Kinetics of carbon dioxide and methane hydrate formation

Experimental data on the kinetics of carbon dioxide hydrate formation and its solubility in distilled water are reported. The experiments were carried out in a semi-batch stirred tank reactor at nominal temperatures of 274, 276 and 278 K and at pressure ranging from 1.59 to 2.79 MPa for the kinetics experiments and at pressure ranging from 0.89 to 2.09 MPa for the solubility experiments. A minor inconsistency in the kinetic model developed by Englezos et al. (1987a) was removed and the model was modified to determine the intrinsic kinetic rate constant for carbon dioxide hydrate formation. The same model was also used to re-determine the intrinsic kinetic rate constant for methane hydrate formation. The model is based on the crystallization theory coupled with the two-film theory for gas absorption in the liquid phase. The Henry's constant (H) and apparent dissolution rate constant (K_La) required in the model were determined using the experimental solubility data. The kinetic model describes the experimental data very well. The kinetic rate constant obtained for the carbon dioxide hydrate formation was found to be higher than that for methane.     

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.     

Separation of carbon dioxide and methane in continuous countercurrent gas centrifuges

The goal of this study is to determine the order of magnitude of the maximum achievable separation for decontaminating a natural gas well using a gas centrifuge. Previously established analytical approximations are not applicable for natural gas decontamination. Numerical simulations based on the batch case show that although the separative strength of the centrifuge is quite good, its throughput is very limited. Both enrichment and throughput are only a function of length and peripheral velocity. A centrifuge with a length of 5 m and a peripheral velocity of approximately 800 m/s would have a throughput of 0.57 mol/s and a product flow of 0.17 mol/s. These numbers are calculated with the assumption that the centrifuge is refilled and spun up instantaneously. The results for the countercurrent centrifuge show how the production rate varies as a function of internal circulation, product-feed ratio, peripheral velocity and centrifuge length and radius. Under conditions similar to those of the batch case the production is approximately half compared to the batch case, i.e., 0.08 mol/s. Optimization can yield a higher production at the cost of lower enrichment. Considering the current natural gas prices and the low production rate of the centrifuge, it is certain that the gas centrifuge will not generate enough revenue to make up for the high investment costs.     

Adsorption of hydrogen sulfide,carbon dioxide,methane, and their mixtures on activated carbon

Abstract

H₂S and CO₂ are acid contaminants of natural gas and biogas, which removal have been studied using adsorption data for monocomponent and binary mixtures. However, equilibrium adsorption data for H₂S?+?CO₂ + CH₄ mixture has not been investigated yet. In this work, H₂S and CO₂ partition coefficients (K) and activated carbon (AC) selectivity (S) for H₂S?+?CO₂ + CH₄ mixture separation at high-pressure and different temperatures were determined. To reach this goal, monocomponent isotherms for H₂S, CO₂ and CH₄ on Brazilian babassu coconut hush AC were experimentally determined at different temperatures and pressures. Then, obtained data were correlated by Langmuir and Tóth models, and multicomponent adsorption was predicted using Extended Langmuir, Extended Tóth and Ideal Adsorption Solution Theory (IAST) methods. Results indicate AC captures approximately 26?wt% of H₂S or CO₂. K values for CO₂ and H₂S reached more than 3 and 26, respectively, depending on the predictive model utilized and were higher for diluted mixtures (high CH₄ content in gas phase). S values for CO₂ and H₂S can reach values greater than 25 for Tóth?+?IAST. Furthermore, selectivity toward H₂S is approximately 5.6 times greater than CO₂. The effect of temperature on multicomponent results indicate K and S values decrease as temperature increases. Therefore, results obtained herein show that is possible to separate H₂S and CO₂ from mixture containing CH₄ using this AC as adsorbent and better separation performance was observed for low H₂S and CO₂ concentrations and lower temperatures.     

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.     

