0℃以下含SDS的甲烷水合物生成方式及过程对其分解速率的影响

The dissociation rates of methane hydrates formed with and without the presence of sodium dodecyl sulfate(methane-SDS hydrates),were measured under atmospheric pressure and temperatures below ice point to investigate the influence of the hydrate production conditions and manners upon its dissociation kinetic behavior.The experimental results demonstrated that the dissociation rate of methane hydrate below ice point is strongly dependent on the manners of hydrate formation and processing.The dissociation rate of hydrate formed quiescently was lower than that of hydrate formed with stirring;the dissociation rate of hydrate formed at lower pressure was higher than that of hydrate formed at higher pressure;the compaction of hydrate after its formation lowered its stability,i.e.,increased its dissociation rate.The stability of hydrate could be increased by prolonging the time period for which hydrate was held at formation temperature and pressure before it was cooled down,or by prolonging the time period for which hydrate was held at dissociation temperature and formation pressure before it was depressurized to atmospheric pressure.It was found that the dissociation rate of methane hydrate varied with the temperature(ranging from 245.2 to 272.2 K) anomalously as reported on the dissociation of methane hydrate without the presence of surfactant as kinetic promoter.The dissociation rate at 268 K was found to be the lowest when the manners and conditions at which hydrates were formed and processed were fixed.     

EXPERIMENTAL STUDY OF HFC-134a GAS HYDRATE FORMATION PROCESS

Refrigerant gas hydrates have brilliant prospects as cool storage material of air-conditioning system. In this paper, when the ratio of the weight of HFC-134a to that of water is 2.17%, systematic experiments have been carried out on the formation process of the HFC-134a gas hydrate including of the phase equilibrium, the influence of supercooling degree, and the influence of agitation. The results indicate that the critical decomposition temperature and the critical decomposition pressure of R134a hydrate is 283.4K and 414K respectively, the formation of gas hydrate was promoted with increasing the supercooling degree and the agitation. However, it is desired that the supercooling degree is smaller. Therefore, it is important problem that the study of optimum of supercooling degree for cool storage system.     

天然气水合物生成焓的实验研究

This paper reports the measurements of enthalpies of natural gas hydrates in typical natural gas mixture containing methane, ethane, propane and iso-butane at pressure in the vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a multi-cell differential scanning calorimeter using modified high pressure cells. The enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined from the calorimeter response during slow temperature scanning at constant pressure. The amount of gas released from the dissociation of hydrate was determined from the pumped volume of the high pressure pump. The occupation ratio (mole ratio) of the water to gas and the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that the enthalpy of hydrate formation and the occupation ratio are essentially independent of pressure.     

环戊烷/水乳化液水合法捕获烟道气中CO_2(英文)

Capture of CO2 by hydrate is one of the attractive technologies for reducing greenhouse effect.The primary challenges are the large energy consumption,low hydrate formation rate and separation efficiency.This work presents a new method for capture of CO2 from simulated flue gasCO2(16.60%,by mole) /N2 binary mixture by formation of cyclopentane(CP) hydrates at initial temperature of 8.1°C with the feed pressures from 2.49 to 3.95 MPa.The effect of cyclopentane and cyclopentane/water emulsion on the hydrate formation rate and CO2 separation efficiency was studied in a 1000 ml stirred reactor.The results showed the hydrate formation rate could be increased remarkably with cyclopentane/water emulsion.CO2 could be enriched to 43.97%(by mole) and 35.29%(by mole) from simulated flue gas with cyclopentane and cyclopentane/water(O/W) emulsion,respectively,by one stage hydrate separation under low feed pressure.CO2 separation factor with cyclopentane was 6.18,higher than that with cyclopentane/water emulsion(4.01) ,in the range of the feed pressure.The results demonstrated that cyclopentane/water emulsion is a good additive for efficient hydrate capture of CO2.     

高温高压下湿空气循环中增湿塔的计算研究

Humidification is an important step in humid air turbine system. The calculation on humidification is carried out at 423.15—573.15K, 5—15MPa. The results suggest that to produce high-enthalpy moist air, high water temperature and large water flow are needed. The water temperature is the most sensitive parameter to the humidification tower. And it is better for the humidification tower to work at temperature higher than 523 K when the system pressure is higher than 5 MPa. The comparison between the model used in this paper and ideal model shows that the ideal model can be used in simulation to simply the calculation when the temperature is lower than 473 K and pressure is lower than 5 MPa.     

