水合物法分离低浓度煤层气中的甲烷

向模拟煤层气(13.11vol% CH4+86.89vol% N2)中添加5.8mol%四氢呋喃(THF)?0.03mol%十二烷基硫酸钠(SDS)促进剂溶液分离提纯煤层气,考察了压力、温度、反应时间对气体消耗量、反应速率、分解气中甲烷浓度、甲烷回收率和甲烷分离因子的影响,采用色谱分析法分别测定了CH4在剩余气相和分解气相中的浓度。结果表明,压力增加,CH4回收率增大,CH4分离因子增大,CH4分离效果越好;温度是影响甲烷分离因子的关键因素,温度降低,氮气和甲烷竞争进入水合物晶体中,导致水合物相中甲烷浓度降低;温度升高有利于提高水合物对甲烷的选择性。甲烷回收效率最高可达98.65%,分离因子最大为14.83。随反应时间增加,分解气中CH4浓度升高。     

Structural phase transitions of methane+ethane mixed-gas hydrate induced by 1,1-dimethylcyclohexane

Methane+ethane+1,1-dimethylcyclohexane+water system was investigated by using Raman spectroscopy and isothermal phase equilibrium measurements under four-phase (gas+aqueous+large guest species+hydrate phases) equilibrium conditions at 288.15 K. The results suggest that three kinds of hydrate structures emerge at 288.15 K in the methane+ethane+1,1-dimethylcyclohexane+water system. The hydrate structure for this system changed from structure-H to structure-I via structure-II with increase in the mole ratio of ethane to methane.     

The partition coefficients of ethylene between hydrate and vapor for methane + ethylene + water and methane + ethylene + SDS + water systems

The hydrate formation of CH₄+C₂H₄ mixture was studied experimentally in two different cases, with and without the presence of sodium dodecyl sulfate (SDS) in water. The results manifested that the presence of SDS could not only accelerate the hydrate formation process, but also increase the partition coefficient of ethylene between hydrate and vapor drastically. The partition coefficients of ethylene between hydrate and vapor for methane + ethylene + water with the presence of 500 ppm SDS in water were then systematically measured. The experimental temperature ranged from 273.15 to 278.15 K, the pressure ranged from 2.5 to 5.5 MPa, the initial gas-liquid volume ratio ranged from 95 to 240 standard volumes of gas per volume of liquid, and the mole percentage of ethylene in feed gas mixture ranged from 5.28% to 79.36%. The results demonstrated that ethylene could be enriched in hydrate phase and partition coefficients were increased with the presence of SDS in water. This conclusion is of industrial significance; it implies that it is feasible to recover ethylene from gas mixture, e.g., various kinds of refinery gases or cracking gases in ethylene plant, by forming hydrate.     

Thermodynamic and Raman spectroscopic studies on hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrates

Thermodynamic stability and hydrogen occupancy on the hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate have been investigated by means of phase equilibrium (pressure-temperature) measurements and Raman spectroscopic analyses for two mole fractions, 0.018 and 0.034 (stoichiometric for the cubic structure) of tetra-n-butyl ammonium fluoride aqueous solutions. In the case of higher concentration (0.034), the stability boundary curve of hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate locates at about 23 K higher temperature than that of hydrogen+tetrahydrofuran mixed gas hydrate. The storage capacity of hydrogen in the cubic structure for the hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate is smaller than that of hydrogen+tetrahydrofuran mixed gas hydrate. In the case of hydrate prepared from the lower concentration (0.018) of aqueous solution, the Raman spectra and phase behavior reveal that the cubic structure of semi-clathrate hydrate is changed to a different one at about 9 MPa and 299.2 K. The new structure can entrap larger amount of hydrogen than the cubic one. The stability boundary curve of hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate obtained in the aqueous solution of lower mole fraction (0.018) is shifted to slightly low-temperature or high-pressure side from that of higher mole fraction (0.034).     

液态二氧化碳置换整形甲烷水合物过程特性

通过可视化水合物反应装置和影像设备,研究了注入液态CO2分解CH4水合物同时原位生成气体水合物并保持整块水合物结构稳定的完整过程,验证了水合物分解和生成同时进行的第二类原位置换过程的可行性. 通过控制压力实现在CO2?CH4混合水合物四相区(水合物?水?液相?气相)的CH4置换过程,得到富CH4气体产物. 通过分析气相色谱和测定产气量得到CH4产气特性和CO2对CH4水合物的置换率. 结果表明,低压有利于获得较优的置换效果,4.5 MPa下的置换过程较5 MPa时产气量提高14.6%,甲烷水合物置换率提高13.7%.     

