Nanofluid-assisted gas to hydrate (GTH) energy conversion for promoting CO2 recovery and sequestration processes in the petroleum industry

In this work the enhancement of gas to hydrate conversion employing the nanographene oxide (NGO)–based nanofluid regarding CO₂ capture and sequestration recovery is investigated. A new series of experiments are carried out at different pressures, temperatures, agitation intensities and NGO promoter concentrations by using a newly developed fully automated GTH (gas to hydrate) energy converter. According to the presented results at the 3 MPa and 275.15 K and in the presence of 30 ppm NGO, it is possible to reach a CO₂ gas to hydrate conversion of 95% at a low impeller speed in less than 2.5 h, which is quite interesting from an energy consumption standpoint. The presented approach can have potential application for development of low cost hydrate-based carbon dioxide recovery plants in petroleum industry.     

Optimal activated carbon for separation of CO2 from (H2 + CO2) gas mixture

Seven types of activated carbon were used to investigate the effect of their structure on separation of CO₂ from (H₂ + CO₂) gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO₂ from 53.6 mol% H₂ + 46.4 mol% CO₂ mixture and from 85.1 mol% H₂ + 14.9 mol% CO₂ mixture were different at 20 C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about 2.07 lm for 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture and 1.41 lm for 85.1 mol% H₂ + 14.9 mol% CO₂ mixture. The effect of specific area and pore diameter of activated carbon on separation CO₂ from 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture was more significant than that from 85.1 mol% H₂ ? 14.9 mol% CO₂ mixture. CO₂ in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.     

Prediction of hydrate formation conditions to separate carbon dioxide from fuel gas mixture in the presence of various promoters

In this study estimation of hydrate formation conditions to separate carbon dioxide (CO₂) from fuel gas mixture (CO₂+H₂) was investigated in the presence of promoters such as tetra-n-butylammonium bromide (TBAB), tetra-n-butylammonium fluoride (TBAF), and tetra-n-butyl ammonium nitrate (TBANO₃). The emission of CO₂ from the combustion of fuels has been considered as the dominant contributor to global warming and environmental problems. Separation of CO₂ from fuel gas can be an effective factor to prevent many of environmental impacts. Gas hydrate process is a novel method to separate and storage some gasses. In this communication, a feed-forward artificial neural network algorithm has been developed. To develop this algorithm, the experimental data reported in the literature for hydrate formation conditions in the fuel gas system with different concentrations of promoters in aqueous phase have been used. Finally, experimental data compared with estimated data and with calculation of efficiency coefficient, mean squared error, and mean absolute error show that the experimental data and predicted data are in acceptable agreement which demonstrate the reliability of this algorithm as a predictive tool.     

Influence of hydrogen sulfide on the efficiency of xenon recovery from natural gas by gas hydrate crystallisation

A mathematical simulation of the gas hydrate formation based on a gas mixture approximated to natural gas composition – CH₄+H₂S?+?CO₂+Xe at a normalized increase in hydrogen sulfide (H₂S) concentration in gas mixture from 3.08·10^?4?vol.% to 4.88?vol.%, at changes in the gas hydrate formation temperatures from 273.15?K to 283.15?K. It is shown that xenon (Xe) distribution coefficient decreases from 12.37 to 5.90, and is more dependent on the change in H₂S concentration than on the change in the gas hydrate formation temperature. Effective Xe recovery from natural gas at the gas hydrate formation temperature is 273.15?K, and at a minimum impurity concentration with a dissociation pressure close to Xe.     

Modelling of CO2 capture and separation from different gas mixtures using semiclathrate hydrates

In this work we present a model for predicting hydrate formation condition to separate carbon dioxide (CO₂) from different gas mixtures such as fuel gas (H₂+CO₂), flue gas (N₂+CO₂), and biogas gas (CH₄+CO₂) in the presence of different promoters such as tetra-n-butylammonium bromide (TBAB), tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium fluoride (TBAF), tetra-n-butyl ammonium nitrate (TBANO₃), and tetra-n-butylphosphonium bromide (TBPB). The proposed method was optimized by genetic algorithm. In the proposed model, hydrate formation pressure is a function of temperature and a new variable in term of Z, which used to cover different concentrations of studied systems. The study shows experimental data and predicted values are in acceptable agreement.     

