Experimental determination of methane hydrate dissociation curve up to 55 MPa by using a small amount of surfactant as hydrate promoter

Methane hydrate equilibrium has been studied upon continuous heating of the water-hydrate-gas system within the temperature range of 275-300 K. This temperature range corresponds to equilibrium pressures of 3.15-55 MPa. The hydrate formation/dissociation experiments were carried out in a high-pressure reactor under isochoric conditions and with no agitation. A small amount of surfactant (0.02 wt% sodium dodecyl sulfate, SDS) was added to water to promote hydrate formation. It was demonstrated that SDS did not have any influence on the gas hydrate equilibrium, but increased drastically both the hydrate formation rate and the amount of water converted into hydrate, when compared with the experiments without surfactant. To understand and clarify the influence of SDS on hydrate formation, macroscopic observations of hydrate growth were carried out using gas propane as hydrate former in a fully transparent reactor. We observed that 10^-3 wt% SDS (230 times less than the Critical Micellar Concentration of SDS) were sufficient to prevent hydrate particles from agglomerating and forming a rigid hydrate film at the liquid-gas interface. In the presence of SDS, hydrates grew mainly on the reactor walls as a porous structure, which sucked the solution due to capillary forces. Hydrates grew with a high rate until about 97 wt% of the water present in the reactor was transformed into hydrate.Our data on methane hydrate equilibrium both confirm already published literature data and complement them within the pressure range of 20-55 MPa.     

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.     

Effect of surfactant on the formation and dissociation kinetic behavior of methane hydrate

The effects of anionic surfactant sodium dodecyl sulfate (SDS) on the formation/dissociation kinetic behaviors of methane hydrate have been studied experimentally, with an emphasis put on dissociation kinetic behavior below ice point. The experimental results on hydrate formation show that the formation rates of methane hydrate could be speeded up by adding SDS to water and a critical SDS concentration of 650 ppm corresponding to a maximum storage capacity of 170V/V is determined. The SDS concentrations are fixed at this value in preparing hydrate samples for all dissociation tests. The dissociation experiments have been performed in two ways, at atmospheric pressure where the dissociation rates are determined by measuring the accumulative evolved gas volume, and in a closed system where the dissociation rates are determined by measuring the increasing system pressure profiles. For comparison, the dissociation tests with respect to two different cases, with and without the presence of SDS, are done in parallel. The results from tests in the first way show that the presence of SDS increases the dissociation rate of methane hydrate in whole temperature region below ice point. The results for the second way are somewhat different. The presence of SDS increases the dissociation rate and meta-stable system pressure in temperature region lower than . But when temperature is equal to or higher than , SDS speeds up the dissociation process only in beginning period, it turns to suppress the dissociation of methane hydrate several hours later and leads to a lower meta-stable system pressure compared with the case of without SDS. The experiments in closed system also demonstrate that the dissociating system approaches a meta-stable state with a pressure much lower than equilibrium dissociation pressure.     

Direct measurement of formation and dissociation rate and storage capacity of dry water methane hydrates

Dry water (DW) has been recently demonstrated to be an effective medium for methane storage in a hydrated form. Here, a series of experiments have been carried out on dry water methane hydrates (DW-MH) to investigate their formation and dissociation rates, storage capacity and structural characteristics. The result shows that the storage capacity of MH increases at least 10% by using DW relative to using surfactants like sodium dodecyl sulfate (SDS) solution. Also, it is found that controls on pressure-temperature (P-T) condition have influences on the induction and reaction time of DW-MH formation, i. e. the induction and reaction time are much shorter when the reaction cell is cooled to ~ 3 °C first. On the basis of Raman spectra, the hydration number is calculated as 5.934 ± 0.06 at different positions of the DW-MH, which suggests that the sample is very homogeneous. The dissociation process of the DW-MH sample exhibits a rapid release of methane gas at the first stage of dissociation. Although hydrate dissociation is prevented by the effect of self preservation, most methane gas has released from the hydrate, however, before the self preservation occur.     