CH4、CO2及CH4+C2H6+C3H8在纯水、SDS水溶液和含石英砂体系中水合物相平衡条件的测定

Phase equilibrium conditions of gas hydrate in several systems were measured by the step-heating method using the cylindrical transparent sapphire cell device. The experimental data for pure CH4 or CO2 + deionized water systems showed good agreement with those in the literatures. This kind of method was then applied to CH4/CO2 + sodium dodecyl sulfate (SDS) aqueous solution, CH4/CO2 + SDS aqueous solution + silica sand, and (CH4 + C2H6 + C3H8) gas mixture + SDS aqueous solution systems, where SDS was added to increase the hydrate formation rate without evident influence on the equilibrium conditions. The feasibility and reliability of the step-heating method, especially for porous media systems and gas mixtures systems were determined. The experimental data for CO2 + silica sand data shows that the equilibrium pressure will change significantly when the particle size of silica sand is less than 96 μm. The formation equilibrium pressure was also measured by the reformation of hydrate.     

次氯酸钙对水合物中甲烷储气量的影响

1 INTRODUCTION At present,natural gas accounts for 3% of the total energy consumption in China.It will go up to 5% in 2005 and 8% in 2010. Natural gas storage is a subject of great interest to many industries and particularly to transportation.Compressed natural gas,liquefied natural gas and adsorbed natural gas are techniques widely used.The possibility of developing a convenient storage system based on hydrate has been explored for about ten years around the world[1-5].Gudmundsson[1] has focused on the storage and transportation of gas as hydrate at atmospheric pressure since 1990.Khokhar[2] used 1,3-dimethylcyclohexane and polyvinyl-pyrrolidone as additives to lower hydrate formation pressure. Saito[3] surveyed the effects of tetrahydrofuran and acetone.Rogers[3] used sodium dodecyl sulfate as accelerator to natural gas hydrate formation. In this work,the effects of calcium hypochlorite on hydrate formation are investigated.The data show that it can lower the degree of supercooling and enhance the relative cage occupancy.     

RECENT ADVANCES IN HYDRATE-BASED TECHNOLOGIES FOR NATURAL GAS STORAGE——A REVIEW

Interest in the possibility of storing and transporting natural gas in the form of clathrate hydrates has been increasing in recent years, particularly in some gas-importing and exporting countries. The technologies necessary for realizing this possibility may be classified into those relevant to the four serial processes——(a) the formation of a hydrate, (b) the processing (dewatering, pelletizing, etc.) of the formed hydrate, (c) the storage and transportation of the processed hydrate, and (d) the regasification (dissociation) of the hydrate. The technological development of any of these processes is still at an early stage. For hydrate formation, for example, various rival operations have been proposed. However, many of them have never been subjected to actual tests for practical use. More efforts are required for examining the different hydrate-formation technologies and for rating them by comparison. The general design of the processing of the formed hydrate inevitably depends on both the hydrate-ormation process and the storage/transportation process, hence it has a wide variability. The major uncertainty in the storage-process design lies in the as-yet unclarified utility of the "self-preservation" effect of the naturalgas hydrates. The process design as well as the relevant cost evaluation should strongly depend on whether the hydrates are well preserved at atmospheric pressure in large-scale storage facilities. The regasification process has been studied less extensively than the former processes. The state of the art of the technological development in each of the serial processes is reviewed, placing emphasis on the hydrate formation process.     

天然石英砂中CO_2水合物的分解动力学

The decomposition kinetics for formation of CO2 hydrates in 90 cm3 wet natural silica sands were studied systematically using the depressurization method at the temperatures ranging from 273.2 to 277.2 K and the pressures from 0.5 to 1.0 MPa. The effects of temperature, pressure, particle diameter, porosity, and salinity of formation water on the decomposition kinetics were investigated. The results show that the dissociation percentage increases as temperature increases or as the initial decomposition pressure decreases. An increase in porosity or a decrease in particle diameter of silica sands accelerates the decomposition. Increasing the salinity of the formation water gives rise to a faster decomposition. However, a combination of the present results with the observa-tions in literature reveals that the effect of the coexisting ionic solute depends on its chemical structure.     

