Hydrate Equilibrium Research Articles

The Experimental and Modeling Study on the Thermodynamic Equilibrium Hydrate Formation Pressure of Helium-Rich Natural Gas in the Presence of Tetrahydrofuran.

Hydrate-based gas separation (HBGS) has good potential in the separation of helium from helium-rich natural gas. HBGS should be carried out under a pressure higher than the thermodynamic equilibrium hydrate formation pressure (Peq) to ensure the formation of hydrate so that the accurate prediction of Peq is the basis of the determination of HBGS pressure. In this work, the Peq of the helium-rich natural gases with different helium contents (1 mol%, 10 mol%, and 50 mol%) in gas and different tetrahydrofuran (THF) contents (5 wt%, 10 wt%, and 19 wt%) in liquid at different temperatures were experimentally investigated through the isothermal pressure search method. A new thermodynamic model was proposed to predict the Peq of helium-rich natural gas. This model can quantitatively describe the effects of THF and helium on Peq, and it predicts the Peq of the helium-rich natural gases in this work accurately. The average relative deviation of the model is less than 3%. This model can guide the determination of the operating condition of the HBGS of helium-rich natural gas.

On the Significance of Hydrate Formation/Dissociation during CO2 Injection in Depleted Gas Reservoirs

Summary The study aims to quantitatively assess the risk of hydrate formation within the porous formation and its consequences on injectivity during storage of CO2 in depleted gas reservoirs considering low temperatures caused by the Joule-Thomson (JT) effect and hydrate kinetics. Hydrates formed during CO2 storage operation can occupy porous spaces in the reservoir rock, reducing the rock’s permeability and thus becoming a hindrance to the storage project. The aim was to understand which mechanisms can mitigate or prevent the formation of hydrates. The key mechanisms we studied included water dry-out, heat exchange with surrounding rock formation, and capillary pressure. A semicompositional thermal reservoir simulator is used to model the fluid and heat flow of CO2 through a reservoir initially composed of brine and methane. The simulator can model the formation and dissociation of both methane and CO2 hydrates using kinetic reactions. This approach has the advantage of computing the amount of hydrate deposited and estimating its effects on the porosity and permeability alteration. Sensitivity analyses are also carried out to investigate the impact of different parameters and mechanisms on the deposition of hydrates and the injectivity of CO2. Simulation results for a simplified model were verified with results from the literature. The key results of this work are as follows: (1) The JT effect strongly depends on the reservoir permeability and initial pressure and could lead to the formation of hydrates within the porous media even when the injected CO2 temperature was higher than the hydrate equilibrium temperature; (2) the heat gain from underburden and overburden rock formations could prevent hydrates formed at late time; (3) permeability reduction increased the formation of hydrates due to an increased JT cooling; and (4) water dry-out near the wellbore did not prevent hydrate formation. Finally, the role of capillary pressure was quite complex, as it reduced the formation of hydrates in certain cases and increased in other cases. Simulating this process with heat flow and hydrate reactions was also shown to present severe numerical issues. It was critical to select convergence criteria and linear system tolerances to avoid large material balance and numerical errors.

A new set of gas-structure-dependent parameters to improve gas hydrate equilibrium calculations and structure descriptions by van der Waals-Platteeuw model

The traditional Kihara potential parameters employed in the van der Waals-Platteeuw (vdW-P) model were only related to the species of hydrate-forming gases. Although our previous study (Chemical Engineering Science 248, 117213) proposed a framework for optimizing the gas-dependent Kihara potential parameters in vdW-P model to improve the hydrate equilibrium calculations, the predictions for hydrate structures are barely satisfactory. Thus, this study provides a new set of Kihara potential parameters which are dependent on not only the gas species but also the hydrate structures. With the constraints on hydrate structure changes, a novel procedure for fitting the gas-structure-dependent parameters is developed. The calculation results show that the newly obtained parameters improve the performances of vdW-P model in predicting the hydrate equilibria for the pure-gas and gas-mixture systems. Besides, the vdW-P model coupled with gas-structure-dependent parameters can provide reliable temperature-composition phase diagrams and acutely detect the crystalline structures for various gas hydrates.