A new empirical correlation for prediction of carbon dioxide separation from different gas mixtures

Carbon dioxide (CO₂) emission from different systems such as fuel gas (H₂+CO₂), flue gas (N₂+CO₂), and biogas gas (CH₄+CO₂) is one of the main factors of global warming and environmental problems. So, CO₂ separation from different systems is essential. Low energy consumption, environmental friendliness, and low operational cost of hydrate-based gas separation (HBGS) process show the high potential of this approach in separation of some gases such as CO₂. Hydrate phase equilibrium data are required for designing the separation process. So far numerous models has been proposed for prediction of hydrate formation/dissociation conditions in various systems with/without promoters or inhibitors. This study attempts to present a simple and comprehensive model for fast prediction of hydrate formation conditions to separate CO₂ from biogas, fuel gas, and flue gas systems in the presence of promoters such as tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium fluoride, tetra-n-butyl ammonium nitrate, and tetra-n-butylphosphonium bromide. According to the error analysis results, this point can reach the new proposed correlation has better estimation capability in comparison with Sayyad Amin et al. model. On the other hand, hydrate formation temperature can be predicted in the presented correlation with high accuracy.     

Effect of SDS,silver nanoparticles,and SDS + silver nanoparticles on methane hydrate semicompletion time

In this research, the semicompletion time (t_95%) of gas uptake in the process of methane hydrate formation in the presence and absence of sodium dodecyl sulfate (SDS) and silver nanoparticles (SNPs) is investigated. The experiments were carried out in a 460 cm³ stirred batch reactor at temperatures of 273.65 and 275.65 K and initial pressures of 5, 5.7, and 7 MPa. The results showed that the addition of both additives at all tested conditions, noticeably, decreases the semicompletion time of methane uptake, compared to pure water. The semicompletion time of methane uptake in the presence of 500 ppm SDS, 45 μM SNPs, and 500 ppm SDS + 45 μM SNPs is 75.6, 546.3, and 129.9 min, respectively, while that for pure water it is 8729.0 min at 273.65 K and 7 MPa.     

含杂质CO2管道输送水合物形成规律研究

在延长油田产生的CO₂气体输送过程中,管线会发生水合物冰堵,影响气体输送流量,为了探究CO₂水合物在管道输送过程中的形成规律,利用PVTSIM软件生成了CO₂水合物的相平衡曲线,并通过OLGA软件对水平管和弯管输送的水合物形成规律进行了模拟分析。结果表明:在低温高压条件下,水平管和弯管输送过程中均会有水合物形成,其生成过程是一种类似于盐类的结晶过程,通常包括成核和生长两个阶段,然后依靠流体颗粒之间的黏附力致使水合物聚集,与直管段相比,弯管段更容易产生水合物;水合物生成速率均由小到大,然后快速进入稳定阶段,最后趋于0。现场管线的水合物也多发生在弯管处,从而进一步验证了CO₂水合物的形成规律。因此,在管道输送过程中应避免高压出口和低温入口条件,保证管道安全运营。      

The Formation of Natural Gas Hydrate From SDS-Solutions and Decomposition By Microwave Heating in a Static Reactor

Gas mixture hydrates were quiescently produced from sodium dodecyl sulfate solutions of 20 ppm, 50 ppm, and 300 ppm to examine the potential for natural gas storage. Owing to the presence of C₂H₆ and C₃H₈, the concentration of 20 ppm is sufficient to promote the hydrate formation, although higher concentrations are better. The porous hydrate trapping more free water shows better microwave absorption and a higher decomposition rate. While conducting the work, pre-depressurization may weaken the water activity by forming ice.     

Experimental and Theoretical Investigations on the Enhancement of Methane Gas Hydrate Formation Rate by Using the Kinetic Additives

Effects of the most important influencing parameters on the methane gas hydrate formation kinetics at the onset of hydrate formation in the absence or presence of sodium dodecyl sulfate (SDS) kinetic promoter are investigated. At the SDS concentration of 500 ppm, the maximum methane effective diffusion coefficient and the highest conversion rate are obtained. The methane hydrate-liquid interfacial tension according to the suggested mechanism is about 18.6 mJm^–2 for all cases. The overall average absolute deviations between predicted and measured methane consumption rates are about 0.71% and 0.83% regarding nonpromoted and SDS-promoted gas hydrate formation processes, respectively.     