Accelerated methane storage in clathrate hydrates using surfactantstabilized suspension with graphite nanoparticles

In this study, enhanced kinetics of methane hydrate formation in the sodium dodecyl sulfate(SDS) solution with different concentrations of suspended graphite nanoparticles(GNPs) were investigated at 6.1–9.0 MPa and 274.15 K. The GNPs with rough surfaces and excellent thermal conductivity not only provided a considerable number of microsites for hydrate nucleation but also facilitated the fast hydrate heat transfer in the suspension system. At a relatively low pressure of 6.1 MPa, the suspension with 0.4 wt% of GNPs exhibited the minimum induction time of 22 min and maximum methane uptake of 126.1 cm~3·cm~(-3). However, the methane storage performances of the suspensions with higher and lower concentrations of GNPs were not satisfactory. At the applied pressure, the temperature increase arising from the hydrate heat in the suspension system with the optimized concentration(0.4 wt%) of GNPs was more significant than that in the traditional SDS solution. Furthermore,compared with those of the system without GNPs, enhanced hydration rate and storage capacity were achieved in the suspensions with GNPs, and the storage capacities were increased by 3.9%–17.0%. The promotion effect of GNPs on gas hydrate formation at low pressure is much more obvious than that at high pressure.     

Kinetic simulation of methane hydrate formation and dissociation in porous media

The vast amount of hydrocarbon gas deposited in the earth's crust as gas hydrates has significant implications for future energy supply and global climate. A 3-D simulator for methane hydrate formation and dissociation in porous media is developed for designing and interpreting laboratory and field hydrate experiments. Four components (hydrate, methane, water and salt) and five phases (hydrate, gas, aqueous-phase, ice and salt precipitate) are considered in the simulator. The intrinsic kinetics of hydrate formation or dissociation is considered using the Kim-Bishnoi model. Water freezing and ice melting are tracked with primary variable switch method (PVSM) by assuming equilibrium phase transition. Mass transport, including two-phase flow and molecular diffusions, and heat transfer involved in formation or dissociation of hydrates are included in the governing equations, which are discretized with finite volume difference method and are solved in a fully implicit manner. The developed simulator is used here to study the formation and the dissociation of hydrates in laboratory-scale core samples. In hydrate formation from the system of gas and ice (G+I) and in hydrate dissociation systems where ice appears, the equilibrium between aqueous-phase and ice (A-I) is found to have a “blocking” effect on heat transfer when salt is absent from the system. Increase of initial temperature (at constant outlet pressure), introduction of salt component into the system, decrease of outlet pressure, and increase of boundary heat transfer coefficient can lead to faster hydrate dissociation.     

Decomposition of carbon dioxide hydrate in the samples of natural coal with different degrees of metamorphism

Methane and carbon dioxide hydrates are one of the possible forms in which these gases exist in natural coal (for more detailed discussion see Refs [1,2]). In this work, the decomposition of carbon dioxide hydrate in five samples of natural coal differing from each other in metamorphism degree was investigated experimentally. Carbon dioxide hydrate dispersed in coals was synthesized from water adsorbed in these coals. During a linear temperature rise in an autoclave with the coal + hydrate sample the hydrate decomposition manifests itself as a step of increase in gas pressure, accompanied by a decrease/stabilization of the temperature of coal sample. The dependencies of the amount of hydrate formed on initial coal humidity and on gas pressure during hydrate formation were studied. It was demonstrated that each coal sample is characterized by its own humidity threshold below which hydrate formation in natural coal is impossible. With an increase in gas pressure, the amount of water transformed into hydrate increases. For the studied coal samples, the decomposition of carbon dioxide hydrates proceeds within a definite temperature and pressure range, and this range is close to the curve of phase equilibrium for bulk hydrate.     

Comparison between equilibrium and kinetic models for methane hydrate dissociation

Current literature agrees that the equilibrium and kinetic models for methane hydrate dissociation are almost indistinguishable. In this comparison, we used the equilibrium and kinetic models with two kinds of thermal boundary conditions to study the dissociation of methane hydrates in porous media. We found significant deviations between the two models. A systematic parametric study of the kinetic reaction constants clearly shows that the kinetic model results approach the equilibrium model when the intrinsic mole dissociation constant excessively exceeds the range found in the literature. Further, we showed deviations in the dissociation pattern between the equilibrium and kinetic models for both boundary conditions. The equilibrium model exhibits a moving front pattern for hydrate dissociation while the kinetic model shows a moving zone pattern under adiabatic boundary conditions. As for the constant temperature boundary condition, the hydrate dissociates by shrinking in all dimensions for the equilibrium model while, for the kinetic model, it dissociates with no specific pattern throughout the entire reservoir. The parametric studies show that higher activation energy results in a lower rate of hydrate dissociation.     

