An experimental evaluation and molecular simulation of high temperature gas adsorption on nanoporous carbon

A combination of experiments and molecular simulations has been used to further understand the contribution of gas adsorption to the carbon dioxide (CO₂) selectivity of nanoporous carbon (NPC) membranes as a function of temperature and under mixed gas conditions. Whilst there have been various publications on the adsorption of gases onto carbon materials, this study aims to benchmark a simulation model with experimental results using pure gases. The simulation model is then used to predict mixed gas behaviour. These mixed gas results can be used in the assessment of NPC membranes as a suitable technology for both carbon dioxide separations from air-blown syngas and from natural gas. The gas adsorption experiments and molecular simulations have confirmed that CO₂ is more readily adsorbed on nanoporous carbon than methane (CH₄) and nitrogen (N₂). Increasing the temperature reduces the extent of adsorption and the CO₂ selectivity. However, the difference between the CO₂ and N₂ heats of adsorption is significant resulting in good CO₂/N₂ separation even at higher temperatures.     

Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas–water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.     

Adsorption of carbon dioxide, ethane, and methane on titanosilicate type molecular sieves

The separation of carbon dioxide from light hydrocarbons is a vital step in multiple industrial processes that could be achieved by pressure swing adsorption (PSA), if appropriate adsorbents could be identified. To compare candidate PSA adsorbents, carbon dioxide, methane, and ethane adsorption isotherms were measured for cation exchanged forms of the titanosilicate molecular sieves ETS-10, ETS-4, and RPZ. Mixed cation forms, such as Ba/H-ETS-10, may offer appropriate stability, selectivity, and swing capacity to be utilized as adsorbents in CO₂/CH₄ PSA processes. Certain cation exchanged forms of ETS-4 were found to partially or completely exclude ethane by size, and equivalent RPZ materials were observed to exclude both methane and ethane, while allowing carbon dioxide to be substantially adsorbed. Adsorbents such as Ca/H-ETS-4 and Ca/H-RPZ are strong candidates for use in PSA separation processes for both CO₂/C₂H₆ and CO₂/CH₄, potentially replacing current amine scrubber systems.     

A comparative study of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> adsorption using activated carbon prepared from pine cone by phosphoric acid activation

Adsorption of pure carbon dioxide and methane was examined on activated carbon prepared from pine cone by chemical activation with H₃PO₄ to determine the potential for the separation of CO₂ from CH₄. The prepared adsorbent was characterized by N₂ adsorption-desorption, elemental analysis, FTIR, SEM and TEM. The equilibrium adsorption of CO₂ and CH₄ on AC was determined at 298, 308 and 318 K and pressure range of 1–16 bar. The experimental data of both gases were analyzed using Langmuir and Freundlich models. For CO₂, the Langmuir isotherm presented a perfect fit, whereas the isotherm of CH₄ was well described by Freundlich model. The selectivity of CO₂ over CH₄ by AC (CO₂: CH₄=50: 50, 298K, 5 bar), predicted by ideal adsorbed solution theory (IAST) model, was achieved at 1.68. These data demonstrated that pine cone-based AC prepared in this study can be successfully used in separation of CO₂ from CH₄.     

Extraction of methane hydrate energy by carbon dioxide injection-key challenges and a paradigm shift

Significant effort including field work has been devoted to develop a natural gas extraction technology from natural gas hydrate reservoirs through the injection of carbon dioxide. Natural gas hydrate is practically methane hydrate. The hypothesis is that carbon dioxide will be stored as hydrate owing to its favorable stability conditions compared to methane hydrate. Although the dynamics of the CO₂/CH₄ exchange process are not entirely understood it is established that the exchange process is feasible. The extent is limited but even if the CH₄ recovery is optimized there is a need for a CH₄/CO₂ separation plant to enable a complete cyclic sequence of CO₂ capture, injection and CH₄ recovery. In this paper we propose an alternative paradigm to the Inject (CO₂)/Exchange with (CH₄)/Recover (CH₄) one namely Recover (CH₄) first and then Inject (CO₂) for Storage.     