Thermodynamic and Kinetic inhibition of Methane Hydrate with Organic Inhibitors

The present experimental work reports the impact of ethylene glycol, polyethylene glycol and glycerol on formation temperature, pressure and inhibition time of methane hydrate. The inhibition effects of hydroxyl functional group of inhibitors have been studied. It is evaluated in terms of temperature, pressure and induction time. Methane hydrate equilibrium temperature and pressure is also studied. Experimental results disclose that ethylene glycol is a strong candidate to hinder methane hydrate thermodynamically while glycerol is good competitor to discourage hydrate formation in both terms kinetic hindrance and thermodynamic hindrance.

Effect of particle size, water saturation, inorganic salt and methane on the phase equilibrium of CO2 hydrates in sediments

Understanding the thermal stability of gas hydrate in complex marine geological environment is of importance to hydrate-based carbon sequestration. In this work, the factors affecting the equilibrium of CO2 hydrate in ocean sediments, including quartz sands, inorganic salts and gas impurities were quantitatively measured in a temperature range from 273 to 283 K and a phase equilibrium model of hydrate was established. To reveal the distribution in pore structure, the micro-morphologies of hydrate-bearing sediments were measured by cryo-SEM. Results showed that reduction of initial water saturation, addition of NaCl and CH4 were found to have inhibitory effect on CO2 hydrate equilibrium. Initial water saturation reduced the equilibrium temperature by the capillary pressure, but only 0.3–0.7 K temperature depression was observed as the water saturation reduced to 5 %. About 5.7 K in the average temperature depression was found by the addition of 10 wt% NaCl and 24 mol% CH4. NaCl and CH4 influenced the hydrate equilibrium by changing the water activity and chemical potential of hydrate water lattice. SEM images showed that the hydrate formed in pores of quartz sand had porous surface and coated the sand particles like a layer of cells which are 5–20 μm in diameter, suggesting the hydrate layer exists between the liquid and gas phase. Based on the van der Waals-Platteeuw model, a hydrate equilibrium model was developed. The model provided a good prediction of the hydrate equilibrium in the presence of quartz sand, NaCl and CH4 with an averaged deviation of ±4.2 %, which had the potential to be applicated in more complexed ocean sedimentary environment.

Determination of hydrate phase equilibrium (H-L-V) data for the binary CO2–CH4 gas mixture in the presence of 1,3 dioxolane

Present work details the determination of three phase hydrate equilibrium data (H-L-V) using temperature search method for the binary CO2/CH4 gas mixture (50:50 molar ratio) in presence of 1,3 dioxolane (DIOX). DIOX concentration used for phase equilibrium determination were 1,3 and 5.56 mol% respectively. In the presence of DIOX, it was observed that phase equilibrium curve was shifted right with respect to the curve using same gas mixture with no additive (pure water). This indicates that the presence of DIOX moderates the hydrate formation equilibrium conditions. Also, as DIOX concentration increases from 1 mol% to 5.56 mol%, a decrement in phase equilibrium pressure at same temperatures was observed, confirming the potential of DIOX as an effective thermodynamic promoter. Enthalpy of hydrate dissociation was calculated for CO2/CH4 gas mixture in presence of DIOX using Clausius- Clapeyron plot and it was found to be 90.81±6.55 KJ/mol which confirms the sII structure of CO2-CH4-DIOX mixed hydrate. Besides providing the phase equilibrium data of formed hydrates with CO2/CH4 gas mixture using different concentration of DIOX, the present study will aid in determining suitable experimental conditions for examining kinetics and performing separation studies of CO2/CH4 gas mixture through hydrate formation.

