Metastable state of gas hydrate during decomposition: A novel phenomenon

Natural gas hydrates are solid compounds with cage-like structures formed by gas and water. An intriguing phenomenon that gas hydrates can dissociate at a low rate below the ice freezing point has been viewed as the metastability of hydrate. The mechanisms of hydrate metastability have been widely studied, and many mechanisms were proposed involving the self-preservation effect, supercooled water-gas-hydrate metastable equilibrium, and supersaturated liquid–gas-hydrate system etc. The metastable state of hydrate could be of crucial significance in the kinetics of hydrate formation and decomposition, heat and mass transfer during gas production processes, and the application of hydrate-based technique involving desalination, energy storage and transportation, and gas separation and sequestration. Few researches have systematically considered this phenomenon, and its mechanism remains unclear.In this work, various mechanisms and hypothesis explaining the metastable state of gas hydrates were introduced and discussed. Further studies are still required to reveal the intrinsic nature of this metastable state of gas hydrate,and this work could give some implications on the existing theory and current status of relevant efforts.     

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.     

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.     

Intercalation Assembly Method and Intercalation Process Control of Layered Intercalated Functional Materials

Layered intercalated functional materials of layered double hydroxide type are an important class of functional materials developed in recent years. Based on long term studies on these materials in the State Key Laboratory of Chemical Resource Engineering in Beiiing University of Chemical Technology, the orinciole for the design of controlled intercalation processes in the light of tuture production processing requirements has been developed. Intercalation assembly methods and technologies have been invented to control the intercalation process for preparing layered intercalated materials with various structures and functions.     

STUDY FOR NATURAL GAS HYDRATE CONVERSED FROM ICE

Natural gas hydrates are crystalline clathrate compounds composed of water and gases of small molecular diameters that can be used for storage and transport of natural gas as a novel method. In the paper a series of experiments of aspects and kinetics for hydrate formed from natural gas and ice were carried out on the industrial small scale production apparatus. The experimental results show that formation conditions of hydrate conversed from ice are independent of induction time, and bigger degrees of supersaturation and supercooling improved the driving force and advanced the hydrate formation. Superpressure is also favorable for ice particle conversion to hydrate. In addition, it was found there have an optimal reaction time during hydrate formation.     

多孔载体海绵对CH4-N2-O2瓦斯气体水合分离影响（英文）

The findings were presented from laboratory investigations on the hydrate formation and dissociation processes employed to recover methane from coal mine gas.The separation process of coal mine methane(CMM) was carried out at 273.15K under 4.00 MPa.The key process variables of gas formation rate,gas volume stored in hydrate and separation concentration were closely investigated in twelve THF-SDS-sponge-gas systems to verify the sponge effect in these hydrate-based separation processes.The gas volume stored in hydrate is calculated based on the measured gas pressure.The CH4 mole fraction in hydrate phase is measured by gas chromatography to confirm the separation efficiency.Through close examination of the overall results,it was clearly verified that sponges with volumes of 40,60 and 80 cm 3 significantly increase gas hydrate formation rate and the gas volume stored in hydrate,and have little effect on the CH4 mole fraction in hydrate phase.The present study provides references for the application of the kinetic effect of porous sponge media in hydrate-based technology.This will contribute to CMM utilization and to benefit for local and global environment.     

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.     

孔隙尺寸、盐度和气体组分对水合物相平衡的影响(英文)

An experimental device was set up to study the hydrate formation conditions. Effects of pore size, salinity, and gas composition on the formation and dissociation of hydrates were investigated. The result indicates that the induction time for the formation of hydrates in porous media is shorter than that in pure water. The decrease in pore size, by decreasing the size of glass beads, increases the equilibrium pressure when the salinity and temperature are kept constant. In addition, higher salinity causes higher equilibrium pressure when the pore size and temperature are kept constant. It is found that the effects of pore size and salinity on the hydrate equilibrium are quite different. At lower methane concentration, the hydrate equilibrium is achieved at lower pressure and higher temperature.     

