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.     

Adsorption of propane and propylene onto carbon molecular sieve

Equilibrium data for propane and propylene adsorption on a carbon molecular sieve (CMS) 4A from Takeda are presented in the temperature range 343-423 K and 0-300 kPa pressure. The pellet adsorption loading is 0.9 mol/kg for propane and 1.2 mol/kg for propylene at 100 kPa and 373 K. The equilibrium selectivity for propylene in the low-pressure range are 2.3 (343 K) and 1.7 (423 K). Experimental data were fitted with the Toth and Dubinin models. Zero length column (ZLC) technique has been used to determine the controlling mechanism and estimate the diffusivity parameters. Transport of both hydrocarbons in the pellets is controlled by micropore diffusion. Breakthrough curves were measured in the same temperature range and atmospheric pressure, at the low partial pressure of adsorbate (linear region of the isotherm). Simple models have been used in the simulation of breakthrough curves.     

Modification of pore size in activated carbon by polymer deposition and its effects on molecular sieve selectivity

The separation of air for nitrogen production can be carried out by pressure-swing-adsorption over a carbon molecular sieve. The separation is kinetically controlled, since the equilibrium adsorption of both oxygen and nitrogen is very similar, but the adsorption kinetics for oxygen is faster than for nitrogen. Several methods to prepare carbon molecular sieves are reported. In this work, we synthesized a carbon molecular sieve from a commercial activated carbon. After deposition of polyfurfuryl alcohol, these materials were subjected to carbonization at 800°C under an inert atmosphere. All the microporous materials were characterized by analysis of kinetics and equilibrium adsorption data. The molecular sieve performance was assessed by the O₂/N₂ uptake ratio. The material prepared by two depositions has characteristics similar to those of commercial CMS.     

Preparation and pore control of highly mesoporous carbon from defluorinated PTFE

Porous carbon having more than 2000 m²/g of BET specific surface area was synthesized by defluorination of polytetrafluoroethylene (PTFE) at 473 K using sodium metal. The porous carbon as-prepared had a large amount of narrow mesopores 2-3 nm in pore width, together with micropores. Control of the pore structure was attempted by simple heat-treatment of the carbon in nitrogen, and change of the porous structures was characterized by nitrogen adsorption techniques. As a result, it was found that the ratio between micro- and mesopores was easily varied. Electric double layer capacitance was measured as one of the applications for the mesoporous carbon with specific porosity, and the effect of pore control on capacitance was investigated.     

Templated pyrolytic carbon: the effect of poly(ethylene glycol) molecular weight on the pore size distribution of poly(furfuryl alcohol)-derived carbon

Poly(ethylene glycol), which has a negligible carbon yield upon pyrolysis, was used as a template to study the controlled formation of mesoporosity in pyrolytic carbons. A series of carbons was produced from mixtures of poly(ethylene glycol) and poly(furfuryl alcohol) with 25, 50 and 75% composition by weight and an M_n of 300 to18?500 g/mol of template. Polydisperse dextran adsorption reveals a maximum in uptake for 8000 g/mol and 50% templated carbons, while materials from 75% mixtures or those from less than 2000 g/mol template yielded negligible dextran uptake. These results correlated well with the intensity ratio of a broad peak between 7 and 11° 2θ in the X-ray diffraction spectrum and the 002 diffraction peak and also qualitatively with micrographs of the internal microstructure of the carbons. The results suggest a templating process dominated by both the molecular size of the template and the rate of expulsion of decomposed template material during the formation of the solid.     

Preparation of molecular sieving carbon from waste resin by chemical vapor deposition

Molecular sieving carbons (MSCs) were prepared from carbonized phenol-formaldehyde resin wastes by the chemical vapor deposition (CVD) of the pyrolyzed carbon from hydrocarbon species. The pore size of the MSCs could be controlled in the range 0.37-0.42 nm by changing the hydrocarbon species pyrolyzed, the pyrolyzing temperature, and the processing time. It is shown that some of the MSCs have an excellent selectivity for separating CO₂ and CH₄, and others for separating C₃H₈ and C₃H₆. As the mechanism for controlling the pore size during CVD processing, we elucidated that the adsorption of hydrocarbon molecules first takes place on the pore surface and then the adsorbed hydrocarbons pyrolyze into carbon. Therefore, the pore size of the MSC can be adjusted by controlling the amount hydrocarbon adsorbed on the phenol-formaldehyde resin char.     