Experimental and Modeling Study on Methane Hydrate Equilibrium Conditions in the Presence of Inorganic Salts.

The aim of this study was to determine the influence of four inorganic salts, KCl, NaCl, KBr and NaBr, on the thermodynamic conditions of methane hydrate formation. In order to achieve this, the vapor-liquid water-hydrate (VLWH) equilibrium conditions of methane (CH4) hydrate were measured in the temperature range of 274.15 K-282.15 K by the isothermal pressure search method. The results demonstrated that, in comparison with deionized water, the four inorganic salts exhibited a significant thermodynamic inhibition on CH4 hydrate. Furthermore, the inhibitory effect of Na+ on methane hydrate is more pronounced than that of K+, where there is no discernible difference between Cl- and Br-. The dissociation enthalpy (∆Hdiss) of CH4 hydrate in the four inorganic salt solutions is comparable to that of deionized water, indicating that the inorganic salt does not participate in the formation of hydrate crystals. The Chen-Guo hydrate model and N-NRTL-NRF activity model were employed to forecast the equilibrium conditions of CH4 hydrate in electrolyte solution. The absolute relative deviation (AARD) between the predicted and experimental values were 1.24%, 1.08%, 1.18% and 1.21%, respectively. The model demonstrated satisfactory universality and accuracy. This study presents a novel approach to elucidating the mechanism and model prediction of inorganic salt inhibition of hydrate.

The Phase Equilibria of Natural Gas Hydrate in the Presence of 1,3-Dimethylcyclohexane and Octyl-β-D-glucopyranoside.

The thermodynamic effect of octyl-β-D-glucopyranoside (OGP) on the formation of methane-1,3-dimethylcyclohexane (DMCH) hydrate was studied in this work. The thermodynamic equilibrium hydrate formation pressures between 275.15 K and 283.15 K were measured by the isothermal pressure search method. Different OGP aqueous solutions (0, 0.1, and 1 wt%) were used in this work. The experimental results show that OGP had no obvious thermodynamic inhibition on methane-DMCH hydrate formation when its concentration was low (0.1 wt%), whereas it had an inhibition on methane-DMCH hydrate formation when its concentration was high (1 wt%). The phase equilibrium hydrate formation pressure of the methane-DMCH-OGP system is about 0.1 MPa higher than that of the methane-DMCH system. The dissociation enthalpies of methane hydrate in different solutions remained uniform, which indicates that OGP was not involved in methane-DMCH hydrate formation. This phenomenon is explained from the perspective of the molecular structure of OGP. As a renewable and biological nonionic surfactant, the concentration of OGP in the liquid phase is low, so OGP can be added to the methane-DMCH system without significant thermodynamic inhibition.

Fundamental insights into multistep depressurization of CH4/CO2 hydrates in the presence of N2 or air

Exploitation of natural gas hydrates provides an alternative way to address energy crisis. Dilute CO2 gas (13–30mol%CO2 with remaining N2/Air) injection into CH4 hydrates for hydrate swapping (SW) allows cheaper and more practical CH4 recovery and in-situ CO2 sequestration. However, the roles of N2/Air in dilute CO2 gas during exploitation remain unknown. It is unclear whether depressurization should be coupled after SW and continued below CH4 hydrate stability pressure. This work employed multistep depressurization (MD) to dissociate the mixed hydrates formed after SW from 86.5 to 97.9 bar at 0.7–1.2 °C in bulk-water and sandpack with CH4 hydrate saturation of 4.1–25.3 %. Effects of N2/Air on exploitation were investigated by examining hydrate morphologies and gas compositions. Morphological results in bulk-water indicated higher N2 fraction in 20mol%CO2/N2 triggered more CO2-rich hydrate reformation and CH4-rich hydrate dissociation. Exploitation results in sandpack indicated 13mol%CO2/N2 produced the highest CH4 swapping percent (46.6 %) and CO2 hydrate sequestration percent (29.1 %). Air exerted weaker promoting effects on exploitation compared with equivalent N2. The promotion of N2/Air on exploitation was dominated by dilute CO2 gas injection altering mixed hydrate equilibrium which varied with time-dependent gaseous compositions during MD. l-methionine of 3000 ppm had stronger promoting effects on CO2 sequestration in sandpack than bulk-water depending on mass transfer and water availability. Ceasing points (13.9–31.4 bar) suggested MD could be continued below CH4/above CO2 hydrate stability pressures and before water production. For the first time, this study provided insights into the roles of N2/Air to determine injection gas types and depressurization schemes for efficient and safe hydrate exploitation in gas-rich hydrate-bearing sediment.