Determination of the intrinsic rate constant and activation energy of CO2 gas hydrate decomposition using in-situ particle size analysis

Experimental data on the rate of decomposition of CO₂ gas hydrates has been obtained using a semi-batch stirred tank reactor, with an in-situ particle size analyser, at temperatures ranging from 274 to and pressures ranging from 1.4 to . A method for calculating the moments of the particle size distribution has been presented. The experimental data was analysed using the kinetic model of Clarke and Bishnoi (Determination of the intrinsic kinetics of gas hydrate decomposition kinetics using particle size analysis, Presented at the Third International Conference on Gas Hydrates, Salt Lake City, Utah, July 18-22, 1999; Chem. Eng. Sci. 55 (2000) 4869) in its differential form in order to account for the slight change in temperature during the decomposition of CO₂ hydrates. The applicability of the new instrument for measuring gas hydrate decomposition kinetics was examined by conducting experiments with ethane at conditions similar to those encountered by Clarke and Bishnoi (2000). It was seen that the previously obtained rate constants for ethane hydrate decomposition were able to predict the new obtained data. A new procedure for regressing the intrinsic rate constant and activation energy has also been described and it is seen that the activation energy is and the intrinsic rate constant is for CO₂ gas hydrate decomposition.     

Unusual kinetic inhibitor effects on gas hydrate formation

Gas hydrate formation experiments were conducted with a methane-ethane mixture at 273.7 or 273.9 K and 5100 kPa and using water droplets or water contained in cylindrical glass columns. The effect of kinetic inhibitors and the water/solid interface on the induction time for hydrate crystallization and on the hydrate growth and decomposition characteristics was studied. It was found that inhibitors GHI 101 and Luvicap EG delayed the onset of hydrate nucleation. While this inhibition effects has been reported previously some unusual behaviour was observed and reported for the first time. In particular, the water droplet containing GHI 101 or Luvicap EG was found to collapse prior to nucleation and spread out on the Teflon surface. Subsequently, hydrate was formed as a layer on the surface. Catastrophic growth and spreading of the hydrate crystals was also observed during hydrate formation in the glass columns in the presence of the kinetic inhibitor. Finally, when polyethylene oxide (PEO) was added into the kinetic inhibitor solution the memory effect on the induction time decreased dramatically.     

Kinetics of structure II gas hydrate formation for propane and ethane using an in-situ particle size analyzer and a Raman spectrometer

The kinetics of structure II gas hydrates, formed from pure propane and a mixture of propane and ethane, were investigated and intrinsic rate constants were regressed from the experimental data. The experiments were conducted in a semi-batch stirred tank reactor equipped with an in-situ particle size analyzer and connected to an external Raman spectrometer. Experiments were conducted with pure propane at temperatures ranging from 274 to 276 K and pressures ranging from 0.39 to 0.43 MPa. The intrinsic rate constant for ethane in structure II was subsequently regressed from experimental data on the formation of hydrates formed from an equimolar mixture of propane and ethane at 274 K and 0.35 MPa. Raman spectroscopy was used to verify that ethane was present only in the large sII cavity.     

Methane and carbon dioxide emissions and nitrogen turnover during liquid manure storage

