Synthesis of carbon molecular sieves from palm shell by carbon vapor deposition

A series of experiments were conducted to produce carbon molecular sieves (CMS) through carbon deposition from a locally available palm shell of Tenera type for separating gaseous mixtures. The process involves three stages; carbonization, physical activation with steam, and carbon deposition by using benzene cracking technique. Carbonization of the dried palm shells was occurred at 900°C for duration of 1 h followed by steam activation at 830°C for 30–420 min to obtain activated carbons with different degree of burn-offs. The highest micropore volume of activated carbon obtained at 53.2% burn-off was used as a precursor for CMS production. Subsequent carbon deposition of the activated sample at temperature range from 600 to 900°C for 30 min has resulted in a series of CMSs with different selectivities of CO₂/CH₄ and O₂/N₂. The kinetic adsorption isotherm of CO₂, CH₄, O₂ and N₂ at room temperature also presented in this work.     

Ultra-thin skin carbon hollow fiber membranes for sustainable molecular separations

A transformative platform is reported to derive ultra-thin carbon molecular sieve (CMS) hollow fiber membranes from dual-layer precursor hollow fibers with independently tuned skin layer and substrate properties. These ultra-thin CMS hollow fiber membranes show attractive CO₂/CH₄ separation factors and excellent CO₂ permeances up to ~1,400% higher than state-of-the-art asymmetric CMS hollow fiber membranes. They provide a unique combination of permeance and selectivity competitive with zeolite membranes, but with much higher membrane packing density and potentially much lower costs.     

Separation of CO2/CH4 through carbon molecular sieve membranes derived from P84 polyimide

The separation of CO₂/CH₄ separation is industrially important especially for natural gas processing. In the past decades, polymeric membranes separation technology has been widely adopted for CO₂/CH₄ separation. However, polymeric membranes are suffering from plasticization by condensable CO₂ molecules. Thus, carbon molecular sieve membranes (CMSMs) with excellent separation performance and stability appear to be a promising candidate for CO₂/CH₄ separation. A commercially available polyimide, P84 has been chosen as a precursor in preparing carbon membranes for this study. P84 displays a very high selectivity among the polyimides. The carbonization process was carried out at 550–800 °C under vacuum environment. WAXD and density measurements were performed to characterize the morphology of carbon membranes. The permeation properties of single and equimolar binary gas mixture through carbon membranes were measured and analyzed. The highest selectivity was attained by carbon membranes pyrolyzed at 800 °C, where the pyrolysis temperatures significantly affected the permeation properties of carbon membranes. A comparison of permeation properties among carbon membranes derived from four commercially available polyimides showed that the P84 carbon membranes exhibited the highest separation efficiency for CO₂/CH₄ separation. The pure gas measurement underestimated the separation efficiency of carbon membranes, due to the restricted diffusion of non-adsorbable gas by adsorbable component in binary mixture.     

Development of new carbon honeycomb structures from cellulose and pitch

In this paper the development of a new, low-cost method for the preparation of carbon honeycomb structures for gas adsorption applications is described. The method comprises the impregnation of a petroleum pitch into a cellulose-based corrugated paper. The resultant material has a high carbon content and retains the original structure of the paper, making it suitable for usage in gas flow applications. TEM and SAD studies on the carbonised material suggest the presence of two different types of carbon structures, a disorganised structure and a more organised one. The porosity of the samples was characterised by CO₂ and N₂ adsorption. The results indicated an appreciable narrow microporosity with a high structural stability to high temperatures (presence of the porosity at high temperatures). Finally, the molecular sieve properties of the materials were studied by CH₄ and CO₂ adsorption kinetics and compared favourably with those of a commercial carbon molecular sieve (CMS), indicating their promise for high temperature applications, such as catalyst supports or for gas separations.     

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.     

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).     

Generalization of effect of oxygen exposure on formation and performance of carbon molecular sieve membranes

Previously, a pyrolysis method was developed to control separation performance of carbon molecular sieve (CMS) membranes by doping with trace oxygen. This method involved oxygen exposure during pyrolysis to tune the selective pore windows. During the development, it was observed that oxygen concentration in inert gas, rather than the total amount of oxygen exposed controls performance. In this study, we hypothesized that mass transfer of oxygen in CMS membranes during pyrolysis is governed by chemical reaction at critical pore opening. Effect of thermal soak time, inert flow rate, and precursor thickness were conducted to test this hypothesis with 6FDA/BPDA-DAM and Matrimid® polymer precursors. Results of oxygen consumption from pyrolysis process and CO₂/CH₄ separation performance showed that the process is likely governed by reaction kinetics. This observation implies simplicity and easy scale-up for the oxygen “doping” method on CMS formation by tuning the oxygen concentration in the pyrolysis atmosphere.     

