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.     

Characterisation of insoluble charcoal in Weipa bauxite

The role of charcoal like components (also referred to as char) in soil organic matter reactivity has become increasingly evident. Recently we have demonstrated the role of such material in bauxite. Sodium hydroxide is used at elevated temperatures to separate aluminium hydroxide from ferric oxide in bauxite in the Bayer process and charcoal like material may interfere with the precipitation of aluminium hydroxide. In this paper we study the solubility, structure and composition of charcoal in the feed stockpile of bauxite ore by solubility, laser Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and pyrolysis gas chromatography mass spectrometry (py-GC/MS). The charcoal was treated under simulated Bayer process conditions of 245 °C in 5 M sodium hydroxide. The alkaline digestion test showed that a large fraction of the charcoal was insoluble (∼90%). Surprisingly, the spectroscopic characterisation revealed not only typical polycyclic aromatic networks expected for charcoals (aromaticity f_a = 0.64), but also showed an aliphatic character and that the sample contained alkyl chains ranging from nC₁₀ to nC₂₃ carbon chain lengths. The role of this material in bauxite refineries is discussed.     

Investigation of porosity of carbon materials and related effects on gas separation properties

Carbon molecular sieving membranes are chemically robust materials with tailorable gas transport properties for O₂/N₂, CO₂/CH₄ and C₃H₆/C₃H₈ separations. Such carbon materials were formed in this study by the pyrolysis of polyimide precursors. The final pyrolysis temperature was varied to alter the carbon structure, which changed the average pore size. Characterization of the porosity of these materials and how this feature changes when pyrolysis conditions are varied could guide the systematic control of these materials. However, the carbon is an amorphous, microporous material, which makes it difficult to characterize compared to crystalline materials. From separation studies of penetrants on these materials it appears that these materials have both ultramicropores (<7 Å) and larger micropores. The ultramicropores are believed to be mainly responsible for molecular sieving while the micropores provide negligible resistance to diffusion but provide high capacity sorption sites for penetrants. Techniques such as wide angle X-ray diffraction and the analysis of carbon dioxide adsorption isotherms using density functional theory were employed to characterize the microporosity of the material. The small dimensions of the key ultramicropores make accurate determination of their pore size distribution difficult. Therefore, to effectively discuss the differences in transport properties when different pyrolysis temperatures are used as well as penetrants with different dimensions, a hypothetical ultramicropore size distribution was used as a tool to discuss and interpret a combination of parameter effects and trends of separation properties.     

Xe NMR studies on carbon replicas of Y zeolite

¹²⁹Xe NMR spectroscopy of xenon gas adsorbed on carbon replicas of Y zeolite was carried out at room temperature. Corresponding carbon replicas have been prepared by using ethylene and HY zeolite in a pressure reactor. Xenon gas was adsorbed on the resulting carbon samples in the pressure range from 40 to 150 kPa. The plot of the chemical shift against xenon pressure was found to be a linear function in the investigated pressure range from 40 to 150 kPa. Intense and narrow peaks have been observed for the synthesized carbon samples indicating chemically pure samples. By comparison of the estimated chemical shift parameter δ_N→0 and the slope δ₁ of the shift versus density plots the existence of different pore sizes could be revealed. These observed differences can be attributed to different types of micropores generated by shrinkage effects during carbon liberation from the parent zeolite host. The obtained carbon replicas of Y zeolite were further characterized by elemental analysis, XPS, ¹³C MAS NMR and ESR spectroscopy.     

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.     

Titanium carbide derived nanoporous carbon for energy-related applications

High surface area nanoporous carbon has been prepared by thermo-chemical etching of titanium carbide TiC in chlorine in the temperature range 200-1200 °C. Structural analysis showed that this carbide-derived carbon (CDC) was highly disordered at all synthesis temperatures. Higher temperature resulted in increasing ordering and formation of bent graphene sheets or thin graphitic ribbons. Soft X-ray absorption near-edge structure spectroscopy demonstrated that CDC consisted mostly of sp² bonded carbon. Small-angle X-ray scattering and argon sorption measurements showed that the uniform carbon-carbon distance in cubic TiC resulted in the formation of small pores with a narrow size distribution at low synthesis temperatures; synthesis temperatures above 800 °C resulted in larger pores. CDC produced at 600-800 °C show great potential for energy-related applications. Hydrogen sorption experiments at −195.8 °C and atmospheric pressure showed a maximum gravimetric capacity of ∼330 cm³/g (3.0 wt.%). Methane sorption at 25 °C demonstrated a maximum capacity above 46 cm³/g (45 vol/vol or 3.1 wt.%) at atmospheric pressure. When tested as electrodes for supercapacitors with an organic electrolyte, the hydrogen-treated CDC showed specific capacitance up to 130 F/g with no degradation after 10 000 cycles.     