Robust and comprehensive predictive models for methane hydrate formation condition in the presence of brines using black-box and white-box intelligent techniques

Accurate estimation of gas hydrate formation condition is crucial for many reasons. In one hand, the gas hydrate formation is a promising approach for gas separation, cold energy storage, seawater desalination, etc. On the other hand, in some industries, this phenomenon may cause some challenges, such as pipelines blockage. The current study was undertaken to develop trustworthy predictive tools for methane hydrate formation temperature (MHFT) in the presence of brines. To achieve this target, 1051 experimental data pertinent to the methane hydrate equilibrium in 26 single and multiple brines over an extensive range of operating conditions were amassed from published studies. Four simple factors, including pressure, brine concentration, salt molecular weight and salt melting temperature were defined as the input variables, and the black-box intelligent techniques, including gaussian process regression (GPR), multilayer perceptron (MLP) and radial basis function (RBF) were employed to link MHFT to the mentioned factors. A plethora of graphical and statistically-based assessments were performed to determine the accuracy level of the proposed models. While all intelligent models had excellent performances, the one established by the GPR method showed the best agreements with experimental data, and gave the AARE and R2 values of 0.14% and 99.17%, respectively, in the testing step. The foregoing model was capable of predicting MHFT over a broad range of conditions with relative deviations mostly below 0.10%. Additionally, it showed an excellent performance in describing the physical variations of MHFT versus operating factors. The authority of the analyzed databank and the presented model was asserted via the William's plot investigation. Moreover, a sensitivity analysis was undertaken in order to determine the most fundamental factors in controlling MHFT. Eventually, a simple mathematical correlation was also derived based on the white-box intelligent approach of gene expression programming (GEP), which allowed the accurate estimation of MHFT with an AARE of 0.56%.

Step-wise ion hydration modeling of aqueous solutions of 1:1 acid neutral electrolytes at different temperatures

In a previous work, we showed that the current stepwise ion hydration framework was promising for modeling electrolyte activities at 298.15 K. Briefly, the model assumes that (1) ions are hydrated in solution and this hydration is governed by an equilibrium between the bound and free water, (2) the mean spherical approximation (MSA) models the long range electrostatic interactions in the solution sufficiently well, and (3) this solution behaves ideally. In this work, we continue developing this model by exploring its temperature dependence. MSA has no temperature-dependent adjustable parameters. The hydration equilibrium constants are temperature dependent due to non-zero enthalpy and specific heat of the hydration equilibrium. Their values were adjusted. The calculated osmotic coefficients from the model are in good agreement with measured values.

Preparation and properties of activated carbon-based Na3PO4 composites for low-temperature thermochemical heat storage

With the advantages of low heat storage temperature, high heat storage density, and a low price, Na3PO4 has been proposed as a thermochemical heat storage candidate material for use in solar low-temperature heat storage engineering applications. However, the application of pure Na3PO4 is limited due to its propensity for agglomeration. In this study, activated carbon-based Na3PO4 (R-AC@Na3PO4) composites with mass fractions of 30 %, 50 %, and 80 % were synthesized by melt impregnation method using activated carbon as the porous matrix. The morphology and structure of the composites were characterized, and their heat storage performances were investigated. The hydration experiments were carried out in a constant temperature and humidity chamber and dehydration experiments were carried out in thermogravimetric analysis and differential scanning calorimetry simultaneously. The results showed that at 30 °C, 60 % relative humidity, the hydration equilibrium time for the composites were only 30 %–40 % of the pure material. Meanwhile, at a mass fraction of 80 %, material's volumetric heat storage can reach 1793 J·cm−3 without agglomeration, and the performance was stable after 20 cyclic tests. This study provides a reference for the research and development of low-temperature thermochemical heat storage materials and offers more possibilities for R-AC@Na3PO4 composites in future engineering applications.

