character. This review probes into the fundamentals of pervaporation especially in terms of the heat required for evaporation. Meanwhile, the separation data of the most representative alcohol-selective pervaporation membranes reported in the literatures are collected and compared with the vapor–liquid equilibrium curve, which represents the distillation selectivity. They include:inorganic membranes, silicon rubber based membranes, Mixed Matrix Membranes and some other special materials. By doing so, the status of alcohol recovery via pervaporation would be more clear for researchers.For ethanol recovery, it is selectivity rather than flux that is in urgent need of solution. While for butanol recovery,membranes with satisfactory selectivity have been developed, increasing the separation capacity would be more pressing.     

High energy storage performances of Bi1−xSmxFe0.95Sc0.05O3 lead-free ceramics synthesized by rapid hot press sintering

Lead-free Bi_1?xSm_xFe_0.95Sc_0.05O₃ (x = 0.15–0.19) ceramics were fabricated by rapid hot press sintering, and their structure, ferroelectric and energy storage properties were comprehensively investigated. All the samples are in the mixed phases with R3c rhombohedral and Pbnm orthorhombic structures. With increasing x, the ferroelectric polarization decreases gradually, while the polarization loop becomes gradually slimed too. An high recoverable energy density (?2.21 J/cm³) and a large efficiency (?76%) with good thermal stability (20 °C–120 °C) are obtained under electric field (230 kV/cm) for the optimized sample x = 0.17. Moreover, transmission electron microscopy and piezo-response force microscopy measurements reveal that the presence of two-phase coexistence favors the formation of polar nano-regions, leading to the linear-towards polarization behaviors and the enhanced dielectric breakdown field, which is responsible for the superior energy storage performance of Bi_1?xSm_xFe_0.95Sc_0.05O₃ ceramics. These results indicate a significant step to tailor lead-free BiFeO₃-based ceramics towards high dielectric energy storage applications.