A型分子筛对甲烷水合物生成的影响

The porous medium has an important effect on hydrate formation. In this paper, the formation process and the gas storage capacity of the methane hydrate were investigated with A-type zeolite and Sodium Dodecyl Sulfate (SDS) existing in the system. The results show that A-type zeolite can influence methane hydrate formation. At the temperature of 273.5 K and pressure of 8.3 MPa, the distilled water with A-type zeolite can form methane hydrate with gaseous methane in 12 hours. The formation process of the system with A-type zeolite was quite steady and the amount of A-type zeolite can influence the gas storage capacity significantly. The adding of A-type zeolite with 0.067 g•(g water)－1 into 2×10－3 g•g－1 SDS-water solution can increase the gas storage capacity, and the maxi-mum increase rate was 31%. Simultaneously the promotion effect on hydrate formation of 3A-type zeolite is much more obvious than that of 5A-type zeolite when the water adding amounts are 0.033 g•g－1 and 0.067 g•g－1 at the experimental conditions.     

VISUAL OBSERBATION OF HCFC141b GAS HYDRATE FORMATION/DECOMPOSITION PROCESS OUTSIDE OF A TUBE

In order to design a kind of heat exchanger suitable to the indirect-touched gas hydrate cool storage vessel, a visual observation of HCFC141b gas hydrate formation/decomposition process was presented through a self-designed small-scale visualization apparatus of gas hydrate cool storage. Based on the shooted photos and recorded temperatures, the formation/decomposition process of HCFC141b are described, some characteristics are concluded, and some suggestions of designing heat exchanger are indicated according to the specific characteristics of HCFC141b gas hydrate formation/decomposition process.     

环戊烷水合物平衡数据

In the oil and gas industry, it is important to determine hydrate phase boundary for avoiding hydrate formation. In general n-butane is regarded as the heaviest hydrocarbon hydrate. But for oil and gas condensate systems, it has been found that some hydrocarbons heavier than n-butane could enter the large cavity of structure-II hydrate due to their effective van der Waal's diameter. The hydrate formation characteristics of benzene[1], cyclohexane[2], and cyclopentane and neopentane in their binaries/tern-aries with methane or/and nitrogen have been reported[3]. Ripmeester et al[4] pointed out that cyclopentane could form gas hydrates without a help gas. However there are no further experimental data to support it.     

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.     

Hydrate formation in oil–water systems: Investigations of the influences of water cut and anti-agglomerant

To investigate the characteristics of hydrate formation in oil–water systems, a high-pressure cell equipped with visual windows was used where a series of hydrate formation experiments were performed from natural gas + diesel oil + water systems at different water cuts and anti-agglomerant concentrations. According to the temperature and pressure profiles in test experiments, the processes of hydrate formation under two kinds of experimental procedures were analyzed first. Then, based on the experimental phenomena observed through the visual windows, the influences of water cut and anti-agglomerant on the places of hydrate formation and distribution, hydrate morphologies and hydrate morphological evolvements were investigated. Hydrate agglomeration, hydrate deposition and hydrate film growth on the wall were observed in experiments. Furthermore, three different mechanisms for hydrate film growth on the wall were identified. In addition, the influences of water cut and anti-agglomerant on the induction time of hydrate formation were also studied.     

SEISMIC STUDIES OF MARINE GAS HYDRATES

We give a brief introduction of developments of seismic methods in the studies of marine gas hydrates. Then we give an example of seismic data processing for BSRs in western Nankai accretionary prism, a typical gas hydrate distribution region. Seismic data processing is proved to be important to obtain better images of BSRs distribution. Studies of velocity structure of hydrated sediments are useful for better understanding the distribution of gas hydrates. Using full waveform inversion, we successfully derived high-resolution velocity model of a double BSR in eastern Nankai Trough area. Recent survey and research show that gas hydrates occur in the marine sediments of the South China Sea and East China Sea. But we would like to say seismic researches on gas hydrate in China are very preliminary.     