Preparation and properties of phenolic resin-based activated carbon spheres with controlled pore size distribution

Three kinds of phenolic resin-based activated carbon spheres (P-ACS) with different pore size distribution were prepared successfully by adding pore-forming agents to novolac-type phenolic resin. Polyethylene glycol and polyvinyl butyral, serving as pore-forming agents, evaporated during pyrolysis and left a small amount of carbon residue in the matrix of the phenolic resin-based carbon, thus changing the carbonization and activation behavior of the resin. Mesopores between 3 and 5 nm were created in the P-ACS, which possessed excellent adsorption properties for creatinine. Ferrocene has little effect on the carbonization process of the phenolic resin, but has a great impact on the activation process. Mesopores and macropores with a range from 3-5 to 10-90 nm were produced in the P-ACS, which exhibited large adsorption properties for VB₁₂, a larger molecule than creatinine. P-ACS without pore-forming agents exhibited a small specific surface area and mainly micropores, which resulted in a very small amount of creatinine and VB₁₂ adsorbed.     

Structural changes in carbon aerogels with high temperature treatment

The structural change of carbon aerogels at high temperatures up to 2800°C has been investigated. Change in microtexture of fine particles, which constitute carbon aerogels derived from phenolic resin, was of a typical non-graphitized carbon. The microporosity decreased with an increase of heat-treatment temperature, and disappeared at 2000°C. The mesoporosity still remained even after heat-treatment up to 2800°C, though 50% of mesopore volume was lost because of the fusion of the particles with the change of carbon microtexture.     

Temperature- and pressure-dependent transient analysis of single component permeation through nanoporous carbon membranes

Using a transient analysis of permeation, i.e. the time lag method, as a function of temperature and pressure, it is shown that each of the parameters needed to fully evaluate adsorption and diffusion can be obtained in situ. These experiments were conducted on a supported tubular nanoporous carbon membrane, 5.1 cm² in area and prepared by ultrasonic deposition of poly(furfuryl alcohol) onto a porous stainless steel support. The permeation experiments were conducted at temperatures ranging from 25 to 225°C and over a range of pressures from 100 to 700 kPa. Under these conditions the fluxes ranged from 10⁻⁷ to 10⁻⁴ mol/m²/s with permeances ranging between 10⁻¹² and 10⁻⁹ mol/m²/s/Pa. Heats of adsorption were found to be 2.5, 2.21, 3.05 and 2.52 kcal/mol for N₂, O_2, Ar and CO₂, respectively, and generally lower than those reported for granular nanoporous carbons. The apparent activation barriers to diffusion were also found to be low at 2.06, 5.87, 4.12, 5.89 and 2.19 kcal/mol for He, N₂, O₂, Ar and CO₂. These results point to the presence of two parallel pathways for transport — the major one through the nanopores but a second through a few defect pores. Assumed to be on the order of 50 nm in diameter, these defects were calculated to represent a total area fraction of 3.43×10⁻⁹.     

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.     

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.     

Organic and carbon aerogels derived from poly(vinyl chloride)

Organic aerogels were derived from dimethylformamide solution of poly(vinyl chloride) (PVC) via dehydrochlorination using a strong base, 1,8-diazabicyclo[5,4,0]undec-7-ene, and supercritical drying using carbon dioxide. From these organic aerogels, carbon aerogels were yielded via stabilization and carbonization. Changes in the porous structure of the aerogels during the preparation process and influences of the preparation conditions on the porous structure were investigated. The framework of the aerogels composed the walls of the meso- and macropores. The volume and the size of these pores were reduced during stabilization and carbonization due to the shrinkage of the framework caused by the release of decomposition gases and densification of the material. Simultaneously, the release of decomposition gases produced additional micropores. The extent of dehydrochlorination, the concentration of PVC in the starting solution and the molecular weight of PVC were the factors with which the porous structure of the aerogels could be controlled over a wide range. In addition, the stabilization conditions notably influenced the carbonization behavior of the organic aerogels and the porous structure of the carbon aerogels. The optimum stabilization conditions that minimized the loss of mass and maximized the pore volume of the carbon aerogels were determined.     

Preparation and characterization of carbon cryogel microspheres

Carbon cryogel microspheres (CC microspheres) were successfully synthesized by an inverse emulsion polymerization of resorcinol with formaldehyde, followed by freeze drying and pyrolysis in an inert atmosphere. CC microspheres were characterized by scanning electron microscopy, elemental analysis and various gas adsorption measurements. By changing both the temperature for preparing the emulsion and pyrolysis temperature, it was possible to prepare both mesoporous microspheres and microspheres covered with ultramicroporous surfaces which pore sizes were smaller than the minimum molecular dimensions of ethane or carbon dioxide. Hydrophobicity of the obtained CC microspheres increased with the increase in pyrolysis temperature. The possibility of using the obtained mesoporous CC microspheres as column packing materials for high-performance liquid chromatography was also shown.     

