Experimental study on flow characteristics of tetrahydrofuran hydrate slurry in pipelines

Tetrahydrofuran（THF） was selected as the substitute to study the flow behaviors and the mechanism of the hydrates blockage in pipelines.The slurrylike hydrates and slushlike hydrates are observed with the formation of hydrates in pipeline.There is a critical hydrate volume concentration of 50.6% for THF slurries and pipeline will be free of hydrate blockage while the hydrate volume concentration is lower than the critical volume concentration;otherwise,pipeline will be easy to be blocked.Fully turbulent flow occurs and friction factors tend to be constant when the velocity reaches 1.5 m/s.And then,constant values of friction factors that depend on the volume concentrations in the slurry were regressed to estimate the pressure drops of THF hydrate slurry at large mean velocity.Finally,a safe region,defined according to the critical hydrate volume concentration,was proposed for THF hydrate slurry,which may provide some insight for further studying the natural gas hydrate slurries and judge whether the pipeline can be run safely or not.

CO_2 capture from binary mixture via forming hydrate with the help of tetra-n-butyl ammonium bromide

Hydrate formation rate and separation effect on the capture of CO2 from binary mixture via forming hydrate with 5 wt% tetra-n-butyl ammonium bromide （TBAB） solution were studied. The results showed that the induction time was 5 min, and the hydrate formation process finished in 1 h at 4.5 ℃ and 4.01 MPa. The hydrate formation rate constant reached the maximum of 1.84× 10^-7 molZ/（s.J） with the feed pressure of 7.30 MPa. The CO2 recovery was about 45 % in the feed pressure range from 4.30 to 7.30 MPa. Under the feed pressure of 4.30 MPa, the maximum separation factor and CO2 concentration in hydrate phase were 7.3 and 38.2 mol%, respectively. The results demonstrated that TBAB accelerated hydrate formation and enriched CO2 in hydrate phase under the gentle condition.

Inhibitory effects of novel green inhibitors on gas hydrate formation

Natural gas hydrates easily form in pipelines,causing potential safety issues during oil and gas production and transportation.Injecting gas hydrate inhibitors is one of the most effective methods for preventing gas hydrate formation or aggregation.However,some thermodynamic hydrate inhibitors are toxic and harmful to the environment,whereas degradation of kinetic inhibitors is difficult.Therefore,environmentally friendly and easily biodegradable novel green inhibitors have been proposed and investigated.This paper provides a short but systematic review of the inhibitory performance of amino acids,antifreeze proteins,and ionic liquids.For different hydrate formation systems,the influences of the inhibitor type,structure,and concentration on the inhibitory effects are summarized.The mechanism of green inhibitors as kinetic inhibitors is also discussed.The progress described here will facilitate further developments of such green inhibitors for gas hydrate formation.

Use of Electrical Resistance to Detect the Formation and Decomposition of Methane Hydrate

电的抵抗(R) 的变化同时在 CH4 水合物形成和分解的过程试验性地被学习，用象辅助检测方法的温度和压力。实验结果证明 R 与水合物形成增加并且与水合物 decompositon 减少。R 比温度或压力对水合物形成和 decompositon 更敏感，它显示 R 的察觉将是为检测天然气的一个有效工具水合物(NGH ) 份量上。

Molecular dynamics simulations for the growth of CH_4-CO_2 mixed hydrate

Molecular dynamics simulations are performed to study the growth mechanism of CH4-CO2 mixed hydrate in xco2 = 75%, xco2 = 50%, and zco2 = 25% systems at T = 250 K, 255 K and 260 K, respectively. Our simulation results show that the growth rate of CH4-CO2 mixed hydrate increases as the CO2 concentration in the initial solution phase increases and the temperature decreases. Via hydrate formation, the composition of CO2 in hydrate phase is higher than that in initial solution phase and the encaging capacity of CO2 in hydrates increases with the decrease in temperature. By analysis of the cage occupancy ratio of CH4 molecules and CO2 molecules in large cages to small cages, we find that CO2 molecules are preferably encaged into the large cages of the hydrate crystal as compared with CH4 molecules. Interestingly, CH4 molecules and CO2 molecules frequently replace with each other in some particular cage sites adjacent to hydrate/solution interface during the crystal growth process. These two species of guest molecules eventually act to stabilize the newly formed hydrates, with CO2 molecules occupying large cages and CH4 molecules occupying small cages in hydrate.

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(150–250μm)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.

Estimation of ultra-stability of methane hydrate at 1 atm by thermal conductivity measurement

Thermal conductivity of methane hydrate was measured in hydrate dissociation self-preservation zone by means of the transient plane source（TPS） technique developed by Gustafsson.The sample was formed from 99.9%（volume ratio） methane gas with 280 ppm sodium dodecyl sulfate（SDS） solution under 6.6 MPa and 273.15 K.The methane hydrate sample was taken out of the cell and moved into a low temperature chamber when the conversion ratio of water was more than 90%.In order to measure the thermal conductivity,the sample was compacted into two columnar parts by compact tool at 268.15 K.The measurements are carried out in the temperature ranging from 263.15 K to 271.15 K at atmospheric pressure.Additionally,the relationship between thermal conductivity and time is also investigated at 263.15 K and 268.15 K,respectively.In 24 h,thermal conductivity increases only 5.45% at 268.15 K,but thermal conductivity increases 196.29% at 263.15 K.Methane hydrates exhibit only minimal decomposition at 1 atm and the temperature ranging from 263.15 K to 271.15 K.At 1 atm and 268.15 K,the total gas that evolved after 24 h was amounted to less than 0.71% of the originally stored gas,and this ultra-stability was maintained if the test was lasted for more than two hundreds hours before terminating.