Nucleation of methane hydrate and ice in emulsions of water in crude oils and decane under non-isothermal conditions

Achievable supercooling for the formation of methane hydrate from water emulsions was studied in seven different crude oils and in decane. The experiments were performed under constant rate cooling from + 20 to-15 °C and a pressure of methane of 12 MPa. It was demonstrated that the shapes and positions of the resulting survival curves depend on the density, viscosity and dispersive power of oil samples used in the experiments, as well as on the degree of oil oxidation. In addition, results of the experiments on ice freezing under the same emulsions are presented. The results obtained in the work allowed us to discuss the possibility and features of primary and secondary nucleation of the hydrate and ice in the systems under consideration.     

生物质热裂解实验和模型研究(英文)

The analysis on the feedstock pyrolysis characteristic and the impacts of process parameters on pyrolysis outcomes can assist in the designing,operating and optimizing pyrolysis processes.This work aims to utilize both experimental and modelling approaches to perform the analysis on three biomass feedstocks—wood sawdust,bamboo shred and Jatropha Curcas seed cake residue,and to provide insights for the design and operation of pyrolysis processes.For the experimental part,the study investigated the effect of heating rate,final pyrolysis temperature and sample size on pyrolysis using common thermal analysis techniques.For the modelling part,a transient mathematical model that integrates the feedstock characteristic from the experimental study was used to simulate the pyrolysis progress of selected biomass feedstock particles for reactor scenarios.The model composes of several sub-models that describe pyrolysis kinetic and heat flow,particle heat transfer,particle shrinking and reactor operation.With better understanding of the effects of process conditions and feedstock characteristics on pyrolysis through both experimental and modelling studies,this work discusses on the considerations of and interrelation between feedstock size,pyrolysis energy usage,processing time and product quality for the design and operation of pyrolysis processes.     

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.     

Molar volume of eutectic solvents as a function of molar composition and temperature☆

The conventional Rackett model for predicting liquid molar volume has been modified to cater for the effect of molar composition of the Deep Eutectic Solvents (DES). The experimental molar volume data for a group of commonly used DES has been used for optimizing the improved model. The data involved different molar compositions of each DES. The validation of the new model was performed on another set of DESs. The average relative deviation of the model on the training and validation datasets was approximately 0.1%while the Rackett model gave a relative deviation of more than 1.6%. The modified model deals with variations in DES molar com-position and temperature in a more consistent way than the original Rackett model which exhibits monotonic performance degradation as temperature moves away from reference conditions. Having the composition of the DES as a model variable enhances the practical utilization of the predicting model in diverse design and process simulation applications.     

A review of extractive distillation from an azeotropic phenomenon for dynamic control

Extractive distillation is an effective method for separating azeotropic or close boiling point mixtures by adding a third component. Various technologies for performing the extractive distillation process have been explored to protect the environment and save resources. This paper focuses on the improvement of these advanced technologies in recent years. Extractive distillation is retrieved and analyzed from the view of phase equilibrium, selection of solvent in extractive distillation, process design, energy conservation, and dynamic control. The quantitative structure–property relationship used in extractive distillation is discussed, and the future development of extractive distillation is proposed to determine how the solvent affects the relative volatility of the separated mixture. In the steady state design, the relationship between the curvature of the residue curve and parameters of the optimal steady state is also highlighted as another field worthy of further study to simplify the distillation process.     

Computational design of heterogeneous catalysts and gas separation materials for advanced chemical processing

Functional materials are widely used in chemical industry in order to reduce the process cost while simultaneously increase the product quality.Considering their significant effects,systematic methods for the optimal selection and design of materials are essential.The conventional synthesis-and-test method for materials development is inefficient and costly.Additionally,the performance of the resulting materials is usually limited by the designer’s expertise.During the past few decades,computational methods have been significantly developed and they now become a very important tool for the optimal design of functional materials for various chemical processes.This article selectively focuses on two important process functional materials,namely heterogeneous catalyst and gas separation agent.Theoretical methods and representative works for computational screening and design of these materials are reviewed.