Induction time,storage capacity,and rate of methane hydrate formation in the presence of SDS and silver nanoparticles

In this communication, the kinetic parameters of methane hydrate formation (induction time, quantity and rate of gas uptake, storage capacity (SC), and apparent rate constant) in the presence of sodium dodecyl sulfate (SDS), synthetized silver nanoparticles (SNPs), and mixture of SDS?+?SNPs have been studied. Experimental measurements were performed at temperature of 273.65?K and initial pressure of 7?MPa in a 460?cm³ stirred batch reactor. Our results show that adding SDS, SNPs and their mixture increases the quantity of gas uptake, water to hydrate conversion, and SC of methane hydrate formation, noticeably. Using 300?ppm SDS increases the SC and the quantity of methane uptake 615, and 770%, respectively, compared with pure water. Investigating the hydrate growth rate at the start of hydrate formation process shows that, using SNPs, SDS, and their mixture increases the initial apparent rate constant of hydrate rate, considerably. Our results show that the system of methane?+?water?+?SDS 500?ppm?+?SNPs 45?µM represents the maximum value of initial apparent rate constant, compared with other tested systems.     

Experimental and theoretical study of gas hydrate formation in a high‐pressure flow loop

A set of mathematical models are developed based on thermodynamics, mass transfer, and crystallisation concepts to predict hydrate formation rate and the aqueous phase composition in the flow loop. In order to validate the model, experimental study is carried out in a 10 m loop with the inside diameter of 10.6 mm using gas mixture of 73% methane and 27% propane to measure the hydrate formation rate. The experimental conditions include temperature from 4 to 5°C and pressures between 2 and 3 MPa. Good agreements are noticed when the experimental and theoretical hydrate formation rates are compared at different operating conditions.     

Spectroscopic analysis of carbon dioxide and nitrogen mixed gas hydrates in silica gel for CO2 separation

In this study solid-state NMR spectroscopy was used to identify structure and guest distribution of the mixed N₂ + CO₂ hydrates. These results show that it is possible to recover CO₂ from flue gas by forming a mixed hydrate that removes CO₂ preferentially from CO₂/N₂ gas mixture. Hydrate phase equilibria for the ternary CO₂–N₂–water system in silica gel pores were measured, which show that the three-phase H–L_w–V equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO₂ in the vapor phase decreased. ¹³C cross-polarization (CP) NMR spectra of the mixed hydrates at gas compositions of more than 10 mol% CO₂ with the balance N₂ identified that the crystal structure of mixed hydrates as structure I, and that the CO₂ molecules occupy mainly the abundant 5¹²6² cages. This makes it possible to achieve concentrations of more than 96 mol% CO₂ gas in the product after three cycles of hydrate formation and dissociation.     

操作工况对酸性天然气水合物生成动力学的影响分析

水合物的快速生成受诸多因素的影响,操作工况是其主要的影响因素之一。以67.7%CH4+32.3%CO2（摩尔分数）混合气为例模拟酸性天然气,采用自行设计的水合物动力学实验装置,分别对初始压力为3.0 MPa、3.5 MPa、4.2 MPa、5.0 MPa和实验温度分别为1.42 ℃、3.27 ℃、5.48 ℃、7.45 ℃时的水合物生成动力学进行实验研究。定义诱导期、平衡总耗时、生长速率为水合物动力学评价指标,指标通过分析水合物生成过程中的压力及气相组成变化得到,进而综合分析了操作工况对酸性天然气水合物生成动力学的影响。实验结果表明：初始压力越高,实验温度越低,水合物平衡时气相CO2的浓度越低,水合物的生成量和生长速率越大;此外,初始压力对体系诱导期影响不够显著,而操作温度的降低可以明显缩短体系诱导期。     

Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas–water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.     

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.     