Diffusion of gases in metal containing carbon aerogels

Carbon aerogels containing Fe, Ni, Cu or no metal were prepared by carbonisation of polymer aerogels synthesised from 2,4-dihydroxybenzoic acid and formaldehyde and modified by CVD of benzene. Uptakes and diffusion coefficients of CO₂, CH₄, N₂ and O₂ were measured and the results compared with those obtained using a commercial carbon molecular sieve. The results indicated that the diffusion of light gas molecules in carbon aerogels cannot be interpreted solely on the basis of micropore diffusion, but that the very high mesopore volumes of the aerogel monoliths exert a strong influence on the kinetics of diffusion in these materials. The mesoporosity is decreased when the % solids used during synthesis of the polymer precursor increases and this resulted in kinetic behaviour which was more similar to that predicted by Fickian or LDF models. Increasing % solids was also accompanied by generally slower diffusion rates and generally lower uptakes. The single gas uptakes and diffusion coefficients could be altered by varying the % solids used during synthesis of the polymer precursor, by introducing different metals into the polymer hydrogel by ion exchange, or by CVD of benzene on the carbon aerogel.     

Co-generation of synthesis gas and C2+ hydrocarbons from methane and carbon dioxide in a hybrid catalytic-plasma reactor: A review

The topics on conversion and utilization of methane and carbon dioxide are important issues in tackling the global warming effects from the two greenhouse gases. Several technologies including catalytic and plasma have been proposed to improve the process involving conversion and utilization of methane and carbon dioxide. In this paper, an overview of the basic principles, and the effects of CH₄/CO₂ feed ratio, total feed flow rate, discharge power, catalyst, applied voltage, wall temperature, and system pressure in dielectric-barrier discharge (DBD) plasma reactor are addressed. The discharge power, discharge gap, applied voltage and CH₄/CO₂ ratio in the feed showed the most significant effects on the reactor performance. Co-feeding carbon dioxide with the methane feed stream reduced coking and increased methane conversion. The H₂/CO ratio in the products was significantly affected by CH₄/CO₂ ratio. The synergism of the catalyst placed in the discharge gap and the plasma affected the products distribution significantly. Methane and carbon dioxide conversions were influenced significantly by discharge power and applied voltage. The drawbacks of DBD plasma application in the CH₄–CO₂ conversion should be taken into consideration before a new plausible reactor system can be implemented.     

Adsorption separation of N2, O2, CO2 and CH4 gases by β-zeolite

In the present study, adsorption equilibrium and kinetic separation potential of β-zeolite is investigated for N₂, O₂, CO₂ and CH₄ gases by using concentration pulse chromatography. Adsorption equilibrium and kinetic parameters have been studied. Henry’s Law constants, heat of adsorption values, micro-pore diffusion coefficients and adsorption activation energies are determined experimentally. The three different mass transfer mechanisms, that have to take place for adsorption to occur, are discussed. From the equilibrium and kinetic data, the equilibrium and kinetic selectivities are determined for the separation of the gases studied.With β-zeolite, carbon dioxide has the highest adsorption Henry’s Law constant at all the temperatures studied, followed by methane, nitrogen and oxygen. Carbon dioxide separation from oxygen, nitrogen and methane has good equilibrium separation factors. This factor is not very high for methane/nitrogen and methane/oxygen systems and is the lowest for nitrogen/oxygen system. Micro-pore diffusion is the dominant mass transfer mechanism for all the systems studied, except CH₄, with β-zeolite. The kinetic separation factors are very small at high temperatures for all the systems studied. Nitrogen/carbon dioxide and oxygen/carbon dioxide can be separated in kinetic processes with reasonable separation factors at low temperatures. Both equilibrium and kinetic separation factors decrease as column temperature increases. Considering all the observations from this study, it was concluded that β-zeolite is a good candidate for applications in flue gas separations, as well as natural gas and landfill gas purifications.     