Coupling amino acid injection and slow depressurization with hydrate swapping exploitation: An effective strategy to enhance in-situ CO2 storage in hydrate-bearing sediment

Natural gas (mainly methane, CH4) hydrates are a prospective energy resource. CH4-CO2 hydrate swapping has the advantages of producing CH4 gas for clean energy recovery and simultaneously storing CO2 in-situ for carbon emission reduction. Depressurization is the most feasible strategy to recover CH4 from hydrate-bearing sediments. The combination of these two methods has been proved feasible to produce CH4-rich gas and store CO2-rich hydrate. However, the efficiencies of CH4 recovery and CO2 storage decrease significantly when the reservoir is depressurized to the points below CH4/CO2 mixed hydrate equilibrium pressure causing unwanted CO2-rich hydrate dissociation. In this work, amino acid injection (AAI) (L-tryptophan or L-methionine) was employed for CH4/CO2 mixed hydrate formation with enhanced CO2 storage, followed by slow depressurization in various controlled manners, i.e., multistep depressurization, constant-pressure depressurization or multistep constant-pressure depressurization (MCPD) to recover CH4 from the mixed hydrates. In-situ Raman and gas chromatograph (GC) were employed to confirm the compositions of mixed hydrates formed and mixed gases produced. The results showed that AAI decreased CO2 fraction from 30 mol% to 3.1–8.4 mol% in the residual gas, indicating the technique helped regaining reservoir pressure and kinetically promoting further hydrate formation. The pressure recovered by AAI compensated the performance discrepancy caused by different solutions injected. Raman spectra and GC results confirmed CO2-rich hydrate formation, and up to 91.3% CO2 was stored in the sediments. During mixed hydrate dissociation, slow depressurization maintained high CH4-rich gas production (CH4 fraction over 87.5 mol%), with 9.7–30.6% CH4-rich gas recovered and 5.8–17.9% water produced among various trials. The best performance of CO2 storage and CH4 recovery was achieved by AAI of 1000 ppm L-tryptophan at 33.2 bar and MCPD to 20.9 bar, showing a final CO2 storage efficiency of 82.3%, gas recovery percentage of 30.6% and gas/water production ratio of 37.9 STP m3/m3. These findings provided guidance to enhance CO2-rich hydrate storage and CH4-rich gas production by multiple AAI and slow depressurization at controlled depletion pressures after hydrate swapping.

Thermal stabilities of CH4 and CO2 hydrates in quartz sands and modeling

Forming an impermeable hydrate bearing layer is a novel path to prevent CO2 leakage during marine carbon storage. To make an accurate description of the formation of impermeable hydrate bearing layer, the equilibria of CH4 and CO2 hydrates in quartz sands were measured in a temperature range from 273 to 283 K using isochoric pressure search method and HP-μDSC. The influence of particle size from 0.025 to 0.3 mm and water saturation from 5 to 30 % on the hydrate equilibrium were analyzed. Based on the typical hydrate equilibrium model, van Genuchten model was employed to describe the capillary effect. Results showed that particle size had negligible effect on the equilibria of CH4 and CO2 hydrates, but a decrease in water saturation was found to lead an exponential growth in temperature depression. As the water saturation reduced down to 10 % and below, the temperature depression surged from about 0.1 up to 0.89 K in maximum. The dissociation enthalpies of CH4 and CO2 hydrates were determined as 56.01 ± 1.29 and 64.98 ± 1.90 kJ/mol respectively. The reduction of water saturation from 30 to 5 % was found to enhance the dissociation enthalpy for CH4 hydrate, but no similar effect was observed for CO2 hydrate.