Animal slurry stored in-house and outside is a significant source of atmospheric methane (CH₄). The CH₄ source strength of stored slurry is greatly affected by temperature. To improve emission calculations on a global scale there is a need for knowledge about the relationship between production of CH₄ in slurry and temperature. In this study, the filling of slurry channels was reproduced in the laboratory by gradually filling 1 m-high PVC vessels during 9 days followed by incubation for 100–200 days. A preliminary test showed that little CH₄ was produced from animal slurry during 10 days of incubation at 20°C, if no inoculum (slurry incubated anaerobically at the test temperature for 1.5–2 months) was present. However, the addition of 7.6% inoculum supported an immediate production of CH₄. Vessels amended with inoculum and gradually filled with cattle or pig slurry were then incubated at 10, 15 and 20°C. Methane production from stored pig and cattle slurry was not significant at temperatures below 15°C, where CO₂ was the main product of decomposition processes. In contrast, the anaerobic production of CH₄ was high and significant relative to the production of CO₂ at 20°C. Peak emissions of CH₄ averaging 0.012 and 0.02 g C h⁻¹ kg⁻¹ volatile solids (VS) were reached within about 10 days at 10 and 15°C, respectively. At 20°C, the emission of CH₄ from pig slurry was about 0.01 g C h⁻¹ kg⁻¹ for 10 days, and thereafter emissions increased to about 0.10 g C h⁻¹ kg⁻¹ VS. For cattle slurry a peak emission of 0.08 g C h⁻¹ kg⁻¹ VS was measured after 180 days. Degradation of organic nitrogen (N) in cattle slurry was related to the reduction of organic material as reflected in CO₂ and CH₄ emission. The mineralization of organic N during storage represented 10–80% of organic N in cattle slurry, and 40–80% of the organic N in pig slurry.     

Hydrogenation of vegetable oils using mixtures of supercritical carbon dioxide and hydrogen

Hydrogenation of vegetable oils under supercritical conditions can involve a homogeneous one-phase system, or alternatively two supercritical components in the presence of a condensed phase consisting of oil and a solid catalyst. The former operation is usually conducted in flow reactors while the latter mode is more amenable to stirred, batch-reactor technology. Although many advantages have been cited for the one-phase hydrogenation of oils or oleochemicals using supercritical carbon dioxide or propane, its ultimate productivity is limited by the oil solubility in the supercritical fluid phase as well as unconventional conditions that affect the hydrogenation. In this study, a dead-end reactor has been utilized in conjunction with a head-space consisting of either a binary fluid phase consisting of varying amounts of carbon dioxide mixed with hydrogen or neat hydrogen for comparison purposes. Reaction pressures up to 2000 psi and temperatures in the range of 120–140°C have been utilized with a conventional nickel catalyst to hydrogenate soybean oil. Depending on the chosen reaction conditions, a wide variety of end products can be produced having different iodine values, percentage trans fatty acid content, and dropping points or solid fat indices. Although addition of carbon dioxide to the fluid phase containing hydrogen retards the overall reaction rate in most of the studied cases, the majority of products have low trans fatty acid content, consistent with a nonselective mode of hydrogenation.     

Facilitated-transport supported ionic liquid membranes for the simultaneous recovery of hydrogen and carbon monoxide from nitrogen-enriched gas mixtures

Off-gases with high content of carbon monoxide and hydrogen are often generated after a partial combustion of hydrocarbons in some industrial processes performed in reductive conditions. In these mixtures, both gases are usually accompanied by nitrogen. The selective recovery of these valuable compounds, H₂ and CO, employing an efficient membrane technology is sought as a means to reduce the environmental footprint of the industrial activity. In this respect, this work provides fundamental knowledge on the transport properties of H₂ through supported ionic liquid membranes (SILMs) prepared with an imidazolium-based room-temperature ionic liquid (RTIL) combined with either a chloride or a chlorocuprate(I) anion; this latter anion has already proved to enhance CO permeability across these SILMs due to a facilitated transport mechanism. Results showed that H₂ is more permeable than CO and N₂ through these RTILs due to its higher diffusivity. The H₂/N₂ and H₂/CO selectivities through the chloride-based RTIL are 11 and 6, respectively. However, when the RTIL with the chlorocuprate(I) anion is employed instead of the chloride anion, the H₂/N₂ selectivity does not change whereas the H₂/CO selectivity decreases, hence allowing obtaining a gas permeate stream with high content of both H₂ and CO, and very low content of N₂.     