Static Formation and Dissociation of Methane+Methylcyclohexane Hydrate for Gas Hydrate Production and Regasification

The formation and decomposition of methane+methylcyclohexane (MCH) hydrate in a static batch reactor, which was also designed as a high‐pressure microwave reactor, were investigated. The addition of 300 ppm sodium dodecyl sulfate (SDS) provides continuous formation of CH₄+MCH hydrate under static conditions. Increasing the initial pressure within the narrow range of 2.7 to 4.6 MPa at 274 K enhances the formation rate by even several times. The gas storage capacity can be largely improved with partial coexisting of sI CH₄ hydrate. Unlike a stirred formation, an increase of nonaqueous MCH inhibits the static formation of sH hydrate. The following regasification by 2.45 GHz microwave heating indicates that the dissociation is rate‐controlled by the parallel connection of efficient internal heating and conventional external heating. The multiphase convection characterized by osmotic dehydration and driven by intensified regasification is considered as the dominant mechanism affecting the quiescent dissociation.     

EXPERIMENTAL INVESTIGATION ON GAS HYDRATE FORMATION IN PRESENCE OF ADDITIVE COMPONENTS

Additives were used to increase gas hydrate formation rate and storage capacity. Experimental tests of methane hydrate formation were carried out in surfactant water solutions in a high-pressure cell. Sodium dodecyl sulfate (SDS) and alkyl polysaccharide glycoside (APG) were used to increase hydrate formation. The effect of SDS on hydrate formation is more pronounced compared APG. Cyclopentane (CP) also improves hydrate formation rates while it cannot increase methane gas storage capacity.     

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.     

Study on the influence of SDS and THF on hydrate-based gas separation performance

Hydrate additives can be used to mitigate hydrate formation conditions, promote hydrate growth rate and improve separation efficiency. CO₂ + N₂ and CO₂ + CH₄ systems with presence of sodium dodecyl sulfate (SDS) or tetrahydrofuran (THF) are studied to analyze the effect of hydrate additives on gas separation performance. The experiment results show that CO₂ can be selectively enriched in the hydrate phase. SDS can speed up the hydrate growth rate by facilitating gas molecules solubilization. When SDS concentration increases, split and loss fraction increase initially and then decrease slightly, resulting in a decreased separation factor. The optimum concentration of SDS exists at the range of 100–300 ppm. As THF can be easily encaged in hydrate cavities, hydrate formation condition can be mitigated greatly with its existence. Additionally, THF can also strengthen hydrate formation. The THF effect on separation performance is related to feed gas components. CO₂ occupies the small cavities of type II hydrate prior to N₂. But the competitiveness of CO₂ and CH₄ to occupy cavities are quite fair. The variations of split fraction, loss fraction and separation factor depend on the concentration of THF added. The work in this paper has a positive role in flue gas CO₂ capture and natural gas de-acidification.     

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.     

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.     

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.     

低温常压条件下水合物法储存甲烷的实验研究

利用水合物法实现对天然气的工业储运,需要提高水合物的储气量并解决水合物的分解速度问题。为此,文章研究了在十二烷基硫酸钠（SDS）体系中,甲烷水合物的储气量和在冰点以下的常压分解规律。研究发现,SDS浓度为650 mg/L时甲烷水合物储气量达到最高值,约为170 V/V。分解温度为268.2~272.2 K区域内,甲烷水合物的分解速率随温度的降低而降低;在268.2 K时,甲烷水合物分解速率最低。     

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.     

表面活性剂吸附对促进甲烷水合物生成效果的影响

基于表面活性剂固-液界面吸附理论,在无搅拌条件下研究了十二烷基硫酸钠（SDS（、脂肪醇聚乙烯醚硫酸钠（AES（、脂肪醇聚乙烯醚（AEO（3种表面活性剂在不锈钢反应釜中对甲烷水合物生成的促进效果。结果表明：水合物的生成形态与表面活性剂吸附金属表面形态有良好的对应关系;SDS与AES在金属表面的吸附作用可使水合物成核速率提高,成核位置增多。由于AEO不能在金属壁面发生吸附,导致对水合物生成促进效果降低,在浓度为300 mg·L^-1的SDS、AES和AEO溶液中,水合物储气密度及平均储气速率分别为131.4、128.3、12.3（体积比（和5.8、7.6、0.07 mmol·min^-1;逐步提高SDS溶液浓度（80~1200 mg·L^-1（和AES溶液浓度（60~1350 mg·L^-1（,水合物储气密度首先增大然后减小,储气速率线性增大。因此,合理选择表面活性剂种类及浓度,可显著促进水合物生成。     

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.     