Kinetic mobility and connectivity in nanopore networks

Experimental results for methane and carbon dioxide diffusion in coal, as reported in the literature, often lead to diffusion rates of CO₂ appearing to be much greater than that of CH₄. The interpretation sometimes offered that the diffusion coefficient for CO₂ is 1–2 orders of magnitude higher than that of CH₄, violates fundamental principles. Nevertheless, the experimental observations require explanation. In this article, we: (a) Develop simplified models for the fast estimation of transport coefficients. These are compared with comprehensive grand canonical Monte Carlo (GCMC) and molecular dynamic (MD) simulations, collectively defined as molecular simulations (MS), which provide theoretical adsorption isotherms and various transport coefficients based on multicenter potential energy equations. The simplified models are shown to have acceptable accuracies. (b) Use the simplified models to compare diffusivities of CO₂ and CH₄ in carbon nanopores. For all cases examined, the diffusivity of CH₄ is always larger than that of CO₂. (c) Offer two explanations for the apparently contradictory experimental observations (that CO₂ sometimes appears to diffuse much faster than the CH₄ molecule, even though CH₄ is lighter and has smaller adsorption affinity): (i) CH₄ mobility could be significantly reduced by directional forces resulting from irregular pore geometries; and (ii) if pores contain throats with sizes close to the CH₄ molecular diameter, the energy barrier that the methane molecules must overcome to proceed through is much larger than that required for CO₂. (d) Demonstrate that both mobility and connectivity issues can be addressed using kinetic theory in association with percolation analysis. Furthermore, this method of understanding pore networks provides a number of important quantitative measures including percolation threshold, size of largest cluster, shortest path and tortuosity. Separating different transport mechanisms, as we propose here, provides improved insights into the complex transport phenomena that occur in carbonaceous porous media. In many cases, diffusivities reported in the literature with mixed mechanisms are better named “apparent transport coefficients,” because they lump in other unrelated phenomena, violating the fundamental basis of, or mathematical assumptions imposed on, the definition of diffusion. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Decomposition of carbon dioxide in the RF plasma environment

Application of radio-frequency (RF) plasma as an alternative technology for the decomposition of carbon dioxide with methane gas is demonstrated. The results of this study revealed that in CO₂/CH₄/Ar plasma, the best decomposition fraction of carbon dioxide was 60·0%, which occurs around 316°C in the condition designed for 5% feeding concentration of CO₂, 5% feeding concentration of CH₄, 20 torr operation pressure, 100 sccm total gas flow rate and 90 watts input power wattage. The CH, CH₂ and CH₃ radicals obtained from the destruction of CH₄ could result effectively in high decomposition of CO₂ in the plasma reactor. The optimal mathematical models based on the experimental data obtained were also developed and tested by means of sensitivity analysis, which shows that the input power wattage (W) was the most sensitive parameter for the CO₂ decomposition. © 1998 Society of Chemical Industry     

A kinetic study of methane and carbon dioxide interconversion over 0.5%Pt/SrTiO3 catalysts

The kinetics of interconversion of methane with carbon dioxide was studied over a 0.5%Pt/SrTiO₃ solid catalyst in the temperature range 813–893 K and partial pressure range 0.083<P_CH4,P_CO2<0.667. The fitting of the experimental data for the rate of methane conversion, R_CH4, using the empirical equation R_CH4=k₁(P_CH4)^m(P_CO2)ⁿ showed that both reaction orders n and m are steady and obtain values equal to m ≈ 1 and n ≈ 0. The results are explained using Langmuir–Hinshelwood kinetics with the reactants adsorbed on distinct and discreet active sites of the solids, namely the methane is weakly adsorbed on the metallic phase and the carbon dioxide is strongly adsorbed on the oxidic phase of the catalyst. The apparent activation energy for the reforming of methane was estimated to be 123 kJ mol⁻¹.The rate of conversion of the carbon dioxide, R_CO2, was also fitted using a similar empirical equation R_CO2=k₂(P_CH4)^m(P_CO2)ⁿ. The results indicate that there is a positive but variable dependence on both reaction orders which increases in the temperature range 813–893 K from m ≈ 0.0 to m ≈ 0.30 and from n ≈ 0.3 to n ≈ 0.6. This variation is attributed to the variable participation of the rate of the reverse water gas shift reaction, R_rwgs, to the overall rate R_CO2 of CO₂ conversion. The dependence of R_rwgs on the partial pressure of CO₂ appears similar to that of R_CH4 on the same reactant but shows strong inhibition by the reaction products. The results are discussed using Langmuir–Hinshelwood kinetics with the reactants and products adsorbed competitively on similar active sites of the catalyst.     

Adsorption of Off‐Gases from Steam Methane Reforming (H2, CO2, CH4, CO and N2) on Activated Carbon

Abstract

Hydrogen is the energy carrier of the future and could be employed in stationary sources for energy production. Commercial sources of hydrogen are actually operating employing the steam reforming of hydrocarbons, normally methane. Separation of hydrogen from other gases is performed by Pressure Swing Adsorption (PSA) units where recovery of high‐purity hydrogen does not exceed 80%.