Thermodynamic modeling of sour gas mixture (CH4/C3H8/H2S) hydrate formation in the presence of thermodynamic inhibitors mono ethylene glycol, NaCl, and CaCl2 using the ion pair concept

Thermodynamic modeling of hydrate equilibrium conditions for sour gas mixture (CH4/C3H8/H2S) in the presence of pure water and thermodynamic inhibitor(s) (MEG, NaCl, and CaCl2) was investigated in this study. Hydrate and vapor phases were evaluated using the van der Waals and Plattueew model, and the Peng-Robinson EoS along with the classic van der Waals mixing rule, respectively. As a different approach, by combining non-synonymous salt ions and forming ion pairs, they can be considered as molecular species. So ion pair concept was used to investigate liquid phase and calculate water activity coefficient in this phase. For short-range and long-range forces, the NRTL molecular model and the Pitzer-Debye-Hückel equation was used, respectively. The results of experimental data in the previous work were compared with the results of the proposed model and PVTsim Nova 3.0 software, and it was discovered that they have an acceptable agreement together. The average deviation in pressure (AARDP %) related to the model is 0.36% to 4.34% and 3.41% to 5.68% related to the software.

A novel model to predict phase equilibrium state of hydrates from the relationship of gas solubility

The study of hydrate phase equilibrium is crucial for ensuring the safety of natural gas pipeline transportation and the process of hydrate recovery. While scientists typically focus on the chemical potential of hydrates, the role of gas solubility in hydrate phase equilibrium remains unclear, and this study fills this gap. This work investigated the solubility of gas at the equilibrium point of the hydrate phase through model calculations. Additionally, a new model of hydrate phase equilibrium is established based on the relationship between solubility. Firstly, a solubility model based on gas-liquid equilibrium theory showed higher prediction accuracy in comparison to the PR equation and Duan model and was then used to calculate gas solubility under hydrate phase equilibrium conditions. Afterwards, a novel model was developed to predict hydrate equilibrium state based on the relationship between gas solubility and hydrate phase equilibrium temperature, and it was further compared with the Chen–Guo model and CSMGem in terms of prediction accuracy under pure water and brine settings. The results showed: (a) The calculation deviation of the solubility model was 0.7–8.7% in pure water settings and 2.6–11.7% in brine settings; (b) A strong linear correlation between the phase equilibrium temperature of hydrates and gas solubility was also found; (c) This proposed model achieved over 10 times the accuracy of the Chen–Guo model and the CSMGem in predicting the phase equilibrium state of N2 and CO2 hydrates, and 3–10 times higher accuracy than that of the Chen–Guo model and CSMGem in brine. This work suggests that the gas solubility equilibrium theory can provide a more accurate prediction of hydrate states.

Effect of Pore Confinement of Ionic Liquids on Solute Diffusion within Mesoporous Silica Microparticles.

The transport properties of the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) confined within silica microparticles with well-ordered, accessible mesopores (5.4 or 9 nm diameter) were investigated. [BMIM][PF6] confinement was confirmed by using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The transport properties of the confined IL were studied using the neutral and cationic fluorescent probes 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) and rhodamine 6G, respectively, through fluorescence recovery after photobleaching (FRAP) in confocal microscopy. The diffusivity of DCM in 9 nm pores is 0.026 ± 0.0091 μm2/s, which is 2 orders of magnitude less than in the bulk ionic liquid. The pore size did not affect the diffusivity of DCM in unmodified silica nanopores. The diffusivity of the cationic probe is reduced by 63% relative to that of the neutral probe. Diffusivity is increased with water content, where equilibrium hydration of the system leads to a 37% increase in DCM diffusivity. The most dramatic impact on diffusivity was caused by tethering an IL-like methylimidazolium chloride group to the pores, which increased the pore hydrophobicity and resulted in 3-fold higher diffusivity of DCM compared to bare silica pores. Subsequent exchange of the chloride anion from the tethering group with PF6- decreased the diffusivity to half that of bare silica. The diffusion of probe molecules is affected most strongly by the pore wall effects on probe interactions rather than by the pore size itself, which suggests that understanding pore wall diffusion is critical to the design of nanoconfined ILs for separations, catalysis, and energy storage.