Effects of Graphene Oxide Nanosheets and Al2O3 Nanoparticles on CO2 Uptake in Semi‐clathrate Hydrates

Gas hydrate/clathrate hydrate formation is an innovative method to trap CO₂ into hydrate cages under appropriate thermodynamic and/or kinetic conditions. Due to their excellent surface properties, nanoparticles can be utilized as hydrate kinetic promoters. Here, the kinetics of the CO₂ + tetra‐n‐butyl ammonium bromide (TBAB) semi‐clathrate hydrates system in the presence of two distinct nanofluid suspensions containing graphene oxide (GO) nanosheets and Al₂O₃ nanoparticles is evaluated. The results reveal that the kinetics of hydrate formation is inhibited by increasing the weight fraction of TBAB in aqueous solution. GO and Al₂O₃ are the most effective kinetic promoters for hydrates of (CO₂ + TBAB). Furthermore, the aqueous solutions of TBAB + GO or Al₂O₃ noticeably increase the storage capacity compared to TBAB aqueous solution systems.     

Prediction of carbon dioxide gas hydrate formation conditions in aqueous electrolyte solutions

A methodology for predicting the incipient equilibrium conditions for carbon dioxide gas hydrates in the presence of electrolytes such as NaCl, KCl and CaCl₂ is presented. The method utilizes the statistical thermodynamics model of van der Waals and Platteeuw (1959) to describe the solid hydrate phase. Three different models were examined for the representation of the liquid phase: Chen and Evans (1986), Zuo and Guo (1991), and Aasberg-Petersen et al. (1991). It was found that the model of Zuo and Guo (1991) gave the best results for predicting incipient CO₂ gas hydrate conditions in aqueous single salt solutions. The model was then extended for prediction of CO₂ gas hydrates in mixed salts solutions. The predictions agree very well with experimental data.     

Influence of adsorbed carbon dioxide on hydrogen electrosorption in palladium-platinum-rhodium alloys

Carbon dioxide electroreduction was applied to examine the processes of hydrogen electrosorption (adsorption, absorption and desorption) by thin electrodeposits of Pd-Pt-Rh alloys under conditions of cyclic voltammetric (CV) experiments. Due to different adsorption characteristics towards the adsorption product of the electroreduction of CO₂ (reduced CO₂) exhibited by the alloy components hydrogen adsorption and hydrogen absorption signals can be distinguished on CV curves. Reduced CO₂ causes partial blocking of hydrogen adsorbed on surface Pt and Rh atoms, without any significant effect on hydrogen absorption into alloy. It reflects the fact that adsorbed hydrogen bonded to Pd atoms does not participate in CO₂ reduction, while hydrogen adsorbed on Pt and Rh surface sites is inactive in the absorption reaction. In contrast, CO is adsorbed on all alloy components and causes a marked inhibition of hydrogen sorption (both adsorption and absorption)/desorption reactions.     

Selective adsorption of carbon dioxide over nitrogen on calcined synthetic hectorites with tailor-made porosity

Hectorites were synthesized using 1-butyl-3-methylimidazolium bromide, 1,3-didecyl-2-methylimidazolium chloride and 1-decyl-3-methylimidazolium chloride as synthesis directing agents at condensation temperature for 48 h. Calcinations of synthetic hectorites resulted mesoporous materials with pore diameters ranging from 3.4 to 5.5 nm. The pore diameters depended on the directing agent. Synthetic and calcined hectorites were characterized by powder X-ray diffraction. Adsorption properties of CO₂ and N₂ on calcined hectorites were investigated by volumetric measurements. The adsorption capacity for CO₂ and N₂ decreased with increasing pore diameter. The calcined hectorites showed very good selectivity for CO₂ over N₂ at lower as well as higher partial pressure at 303 K.     