Preparation of C/CMS composite membranes derived from Poly(furfuryl alcohol) polymerized by iodine catalyst

C/CMS composite membranes derived from poly(furfuryl alcohol) (PFA) polymerized by iodine catalyst were prepared. Gas separation performance was investigated by molecular probe study with pure gases (H₂, CO₂, O₂, N₂, and CH₄) at 25 °C. The pyrolysis behaviour of PFA was studied by TG and DTG. The surface morphology of C/CMS composite membranes was observed by SEM and HRTEM. The results show a C/CMS composite membrane with uniform and defect-free thin top layer can be prepared by the PFA liquid in only one coating step. The C/CMS composite membranes have excellent gas separation properties for the gas pairs such as H₂/N₂, CO₂/N₂, O₂/N₂ and CO₂/CH₄, the permselectivities for above gas pairs in same sequence were 124.72, 12.74, 9.12 and 15.91 respectively. Compared to carbon membranes derived from PFA polymerized by acid catalyst, the carbon membranes obtained from PFA polymerized by iodine catalyst have slightly lower permselectivity, but higher permeance.     

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.     

Ultramicroporous carbon granules with narrow pore size distribution for efficient CH4 separation from coal-bed gases

The adsorptive separation of CH₄ from low-grade coal-bed gas can be performed at decentralized and remote coal mines, and it uses more energy- and is cost-efficient than the traditional cryogenic distillation process. Herein, we present a facile method to prepare ultramicroporous carbon granules with a narrow pore-size distribution at 0.5–0.6 nm. To our knowledge, such centered and uniform pore-size distribution in carbon granules has never been reported. The carbon granules can be directly utilized in adsorption columns without a granulation or pelletization process. The granular oil-tea-shell-derived porous carbon (GOC-2) exhibited a record-high CH₄ uptake of 1.82 mmol/g and CH₄/N₂ selectivity of 5.8 at 1.0 bar and 298 K among carbon granules. The excellent CH₄/N₂ separation performances were confirmed from the results of dynamic breakthrough experiments and pressure swing adsorption simulations. This work provides a novel strategy for developing ultramicroporous carbon granules and guides the future design of efficient CH₄/N₂ separation adsorbents.     

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.     

Molecular sieve properties obtained by cracking of methane on activated carbon fibers

Molecular sieve properties of activated carbon fibers modified by cracking treatment with methane are studied herein. The effect of methane treatment on the porous texture of the samples has been studied while varying temperature and time. These materials have been evaluated for their selectivity during CO₂ and CH₄ separation; their uptakes have been compared with non-treated activated carbon fibers (studied previously), which were considered suitable to be used as molecular sieves. Kinetics of CO₂ and CH₄ uptake have also been investigated in this research. The treatment produced materials exhibiting fast kinetics and high selectivity during CO₂ and CH₄ separation; at the same time however, the CO₂ uptake capacity was diminished.     

Preparation of carbon molecular sieves from carbon micro and nanofibers for sequestration of CO2

In this study, a hierarchal web of carbon micro and nanofibers was used as a precursor for the synthesis of a carbon molecular sieve (CMS). CMSs were prepared by thermal treatment of carbon fibers using a microwave heating device. The heating power and treatment time were optimized for the maximum performance of the prepared CMS for the separation of CO₂ at low concentrations from the gaseous mixture of CO₂ and air under dynamic (flow) conditions. Based on the experimental data, microwave power input of 240 W and treatment time of 15 min were found to be suitable for the maximum uptake of CO₂ by CMS. Adsorption breakthrough curves were obtained at different gas flow rates and CO₂ concentrations. CMSs prepared from the hierarchal web of carbon micro and nanofibers were found to be superior to those prepared from ACF. The CO₂ uptake was determined to be approximately 0.88 mg/g and 10 mg/g at concentrations of 500 ppm and 5000 ppm, respectively, in air.     

Improving CO2/CH4 adsorptive selectivity of carbon nanotubes by functionalization with nitrogen-containing groups

Multi-walled carbon nanotubes containing oxygenated groups (O-MWCNTs) have been functionalized with ammonia to improve the adsorption capacity and selectivity of CO₂/CH₄ in gas adsorption process. The effects of oxygen and nitrogen containing functional groups (e.g. hydroxyl and amine), on CO₂ and CH₄ adsorption were studied. The ideal adsorption capacities of MWCNTs were determined using volumetric method at ambient temperature and moderate pressures (from 0.1 to 3.0 MPa). The MWCNTs containing nitrogen groups (N-MWCNTs) showed much higher adsorption capacity of CO₂ and selectivity of CO₂/CH₄ against the O-MWCNTs at different pressures. The highest selectivity was observed at lower pressures at 298 K for the N-MWCNTs. The dynamic adsorption experiments were carried out with a feed containing one to fivefold of CO₂ to CH₄ in a packed bed of N-MWCNTs at 298 K and atmospheric pressure. The breakthrough curves and breakthrough times of CO₂ and CH₄ were determined for the mixed gases. The results indicated high efficiency of the prepared N-MWCNTs in dynamic separation of CO₂ and CH₄.     