Experimental investigation and modeling on the dissociation kinetics of methane hydrate in clayey silt cores in depressurization

Natural gas hydrate (NGH) in clayey silts might be the majority of its global reserve. A thorough understanding on the dissociation kinetics of NGH in clayey silts is crucial for its safe and efficient exploitation. In this study, the dissociation characteristics of methane hydrate in quartz silts, montmorillonites and South China Sea (SCS) sediments made cores in multi-step depressurization was experimentally studied and modeled. In quartz silt core, methane hydrate thoroughly dissociated once the pressured is lowered to the equilibrium pressure in bulk. In montmorillonite and SCS sediment cores, methane hydrate dissociation initiated at higher pressure than quartz silt. Capillary and clay induced water activity depressions are suggested to be the major causes. Stepwise methane hydrate dissociation was discovered in the montmorillonite and SCS sediment cores in multi-stage depressurization. In one step depressurization, hydrate in the fine grain cores with larger surface area dissociated faster. In montmorillonite and SCS sediment cores, lower water content leads to faster dissociation at the same pressure, which may be attributed to the higher driven force for dissociation (fugacity difference fe-f). A kinetic model for NGH dissociation in clayey silts was established by introducing fitted equivalent diameter and surface area correction factor of hydrate particles to the Kim-Bishnoi model. In the model, the hydrate equilibrium conditions in clayey silts were predicted by the water activity measurement (WAM) technique. With a maximum deviation of 9.81% in gas production, the model prediction and experimental results are in good agreement. The experimental findings and model reported in this work may be helpful to understand the NGH phase transition mechanism in clayey silt sediments.

Direct measurement of hydrate equilibrium temperature in CO2 and CO2 rich fluids with low water content

A high-pressure experimental setup was used to obtain experimental data on the hydrate equilibrium (melting) temperature (HET) of hydrates formed from low water content CO2 and CO2 rich mixtures. A novel method was used to measure hydrate formation temperature in addition to melting temperature directly at realistic temperature/pressure conditions encountered in transport by pipelines or ship. The method can be used to evaluate the likelihood of hydrate formation in pipelines/ships transporting pure CO2 and CO2 coming from capture processes as well as from high CO2 content produced gas. The data generated from the measurement can also be used to investigate the kinetics of hydrate formation and dissociation in low water content fluids at pipeline/ship conditions. This paper details the experimental equipment, methods, test fluids and results. Experimental results are compared against predictions of the simplified cubic plus association equation of state (sCPA-EoS) coupled with the van der Waals and Platteeuw solid solution theory.

Effect of sec-butyl alcohol on CO2 hydrate equilibrium conditions

Thermodynamic inhibitors may be used to inhibit hydrate formation in industry. Alcohol substances, due to their hydrophilic hydroxyl groups in their molecular structure, are prone to form hydrogen bond with water molecules to inhibit hydrate formation. In this work, sec-butyl alcohol is chosen to study the effects on CO2 hydrate dissociation equilibrium conditions, where the step-heating method is utilized to obtain hydrate equilibrium conditions. The equilibrium curve of carbon dioxide hydrate dissociation moves to the region of lower temperatures or higher pressures. The higher mass fraction of sec-butyl alcohol, the better effect of inhibiting hydrate formation. Sec-butyl alcohol can be used as a thermodynamic hydrate inhibitor.