The Induction Time of Hydrate Formation From a Carbon Dioxide-Methane Gas Mixture

Kinetics of hydrate formation from CO₂?CH₄ gas mixture has been investigated. Eight experiments in various pressures, gas compositions, and load factors (volume of injected water/volume of reactor) were performed in a 460 CC vessel. For each gas mixture, the induction time of hydrate formation has been measured and the pressure-temperature-time diagram has been plotted. The results of the experiments show that by increasing the composition of carbon dioxide in the gas, the induction time of hydrate formation decreased and by increasing the load factor, the hydrate formation rate increased.     

Semicompletion time of carbon dioxide uptake in the process of gas hydrate formation in presence and absence of SDS and silver nanoparticles

Carbon dioxide emission to the atmosphere is one of the main causes of the current global warming. Therefore, capturing this greenhouse gas is very important. The effect of sodium dodecyl sulfate (SDS) and silver nanoparticles on semicompletion time (t_95%) of carbon dioxide uptake in the process of gas hydrate formation is investigated in this communication. The tests were performed at temperatures of 273.65 and 275.65 K and initial pressures of 2 and 3 MPa in a 460 cm³ stirred batch reactor. Experimental measurements show that utilization of SDS and silver nanoparticles decreases the semicompletion time of carbon dioxide uptake considerably. The addition of SDS with concentration of 500 ppm and silver nanoparticles with concentration of 45 μM at p = 2 MPa and T = 275.65 K, respectively, decreases the semicompletion time of carbon dioxide uptake 136.09% and 152.88%, compared to pure water. Investigating the effect of temperature on the amount of t_95% in the presence and absence of tested additives shows that this kinetic parameter decreases by increasing the temperature from 273.65 to 275.65 K.     

Exploitation of methane in the hydrate by use of carbon dioxide in the presence of sodium chloride

The replacement process of CH4 from CH4 hydrate formed in NaCl solution by using pressurized CO2 was investigated with a self-designed device at temperatures of 271.05,273.15 and 275.05 K and a constant pressure of 3.30 MPa.The mass fraction of the NaCl solution was either 0.5 wt% or 1.0 wt%.The effects of temperature and concentration of NaCl solution on the replacement process were investigated.Experimental results showed that high temperature was favorable to the replacement reaction but high NaCl concentration had a negative effect on the replacement process.Based on the experimental data,kinetic models of CH4 hydrate decomposition and CO2 hydrate formation in NaCl solution were established.The calculated activation energies suggested that both CH4 hydrate decomposition and CO2 hydrate formation are dominated by diffusion in the hydrate phase.     

Dissociation behavior of （CH4 ＋ C2H4） hydrate in the presence of sodium dodecyl sulfate

Separation of a mixture of CH4+C2H4 gas by forming hydrate in ethylene production has become of interest,and the dissociation behavior of(CH4+C2H4) hydrate is of great importance for this process. The hydrate formation rate could be increased by adding a small amount of sodium dodecyl sulfate(SDS) into water. In this work,the kinetic data of CH4(18.5 mol%) +C2H4(81.5 mol%) hydrate decomposition in the presence of 1000 mg·L-1 SDS at different temperatures and pressures were measured with the depressurizing m...     

Computation of equilibrium hydrate formation temperature for CO2 and hydrocarbon gases containing CO2 in the presence of an alcohol, electrolytes and their mixtures

This work presents the applicability of a unified model to predict the CO₂-rich gas and pure CO₂ hydrate formation conditions in aqueous solutions containing glycerol, methanol, ethylene glycol, electrolytes and their mixtures. A water activity model is introduced that combines the effect of the soluble gases, an alcohol and electrolytes. Then this model is used together with the model of Holder et al. [Holder, G.D., Corbin, G., Papadopoulos, K.D., 1980. Thermodynamic and molecular properties of gas hydrates from mixtures containing methane, argon and krypton. Ind. Eng. Chem. Fundam. 19 (3) 282] to predict CO₂-rich gas and CO₂ hydrate formation conditions. The predictions are in excellent agreement with experimental data.     