Measurements of methane hydrate heat of dissociation using high pressure differential scanning calorimetry

The methane hydrate heat of decomposition was directly measured up to 20 MPa and 292 K using a high pressure differential scanning calorimeter (DSC). The methane hydrate sample was formed ex-situ using granular ice particles and subsequently transferred into the DSC cell under liquid nitrogen. The ice and water impurities in the hydrate sample were reduced by converting any dissociated hydrate into methane hydrate inside the DSC cell before performing the thermal properties measurements. The methane hydrate sample was dissociated by raising the temperature (0.5-1.0 K/min) above the hydrate equilibrium temperature at a constant pressure. The measured methane hydrate heat of dissociation (H→W+G), ΔH_d, remained constant at 54.44±1.45 kJ/mol gas (504.07±13.48 J/gm water or 438.54± 13.78 J/gm hydrate) for pressures up to 20 MPa. The measured ΔH_d is in agreement with the Clapeyron equation predictions at high pressures; however, the Clausius-Clapeyron equation predictions do not agree with the heat of dissociation data at high pressures. In conclusion, it is recommended that the Clapeyron equation should be used for hydrate heat of dissociation estimations at high pressures.     

Solubility study for the purification of hydrogen from high pressure hydrocracker off-gas by an absorption-stripping process

Experiments were carried out to identify a solvent which has a high solubility and selectivity for methane relative to hydrogen at 295 K and pressures from 13.88 to 20.78 MPa. Binary solubilities with pure hydrogen and methane, and ternary solubilities with 73 mol% H₂ and 27 mol% CH₄ were measured at 295 K and for pressures from 6.99 to 20.78 MPa in various organic solvents. This gas mixture simulates hydrocracker and hydrotreater off-gases which are candidates for purification with an absorption-stripper. Of the solvents tested, 2,2,4-trimethylpentane (iso-octane), which showed very high methane solubility and a reasonable selectivity, and methylcyclohexane, which showed a very high selectivity and a reasonable solubility, are the best solvents for methane absorption. Correlations for hydrogen and methane as a function of pressure and solvent solubility parameter were developed with the experimental solubilities. Binary interaction parameters for Peng-Robinson (Peng and Robinson, 1976) and Soave-Redlich-Kwong (Soave, 1972) equations of state were calculated with experimental solubility results. Prediction of gas solubility in a ternary system was compared with experimental and found to be satisfactory when experimental binary interaction parameters were used.     

Structure and thermal expansion of natural gas clathrate hydrates

We report on the structural properties of natural gas hydrate crystals from the Sea of Okhotsk. Using powder X-ray diffraction (PXRD), it was determined that sediments from four locations contained type I gas hydrate, which encage mostly methane (96-98%) and a small amount of carbon dioxide. For all hydrates, the lattice constant was estimated to be at 113 K, which approximately equals that of pure methane hydrate. The result is in good agreement with the structure of artificially synthesized methane + carbon dioxide mixed-gas hydrates. These results suggest that the lattice constant of the natural gas hydrate does not change due to a change of CO₂ gas content. In addition, the thermal expansion of the sampled hydrate was measured for the temperature range of 83-173 K, and the resulting density of the hydrate crystal at 273 K was estimated to be . These results are essential for applying natural gas hydrates as an alternative natural fuel resources.     

Investigation of the hydrate formation process in fine sediments by a binary CO2/N2 gas mixture

To obtain the fundamental data of CO₂/N₂ gas mixture hydrate formation kinetics and CO₂ separation and sequestration mechanisms, the gas hydrate formation process by a binary CO₂/N₂ gas mixture (50:50) in fine sediments (150-250 μm) was investigated in a semibatch vessel at variable temperatures(273, 275, and 277 K)and pressures (5.8-7.8 MPa). During the gas hydrate reaction process, the changes in the gaseous phase composition were determined by gas chromatography. The results indicate that the gas hydrate formation process of the binary CO₂/N₂ gas mixture in fine sediments can be reduced to two stages. Firstly, the dissolved gas containing a large amount of CO₂ formed gas hydrates, and then gaseous N₂ participated in the gas hydrate formation. In the second stage, all the dissolved gas was consumed. Thus, both gaseous CO₂ and N₂ diffused into sediment. The first stage in different experiments lasted for 5-15 h, and >60% of the gas was consumed in this period. The gas consumption rate was greater in the first stage than in the second stage. After the completion of gas hydrate formation, the CO₂ content in the gas hydrate was more than that in the gas phase. This indicates that CO₂ formed hydrate easily than N₂ in the binary mixture. Higher operating pressures and lower temperatures increased the gas consumption rate of the binary gas mixture in gas hydrate formation.     