Interaction of hydrogen with carbon coils at low temperature

Hydrogen was adsorbed on carbon coils under 10 MPa hydrogen gas at liquid nitrogen temperature. The equilibrium pressure of hydrogen desorbed from the as-grown carbon coils with an amorphous structure was three to four times greater than those of multiwall carbon nanotubes (MWNT) and active carbons (AC). The heat treatment of the carbon coils at 850 °C contributed to an increase in hydrogen adsorption by 20% compared to the as-grown carbon coils. On the other hand, the adsorption of hydrogen gas on the carbon coils decreased significantly after heat treatment at a temperature higher than 1000 °C due to formation of capsule-like carbon composed of 10-20 layers on the surface of the carbon coils.     

Comparison of molecular sieve properties in microporous chars from low-rank bituminous coal activated by steam and carbon dioxide

A Polish high volatile bituminous coal was subjected to air oxidation, carbonization and gaseous activation. The activation with steam and carbon dioxide was performed to low levels of burn-off: 5-25%. Sorption measurements of CO₂, as well as of organic vapours with increasing molecular sizes (CH₂Cl₂, C₆H₆, C₆H₁₂, CCl₄) were applied to evaluate the porous structure of the activated chars. Steam and carbon dioxide develop the microporous system according to the same mechanism—opening (burn-off 5-10%) and then widening of the narrow micropores. For char from the oxidized coal mainly a widening of the narrow micropores takes place. Comparing both activating agents, it was stated that for steam greater micropore volumes were obtained. This was confirmed by other authors for chars from brown coal and coking coal, but was in disagreement with the results for olive stones and carbon fibres. This would indicate the importance of the carbon precursor in the formation of the porous structure of carbon materials by different activating agents. In the region of studied burn-offs, among the micropore sizes useful for separation of gases and vapours with small molecules, micropore volumes with widths close to 0.4-0.5 nm are dominating. At very low burn-offs (5-10%), steam activation renders greater micropore volumes within these sizes, than does activation with carbon dioxide. But with increasing burn-off (15-25%), this phenomenon becomes reversed. This effect is still more accentuated for the preoxidized coal.     

Improved activated carbon by thermal treatment in methane and steam: Physicochemical influences on MIB sorption capacity

Thermal treatment by steam or by methane plus steam altered the physicochemical properties of a commercial lignite-based activated carbon; and improved the carbon’s sorption capacity for the odorant 2-methylisoborneol (MIB). Rapid small scale column tests (RSSCTs) revealed that favorable thermal treatment allowed an activated carbon to remove this odorant for up to six times longer before initial MIB breakthrough than did its commercial lignite counterpart. For these RSSCTs (135 ppt), clarified water from a water treatment plant (2.07 mg/L TOC) was spiked with ¹⁴C-MIB; and liquid scintillation protocols facilitated ¹⁴C-MIB detection at 1-3 ppt. The more favorable thermal treatment at 1000 °C increased pore volumes with 5-400 Å widths by twofold; and the bed volume to initial MIB breakthrough correlated fairly well (R² = 0.9) with pore volume in the range of 5-60 or 5-400 Å. Thermal tailoring altered the carbon’s apparent point of zero charge: from pH 6.5 for the commercial lignite carbon, to pH 9.2 for tailored carbon. When methane and steam were used together, the C, H, N and O contents were virtually the same as for the commercial lignite. In contrast, when steam was employed alone, the percent of oxygen increased, and the percent of H, C and N therefore decreased slightly.     

Preparation and characterization of porous carbon beads and their application in dispersing small metal crystallites

Porous carbon beads were prepared by the pyrolysis of poly(vinylidene chloride) beads that were synthesized by suspension polymerization. After prolysis treatment at 180–300 °C under argon stream, the polymeric beads were further carbonized at 1000 °C for 3 h under argon stream to acquire porous carbon beads, of which the specific surface area was about 1000 m²/g, and pore size was mainly in the width range of 0.8–1.2 nm. The carbon structure and surface chemical composition characterized by X-ray diffraction and X-ray photoelectron spectroscopy, depended on the preparation temperature and the relations between them were examined. The characterization of the carbon beads by scanning electron microscopy, atomic force microscopy presented the morphological structure of the carbon beads surface and a global view of pores. The dispersion of nickel crystallites on the carbon beads surface was characterized by electron microprobe analysis. This study reveals that uniform surface morphological structure leads to the fine dispersion of metal crystallites.