化学添加剂对水合物生成和储气的影响

为了研究促进剂对水合物生成的影响,采用自行设计的水合物反应系统,通过恒温定容实验,研究了四氢呋喃(THF)和十二烷基硫酸钠(SDS)对二氧化碳水合物生成的影响。并在实时测量水合物生成过程中系统的温度、压力的基础上,计算得出水合物的生成速率、储气量及表观水合数。结果表明,适宜浓度的SDS能促进气体在液相的溶解,提高水合物的生长速率和储气密度;单独添加THF对水合物生成过程促进效果并不明显;SDS和THF复合添加剂共同作用对水合物促进效果最显著。     

Analysis of coalescence process of methane hydrate in emulsion system

In oil and gas exploitation and pipeline transportation, hydrate formation poses a significant hidden danger to pipeline safety. Hydrates in the pipelines can coalesce easily on the inner wall surface. Therefore, studying the growth characteristics of hydrates in a multicomponent environment is crucial pipeline anti-blocking technology. Hence, two types of white oil emulsion, S85?+?T20 and S85?+?SDS, were prepared using sorbitol three oleic acid ester, polyoxyethylene sorbitol monoanhydride, and sodium dodecyl sulfate as dispersants. The mechanism of methane hydrate blockage in emulsion and particle systems at 40% moisture content was analyzed. The hydration reaction induction time and phenomenon characteristics of the two were compared, and the effect of the first 30?min particle size change on the hydration reaction was observed by focused beam reflectance measurement. The experimental results indicate that adding particles to the S85?+?SDS emulsion system can shorten the time of hydration reaction dissolved gas significantly, while the hydrophilic particle system will reduce the droplet size at a certain concentration, inhibit the heat transfer and mass transfer between molecules, and prolong the induction of hydrate formation.     

Kinetic study of methane hydrate formation in the presence of carbon nanostructures

The effect of synthesized nanostructures,including graphene oxide,chemically reduced graphene oxide with sodium dodecyl sulfate(SDS),chemically reduced graphene oxide with polyvinylpyrrolidone,and multi-walled carbon nanotubes,on the kinetics of methane hydrate formation was investigated in this work.The experiments were carried out at a pressure of 4.5 MPa and a temperature of 0 ℃ in a batch reactor.By adding nanostructures,the induction time decreases,and the shortest induction time appeares at certain concentrations of reduced graphene oxide with SDS and graphene oxide,that is,at a concentration of 360 ppm for reduced graphene oxide with SDS and 180 ppm for graphene oxide,with a 98% decrease in induction time compared to that in pure water.Moreover,utilization of carbon nanostructures increases the amount and the rate of methane consumed during the hydrate formation process.Utilization of multi-walled carbon nanotubes with a concentration of 90 ppm showes the highest amount of methane consumption.The amount of methane consumption increases by 173% in comparison with that in pure water.The addition of carbon nanostructures does not change the storage capacity of methane hydrate in the hydrate formation process,while the percentage of water conversion to hydrate in the presence of carbon nanotubes increases considerably,the greatest value of which occurres at a 90 ppm concentration of carbon nanotubes,that is,a 253% increase in the presence of carbon nanotubes compared to that of pure water.     

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文章利用新建立的实验台研究了十二烷基硫酸钠（SDS）和烷基多糖苷（APG）对天然气水合物形成过程的影响。表面活性剂可促进天然气在水中的溶解，从而提高水合物的形成速度。根据表面活性剂对天然气水合物形成耗气量的影响，实验表明十二烷基硫酸钠和烷基多糖苷在水合物形成体系中的临界胶束浓度分别为300 ppm和500 ppm。在临界胶束浓度表面活性剂溶液体系中，实验结果表明微量的表面活性剂减少了水合物形成诱导时间，提高了水合物形成速度和水合物形成的耗气量，并使水合物在静止系统中快速生长。混合表面活性剂可进一步提高水合物的形成速度，但不利于提高水合物形成的耗气量。