Dual-layer hollow carbon fiber membranes for gas separation consisting of carbon and mixed matrix layers

Hollow carbon fiber membranes for gas separation have been successfully fabricated for the first time by a special type of precursor. This precursor is dual-layer hollow fiber composed of a polysulfone-beta zeolite (PSF-beta) mixed matrix outer layer and a Matrimid inner layer. Pure gas permeation measurements show that the resultant hollow carbon fiber has O₂/N₂ and CO₂/CH₄ selectivities of 9.3 and 150, respectively; this performance is much better than that of the hollow carbon fiber derived from single-layer Matrimid hollow fiber. Mixed gas measurements show the CO₂/CH₄ selectivity of 128. After pyrolysis, the PSF-beta layer in the dual-layer precursor evolves into a continuous structure of closely packed zeolite particles embedded in the PSF carbon residue. TGA spectra suggest that the possible reason for the above observation is that the PSF-beta outer layer and Matrimid inner layer has significantly changed each other’s pyrolysis dynamics and thermal degradation process.     

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.     

Carbon membranes from cellulose and metal loaded cellulose

The focus of this work was to find a low-cost precursor for carbon molecular sieve (CMS) membranes, and a simple way of producing them. In addition, several ways of modifying a carbon material are described. The modification method used in this study was metal doping of carbon. CMS membranes were formed by vacuum carbonization of cellulose and metal loaded cellulose. Metal additives include oxides of Ca, Mg, Fe(III) and Si, and nitrates of Ag, Cu and Fe(III).The carbon membrane containing Fe-nitrate has promising separation performance for the gas pairs O₂/N₂ and CO₂/CH₄. Carbon containing nitrates of Cu or Ag show high selectivity, but reduced O₂ and CO₂ permeability compared to carbon with Fe-nitrate. Element analysis indicates that Cu migrates to the carbon surface, creating an extra layer resistance to gas transport. A silver mirror is also seen on the surface of Ag-nitrate-containing carbon. However, the Ag- and Cu-containing membranes show a high H₂ permeability. Adding metal oxides makes the carbon membranes retard the transport of easily condensable gases (e.g. CO₂). This can be exploited for enhanced H₂/CO₂ separation efficiency.     

A high CO2 permselective mesoporous silica/carbon composite membrane for CO2 separation

Ordered mesoporous silica/carbon composite membranes with a high CO₂ permeability and selectivity were designed and prepared by incorporating SBA-15 or MCM-48 particles into polymeric precursors followed by heat treatment. The as-made composite membranes were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and N₂ adsorption, of which the gas separation performance in terms of gas permeability and selectivity were evaluated using the single gas (CO₂, N₂, CH₄) and gas mixtures (CO₂/N₂ and CO₂/CH₄, 50/50 mol.%). In comparison to the pure carbon membranes and microporous zeolite/C composite membranes, the as-made mesoporous silica/C composite membranes, and the MCM-48/C composite membrane in particular, exhibit an outstanding CO₂ gas permeability and selectivity for the separation of CO₂/CH₄ and CO₂/N₂ gas pairs owing to the smaller gas diffusive resistance through the membrane and additional gas permeation channels created by the incorporation of mesoporous silicas in carbon membrane matrix. The channel shape and dimension of mesoporous silicas are key parameters for governing the gas permeability of the as-made composite membranes. The gas separation mechanism and the functions of porous materials incorporated inside the composite membranes are addressed.     

Adsorption of binary CO2/CH4 mixtures using carbon nanotubes: Effects of confinement and surface functionalization

Effect of confinement and surface functionalization in carbon nanotubes (CNTs) on the competitive adsorption of a binary CO₂/CH₄ mixture has been investigated by grand canonical Monte Carlo simulations. Adsorption using CNTs with different functionalization arrangements, different diameters, different functionalization degrees, and different functional groups, such as –COOH, –CO, –OH, –CH₃, is investigated. Effects of (a) the pore textural properties, such as pore size and accessible surface area, and (b) the gas–adsorbent interaction, especially the electrostatic interaction, are discussed. From these results, we discuss the impact that variables such as confinement and surface functionalization have on the performance for CO₂ separation.     

Simulation of CO2/CH4 high pressure separation on microporous activated carbon

Abstract

Pure component adsorption equilibrium of CH₄ and CO₂ on activated carbon have been studied at three different temperatures, 298, 323, and 348?K within a pressure range of 10–2000?kPa. Binary adsorption equilibrium isotherm was described using extended Sips equation and ideal adsorbed solution theory (IAST) model. Experimental breakthrough curves of CO₂/CH₄ (40:60 in a molar basis) were performed at four different pressures (300, 600, 1200, and 1800?kPa). The experimental results of binary isotherms and breakthrough curves have been compared to the predicted simulation data in order to evaluate the best isotherm model for this scenario. The IAST and Sips models described significantly different results for each adsorbed component when higher pressures are set. These different results cause a significant discrepancy in the estimation of the equilibrium selectivity. Simulated and experimental equilibrium selectivity data provided by IAST presented values of around 4, for CO₂/CH₄, and extended Sips presented values of around 2. Also, simulated breakthrough curves showed that IAST fits better to the experimental data at higher pressures. According to the simulations, in a binary mixture at total pressure over 800?kPa, extended Sips model underestimated significantly the CO₂ adsorbed amount and overestimated the CH₄ adsorbed amount.