In this work we report adsorption equilibrium and kinetics of five pure gases present in off‐gases from steam reforming of methane for hydrogen production (H₂, CO₂, CH₄, CO and N₂). Adsorption equilibrium data were collected in activated carbon at 303, 323, and 343 K between 0‐22 bar and was fitted to a Virial isotherm model. Carbon dioxide is the most adsorbed gas followed by methane, carbon monoxide, nitrogen, and hydrogen. This adsorbent is suitable for selective removal of CO₂ and CH₄. Diffusion of all the gases studied was controlled by micropore resistances. Binary (H₂‐CO₂) and ternary (H₂‐CO₂‐CH₄) breakthrough curves are also reported to describe the behavior of the mixtures in a fixed‐bed column. With the data reported it is possible to completely design a PSA unit for hydrogen purification from steam reforming natural gas in a wide range of pressures.     

Effect of steam and carbon dioxide pretreatments on methane decomposition and carbon gasification over doped-ceria supported nickel catalyst

Effects of steam (H₂O) and carbon dioxide (CO₂) pretreatments on methane (CH₄) decomposition and carbon gasification over doped-ceria supported nickel catalysts have been studied from 400 to 500 °C. The doped ceria employed were gadolinia-doped ceria and samaria-doped ceria. Results indicate that a drastic increase of both H₂O and CO₂ dissociation activities occurs as the temperature increases from 450 to 500 °C. The formation of the surface hydroxyl species during H₂O treatment inhibits the followed CH₄ decomposition. CO but no CO₂ was formed during CH₄ reaction after H₂O treatment. Carbon deposition during CH₄ decomposition is quite large but can be removed via gasification with afterward CO₂ treatment. However, some of the deposited carbon species is in a form which can not be removed with CO₂ treatment but can be removed with O₂ treatment. And, higher values of the oxygen-ion conductivity and the density of the surface oxygen vacancies lead to higher activities for all dissociation and decomposition reactions.     

Response Surface Optimization of Hydrogen-Rich Syngas Production by Greenhouse Gases Reforming

The effect of process interaction and response surface optimization of hydrogen-rich syngas production by catalytic carbon dioxide (CO₂) reforming of methane (CH₄) was evaluated. The Box-Behnken design was applied to investigate the influence of CH₄ partial pressure, CO₂ partial pressure, and temperature on the hydrogen yield. The analysis of variance indicated that temperature and CH₄ partial pressure had the most significant impact on the hydrogen yield. Under optimum conditions a maximum hydrogen yield of 71.38 % was achieved. Model validation with the ideal conditions confirmed close agreement of the predicted hydrogen yields with experimental values.     

Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation

A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs free energy method. The effects of CO₂/CH₄ ratio (0.5-3), reaction temperature (573-1473 K) and pressure (1-25 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical analysis revealed that the optimal working conditions for syngas production in Fischer-Tropsch synthesis were at temperatures higher than 1173 K for CO₂/CH₄ ratio being 1 at which about 4 mol of syngas (H₂/CO = 1) could be produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above 973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO₂/CH₄ ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of CO moles, declined H₂ moles and gradual increment of CO₂ conversion. The simulated reactant conversions and product distribution were compared with experimental results in the literatures to study the differences between the real behavior and thermodynamic equilibrium profile of CO₂ reforming of methane. The potential of producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented carbon deposition and decreased CO and H₂ production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO₂ reforming of methane with equal amount of CH₄ and CO₂ revealed reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed ratio of 1073 K and CO₂:CH₄:O₂ = 1:1:0.1, respectively. The H₂/CO ratio was maintained at unity while water formation was minimized and solid carbon eliminated.     

Production of carbon molecular sieves from palm shell based activated carbon by pore sizes modification with benzene for methane selective separation

Palm shell based activated carbon prepared by K₂CO₃ activation is used as precursor in the production of carbon molecular sieve by chemical vapor deposition (CVD) method using benzene as depositing agent. The influences of deposition temperature, time, and flow rate of benzene on pore development of carbon molecular sieve (CMS) and methane (CH₄) adsorption capacity were investigated. The parameters that varied are the deposition temperature range of 600 to 1000 °C, time from 5.0 to 60 min, and benzene flow rate from 3.0 to 15 mL/min. The results show that in all cases, increasing the deposition temperature, time, and flow rate of benzene result in a decrease in adsorption capacity of N₂, pore volume and pore diameter of CMS. The BET surface area of CMS (approximately 1065 m²/g) and the adsorption capacity of CH₄ were at a maximum value at a deposition temperature of 800 °C, time of 20 min and benzene flow rate of 6 mL/min. The product has a good selectivity for separating CH₄ from carbon dioxide (CO₂), nitrogen (N₂), and oxygen (O₂).     