盐水体系中环戊烷-甲烷水合物相平衡测定与模拟

利用恒温搜索法测定了温度284.4~303.8 K、NaCl质量浓度0~9.978%水溶液中环戊烷-甲烷水合物(II型)的相平衡条件. 结果表明,该体系水合物相平衡压力远低于纯甲烷水合物,且随温度升高和盐度增大逐渐升高. 在Van der Waals-Platteeuw等温吸附模型和Pitzer活度模型的基础上建立了环戊烷-甲烷水合物在盐水体系中的相平衡理论模型,模拟预测值与实验测定值的吻合度较好,平均相对误差为4.07%,能较好地预测盐水体系中环戊烷-甲烷水合物(II型)的相平衡条件.     

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.     

Evidence of liquid water formation during methane hydrates dissociation below the ice point

Dissociation of small methane hydrate samples formed from water droplets of size 0.25-2.5 mm has been investigated below the ice melting point in the temperature range of 240-273 K, where the self-preservation effect is observed for bulk hydrates. The experiments included optical microscopy observations combined with P-T measurements of the dissociation conditions for the methane hydrates. For the first time, the formation of supercooled liquid water during the hydrate dissociation was reliably detected in the temperature range of 253-273 K. The formation of the liquid phase was visually observed. The induction time of the ice nucleation for the metastable liquid water depended from the dissociation temperature and a size of water droplets formed during the hydrate dissociation. It was found that in the temperature range of 253-273 K values of the dissociation pressure for the small hydrate samples fall on the extension of the water-hydrate-gas equilibrium curve into the metastable region where supercooled water exist. The average molar enthalpy of 51.7 kJ/mol for the dissociation of the small methane hydrate samples in the temperature range of 253-273 K was calculated using Clausius-Clapeyron equation. This value agrees with the enthalpy of dissociation of bulk methane hydrates into water and gas at temperatures above 273 K.     

Phase behavior and kinetics properties of gas hydrates in confinement and its application

Massive amounts of gas hydrates occur naturally in the pores of sediments or fractures in permafrost regions and beneath the oceans. For hydrate formation in confinement, the equilibrium condition can shift to harsher conditions, lowering the water activity and subsequently depressing the hydrate freezing temperature at a given pressure. Conversely, the nucleation and rate of hydrate formation, as well as hydrate conversion can be increased in confinement. Therefore, reliable assessment of the hydrate distribution in nature requires accurate thermodynamic and kinetic models of hydrate formation; however, these models tend to be based upon the properties of bulk hydrates. Hydrate formation and growth promotion in confinement are also potentially interesting for hydrate technological applications, such as gas separation, energy storage, and flow assurance. This paper reviews the thermodynamic and kinetic properties and their interrelations of gas hydrates in confined spaces.     

Stability and growth of gas hydrates below the ice–hydrate–gas equilibrium line on the P–T phase diagram

Using a previously developed experimental technique, the behavior of small methane and propane hydrate samples formed from water droplets between 0.25 and 2.5 mm in size has been studied in the pressure–temperature area between the ice–hydrate–gas equilibrium line and the supercooled water–hydrate–gas metastable equilibrium line, where ice is a stable phase. The unusual persistence of the hydrates within the area bounded by these lines and the isotherms at T=253 K for methane hydrate or at T=263 K for propane hydrates was observed. This behavior has not previously been reported. For example, in the experiment carried out at 1.9 MPa and 268 K, the methane hydrates existed in a metastable state (the equilibrium pressure at 268 K is 2.17 MPa) for 2 weeks, then immediately dissociated into liquid supercooled water and gas after the pressure was isothermally decreased slightly below the supercooled water–hydrate–gas metastable equilibrium pressure. It was found that dissociation of metastable hydrate into supercooled water and gas was reversible. The lateral hydrate film growth rates of metastable methane and propane hydrates on the surface of supercooled water at a pressure below the ice–hydrate–gas equilibrium pressure were measured. The temperature range within which supercooled water formed during hydrate dissociation can exist and a role of supercooled water in hydrate self-preservation is discussed.     

Cage occupancy and dissociation enthalpy of hydrocarbon hydrates

An elaborated statistical mechanical theory on clathrate hydrates is applied to exploration of their phase equilibria and dissociation enthalpies. The experimental dissociation pressures of methane, ethane, acetylene, and propane hydrates are well recovered by the method we have proposed. We estimate water/hydrate and hydrate/guest two-phase coexisting conditions in the temperature, pressure, and composition space in addition to three-phase equilibrium conditions. It is shown that the occupancy of guest molecules and the two-phase boundaries in the phase diagram vary depending sensitively on its size. Enthalpy components arising from the host and guest interactions are separately calculated from the temperature dependence of the corresponding free energy values. This enables to evaluate the dissociation enthalpy at any stable and metastable thermodynamic state taking account of the phase transition in the coexisting phase such as melting of ice, notably that along the three-phase equilibrium line.