Methane storage in wet activated carbon: Studies on the charging/discharging process

The dynamic behavior of charging/discharging methane onto/from water-preloaded activated carbon was studied at different conditions. It was shown that methane hydrate could form quickly in the porous space of carbon at the condition of 275 K and pressures beginning with 4.12 MPa. The stored methane could be continuously released at a constant flowrate for the whole discharging process. The packing density of 0.6 g cm⁻³ seemed optimal for the wet carbon tested, which yielded 152 V/V of released methane at charging pressure of 8 MPa. The thermal effect observed on the charging/discharging process was low and did not affect the effective storage capacity.     

Methane sorption on ordered mesoporous carbon in the presence of water

An ordered mesoporous carbon was synthesized using SBA-15 as the template. The sorption isotherms of methane on the synthesized carbon material were collected. Its ordered structure was confirmed by the XRD, SEM and TEM examinations. The BET surface area is 1100-1200 m²/g, the total pore volume is 1.24-1.30 cm³/g, and the pore size distribution is very narrow and centered at 2-5 nm. As high as 41.2 wt.% of methane was stored per unit mass of carbon at 275 K and pressures less than 7 MPa in the presence of 3.86 times more water. This sorption amount is 31% higher than the largest sorption capacity reached by activated carbon in the presence of water, which was equal to or higher than the storage capacity of compression till 20 MPa. The enthalpy change corresponding to the sudden change of isotherms was equal to the enthalpy change of methane hydrate formation; therefore, the mechanism of the enhanced methane storage was considered due to the formation of methane hydrate in the porous carbon material.     

Experimental study on the scale-up effect of gas storage in the form of hydrate in a quiescent reactor

This paper presents the experimental study on the scale-up effect of natural gas storage in the form of hydrates in a quiescent reactor. The hydrate formation experiments with respect to gas storage in the presence of sodium dodecyl sulfate (SDS) were initially performed in a 10 L reactor to study the scale-up effect by adjusting the mass of water loaded. The results demonstrated that the scale-up effect was very obvious, i.e., the specific hydrate formation rate, the moles of gas consumed per unit mass of water and time, decreased rapidly with the increasing mass of water loaded in the reactor. A multi-deck cell-type vessel was devised as the internals of the reactor to eliminate the scale-up effect, where water was loaded in each cell of the vessel instead of being loaded in the reactor directly and the hydrate formed in all cells of the vessel simultaneously. A double-deck cell-type vessel was set-up and a series of hydrate formation experiments were performed to study the influence of the number of deck and the size of each cell upon the specific formation rate and the storage capacity. The experimental results proved the feasibility of the multi-deck cell-type vessel. The influence of water quality was also studied and the results demonstrated that tap water could be used instead of the expensive distilled water in the formation of hydrates and the most suitable concentration of SDS in tap water was 2000 mg/L.     

Methane hydrate dissociation experiment in a middle-sized quiescent reactor using thermal method

Dissociation kinetic behavior of methane hydrate was studied at 268.15 K using thermal method in a closed quiescent middle-sized reactor of 10 L, which with a multi-deck cell-type vessel as the internals and coiled copper tubes placed inside assuring hydrate form or dissociate in all cells of the vessel simultaneously to reduce or eliminate the scale-up effect. A dramatically reduced dissociation rate phenomenon - “buffered dissociation” due to the ice melting was observed. The influences of the water temperature, the heating rate, the quantity of hydrate, and the dissociation pressure upon the dissociation rate and the extent of the buffering effect were investigated experimentally to reveal the gas production mechanism from hydrate below the ice point. The experimental results indicate that the rate of heat transfer and the thermodynamic driving force were the key rate-limiting factors for hydrate dissociation in the closed reactor. The buffering effect of gas production can be eliminated and the dissociation rate can be increased by increasing the temperature of the heating water and lowering the dissociation pressure. However, the temperature buffering behavior cannot be eliminated.     

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.