In situ injection of THF to trigger gas hydrate crystallization: Application to the evaluation of a kinetic hydrate promoter

This paper investigates an original method to efficiently trigger gas hydrate crystallization. This method consists of an in situ injection of a small amount of THF into an aqueous phase in contact with a gas-hydrate-former phase at pressure and temperature conditions inside the hydrate metastable zone. In the presence of a CO₂–CH₄ gas mixture, our results show that the THF injection induces immediate crystallization of a first hydrate containing THF. This triggers the formation of the CO₂–CH₄ binary hydrate as proven by the pressure and temperature reached at equilibrium. This experimental method, which “cancels out” the stochasticity of the hydrate crystallization, was used to evaluate the effect of the anionic surfactant SDS at different concentrations, on the formation kinetics of the CO₂–CH₄ hydrate. The results are discussed and compared with those published in a recent article (Ricaurte et al., 2013), where THF was not injected but present in the aqueous phase from the beginning and at much higher concentrations.     

DSC measurements and modelling of the kinetics of methane hydrate formation in water-in-oil emulsion

The kinetics of formation of clathrate hydrates of methane was investigated in a water-in-oil emulsion using high-pressure differential scanning calorimetry in the range 10-40 MPa, at various temperatures. At high driving force, the heat peak related to the formation of hydrates has a regular and symmetric shape, and its height and width depend on the gas pressure and sub cooling degree. At near equilibrium conditions, hydrate formation is delayed by more than 1 h, but is still clearly observable. A model based on crystal growth theory, coupled with a normal distribution of induction times to take into account the germination in a population of micro-sized droplets, is proposed to represent the hydrate formation rate versus time in the particular case of water-in-oil emulsions. It uses four parameters which appear strongly correlated to the experimental conditions: the growth rate constant, the over saturation of gas in the water phase, the average and standard deviation of the induction time distribution.     

Capture of carbon dioxide by an ion-exchange resin: Influence of gas humidity on capture mechanisms

This paper evaluates moisture content effects on CO₂ capture of an ion-exchange resin (IER) functionalised with a primary amine group. IER capacities were determined by breakthrough with an inlet gas containing 10 vol% CO₂, nitrogen and various moisture contents. Three types of behaviour were identified according to humidity level. In saturated air conditions, the stoichiometry could be justified by carbonates and bicarbonates fixation. In dry conditions, we suspect a joint physical adsorption and reaction mechanism. For intermediate humidity, the stoichiometry of 1 CO₂ for 1 amine group is consistent with a bicarbonate fixation or carbamic acid formation.     

COSMO-RS:An ionic liquid prescreening tool for gas hydrate mitigation

Recently ionic liquids(ILs) are introduced as novel dual function gas hydrate inhibitors. However, no desired gas hydrate inhibition has been reported due to poor IL selection and/or tuning method. Trial error as well as selection based on existing literature are the methods currently employed for selecting and/or tuning ILs. These methods are probabilistic, time consuming, expensive and may not result in selecting high performance ILs for gas hydrate mitigation. In this work, COSMO-RS is considered as a prescreening tool of ILs for gas hydrate mitigation by predicting the hydrogen bonding energies(E_(HB)) of studied IL inhibitors and comparing the predicted E_(HB) to the depression temperature(?) and induction time. Results show that, predicted EHBand chain length of ILs strongly relate and significantly affect the gas hydrate inhibition depression temperature but correlate moderately(R = 0.70) with average induction time in literature. It is deduced from the results that, ? increases with increasing IL EHBand/or decreases with increasing chain length. However, the cation–anion pairing of ILs also affects IL gas hydrate inhibition performance. Furthermore, a visual and better understanding of IL/water behavior for gas hydrate inhibition in terms of hydrogen bond donor and acceptor interaction analysis is also presented by determining the sigma profile and sigma potential of studied IL cations and anions used for gas hydrate mitigation for easy IL selection.     

Low-temperature methanol synthesis from carbon dioxide and hydrogen via formic ester

A new route of methanol synthesis, at 443 K and under pressurized conditions, from carbon dioxide and hydrogen through formic ester was investigated, by using Cu-based catalysts. This one-pot reaction consisted of three steps:

1. formic acid synthesis from CO₂ and H₂,

2. esterification of formic acid by ethanol to ethyl formate, and

3. hydrogenolysis of ethyl formate to methanol and ethanol.