利用吸收-水合耦合法从氨弛放气中回收氢气的研究(英文)

In this work, the absorption-hydration hybrid method was used to recover (hydrogen + nitrogen) from (hydrogen + nitrogen + methane + argon) tail gas mixtures of synthetic ammonia plant through hydrate forma-tion/dissociation. A high-pressure reactor with magnetic stirrer was used to study the separation efficiency. The in-fluences of the concentration of anti-agglomerant, temperature, pressure, initial gas-liquid volume ratio, and oil-water volume ratio on the separation efficiency were systematically investigated in the presence of tetrahydro-furan (THF). Anti-agglomerant was used to disperse hydrate particles into the condensate phase for water-in-oil emulsion system. Since nitrogen is the material for ammonia production, the objective production in our separation process is (hydrogen + nitrogen). Our experimental results show that by adopting appropriate operating conditions, high concentration of (hydrogen + nitrogen) can be obtained using the proposed technology based on forming hydrate.     

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.     

Separation and capture of carbon dioxide from CO2/H2 syngas mixture using semi-clathrate hydrates

The relation between anthropogenic emissions of CO₂ and its increased levels in the atmosphere with global warming and climate change has been well established and accepted. Major portion of carbon dioxide released to the atmosphere, originates from combustion of fossil fuels. Integrated gasification combined cycle (IGCC) offers a promising fossil fuel technology considered as a clean coal-based process for power generation particularly if accompanied by precombustion capture. The latter includes separation of carbon dioxide from a synthesis gas mixture containing 40 mol% CO₂ and 60 mol% H₂.A novel approach for capturing CO₂ from the above gas mixture is to use gas hydrate formation. This process is based on selective partition of CO₂ between hydrate phase and gas phase and has already been studied with promising results. However high-pressure requirement for hydrate formation is a major problem.We have used semiclathrate formation from tetrabutylammonium bromide (TBAB) to experimentally investigate CO₂ capture from a mixture containing 40.2 mol% of CO₂ and 59.8 mol% of H₂. The results shows that in one stage of gas hydrate formation and dissociation, CO₂ can be enriched from 40 mol% to 86 mol% while the concentration of CO₂ in equilibrium gas phase is reduced to 18%. While separation efficiency of processes based on hydrates and semi-clathrates are comparable, the presence of TBAB improves the operating conditions significantly. Furthermore, CO₂ concentration could be increased to 96 mol% by separating CO₂ in two stages.     

Compositional and structural identification of natural gas hydrates collected at site 1249 on ocean drilling program leg 204

In contrast to the structural studies of laboratory-grown gas hydrate, this study has been performed on naturally grown clathrate hydrates from the sea floor. The PXRD pattern of natural gas hydrate shows that the sample had a structure I hydrate. The¹³C NMR spectrum was obtained for the natural gas hydrate sample in order to identify the cage occupancy of guest molecules and determine the hydration number. The NMR spectrum reveal that the natural gas hydrates used in this study contain only methane with no noticeable amount of other hydrocarbons. The existence of two peaks at different chemical shifts indicates that methane molecules are encapsulated in both large and small cages. In addition, Raman spectroscopic analysis is also carried out to identify natural hydrates and compared with the NMR results. Investigating the composition and structure of natural gas hydrates is essential for applying natural gas hydrates as a novel energy source.     

Kinetics of methane hydrate formation in aqueous electrolyte solutions

Experimental data on the kinetics of methane hydrate formation in aqueous electrolyte solutions are reported. The experiments were carried out in a semi-batch stirred tank reactor in three NaCl and two KCl solutions as well as in a solution containing a mixture of NaCl and KCl at three different nominal temperatures from 270 to 274 K and at pressures ranging from 3.78 to 7.08 MPa. The kinetic model developed by Englezos et al. (1987a) was adapted to predict the growth of hydrates. The model is based on the crystallisation theory coupled with the two-film theory for gas absorption in the liquid phase. The kinetic rate constant which appears in the model was that obtained earlier for methane hydrate formation in pure water. The effect of the electrolytes was taken into account through the computation of the three-phase equilibrium conditions and the corresponding fugacities. Overall, the model predictions match the experimental data very well with the largest prediction error being less than 10%.