Kinetic study of methane reforming with carbon dioxide over NiCeMgAl bimodal pore catalyst

The kinetic behavior of NiCeMgAl bimodal pore catalyst for methane reforming with CO₂ was investigated after the elimination of external and internal diffusion effects in a fixed‐bed reactor as a function of temperature and partial pressures of reactants and products. Increase in CO₂ partial pressure favors the consumptions of CH₄ and CO₂ but inhibits the formation of H₂ due to the existence of reverse water gas shift (RWGS) reaction. The reforming rate increased first and then reached a horizontal stage with the rise of CH₄ partial pressure. A Langmuir–Hinshelwood model was developed assuming that the carbon deposition is ignorable but the RWGS reaction is non‐ignorable and the removal of adsorbed carbon intermediate is the rate‐determining step. A nonlinear least‐square method was applied to solve the kinetic parameters. The derived kinetic expression fits the experimental data very well with a R² above 0.97, and also predicts the products flow rate satisfactorily. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2019–2029, 2017     

Sorption kinetics of eight gases on a carbon molecular sieve at elevated pressure

The sorption kinetics of eight different molecules (O₂, N₂, Ar, CO, CO₂, SO₂, CH₄ and H₂) on a carbon molecular sieve was studied over a wide range of pressures up to 15 atm by using a volumetric method. The acentric factor was suggested as a potential factor to estimate the relative sorption rate. Since the apparent time constants of all the components showed much stronger dependence of pressure than those expected by the traditional Darken relation and the structural diffusion model, new models with the diffusion relation at the supercritical condition was proposed to predict the kinetic behaviors in the micropores. The proposed model successfully predicted the apparent time constant up to high pressure. In addition, the semi-empirical model that combined acentric factor with the proposed model was able to predict the strong pressure dependence accurately. However, since the strong adsorbates, CO₂ and SO₂, showed two-stage kinetic behavior with pressure, which was different from that of the other adsorbates. The kinetic behaviors of these molecules could be predicted by using two different sorption models.     

Microstructure relaxation process of polyhexafluoropropylene after swelling in supercritical carbon dioxide

This paper studies the process of relaxation of a polymer after swelling in supercritical carbon dioxide. Polyhexafluoropropylene (PHFP) was chosen as the object for investigation. The relaxation process was monitored by a change of the permeability coefficients for a number of gases. Thin polymeric films of PHFP were modified by different treatments: drying to a constant weight, annealing at a temperature slightly higher than the glass‐transition temperature, and swelling in supercritical carbon dioxide. The permeability coefficients of six gases, He, H₂, O₂ N_2, CO₂, and CH₄, were measured after each stage of the treatment. It was shown that the permeability coefficients in the films were increased by 2.4 times for He, 3.6 for H₂, 5.9 for O₂, 8.1 for N₂, 6.7 for CO₂, and 10.9 for methane. The permeability coefficients of the same gases were measured 50 days later after swelling in supercritical carbon dioxide. A decrease in the permeability coefficient demonstrated that the relaxation process had taken place. Nevertheless, the values exceeded the initial ones for annealed samples by 2.0 times for He, 2.4 for H₂, 1.8 for O₂, 1.7 for N₂, 1.7 for CO₂, and 1.3 for methane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43105.     

Knudsen diffusion through ZIF-8 membranes synthesized by secondary seeded growth

Herein we demonstrate the synthesis of ZIF-8 membranes via secondary seeded growth on tubular stainless steel porous supports. The membranes were characterized and evaluated for the separation of CO₂/N₂ and N₂/CH₄ gas mixtures. The adsorbate polarizability correlated with the adsorption capacity on ZIF-8, and the amounts of gases adsorbed were in the order: CO₂ > CH₄ > N₂. The CO₂/N₂ separation selectivity’s for the ZIF-8 membranes were close to the Knudsen selectivity, suggesting that Knudsen diffusion through non-ZIF pores dominated the separation. On the other hand, the separation selectivity’s for N₂/CH₄ were slightly higher than the Knudsen selectivity, indicating that the flow contribution from the ZIF pores favored the transport of N₂ over CH₄.