Microstructure of carbon derived from mangrove charcoal and its application in Li-ion batteries

In this study, the microstructure of mangrove-charcoal-derived carbon (MC) was studied using XRD, STM and TEM. MC was found to consist of aligned quasi-spherical structural units with diameters of around 5-20 nm. It shows typical hard carbon characteristics, including a strongly disoriented single graphene layer and BSU, formed by two or three graphene layers stacked nearly parallel. Some curved and faceted graphene layers, especially closed carbon nanoparticles with fullerene-like, were observed in the as-prepared samples. MC was also evaluated as an anodic material for Li-ion batteries. MC carbonized at 1000 °C possessed the highest available discharge capacity (below 0.5 V) of 335 mAh g⁻¹, the high first-cycle coulombic efficiency of 73.7%, good rate and cyclic capability and PC-based electrolyte compatibility. ⁷Li nuclear magnetic resonance (NMR) spectra of fully lithiated mangrove charcoal-derived carbons indicated the co-existence of three Li species.     

Synthesis of ordered nanoporous carbon and its application in Li-ion battery

Ordered nanoporous carbon (ONC) was comprehensively tested for the first time as electrode material in lithium-ion battery. Structure characterization shows the order nanoporous structure and tiny crystallite structure of as-synthesized ONC. The electrochemical properties of this carbon were studied by galvanostatic cycling and cyclic voltammetry. Of special interest is that ONC gave no peak on its positive sweep of the cyclic voltammetry, which was different from other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also used to investigate the electrochemical characteristics of ONC.     

Porous amorphous carbon models from periodic Gaussian chains of amorphous polymers

An algorithm has been developed to create structural models for amorphous carbons using Monte Carlo simulations in the canonical ensemble. The simulation method used follows the experimental preparation of nanoporous carbons (NPC) by pyrolysis from polyfurfuryl alcohol as a guideline. The resulting structure exhibits properties that compare favorably to those observed experimentally for real NPCs. These atomistic NPC models are approaching a realistic representation of NPCs used for gas separations and as such, are being used to study the diffusion of small gas molecules in these materials. Limitations of the method and possible improvements are discussed.     

Modeling ideal selectivity variation in nanoporous membranes

A parallel resistance transport model has been developed to describe variations in separation ability (quality) of nanoporous carbon membranes. The model considers transport through high-selectivity, high-resistance nanopores in combination with low-selectivity, low-resistance defect pores. Although few in number or small as a percentage of membrane area, these low-selectivity pores exert a disproportionate influence on permeation. The predictive qualities of the model are demonstrated using permeation data from the literature. Using flux ratios of oxygen to nitrogen, we can predict the area fraction (α) of defect pores. At an area fraction of only 10⁻⁹ defect pores, the oxygen-to-nitrogen ratio falls to near unity—indicating no selectivity for oxygen. Although developed for nanoporous carbon membranes, the approach will work for zeolitic and other forms of nanoporous membranes.     

Lignin-based carbon fibers: Oxidative thermostabilization of kraft lignin

The thermostabilization of lignin fibers used as precursors for carbon fibers was studied at temperatures up to 340 °C at various heating rates in the presence of air. The glass transition temperature (T_g) of the thermally treated lignin varied inversely with hydrogen content and was found to be independent of heating rate or oxidation temperature. A continuous heating transformation (CHT) diagram was constructed from kinetic data and used to predict the optimum heating rate for thermostabilization; a heating rate of 0.06 °C/min or lower was required in order to maintain T_g > T during thermostabilization. Elemental and mass analyses show that carbon and hydrogen content decrease during air oxidation at constant heating rates. The hydrogen loss is sigmoidal, which is consistent with autocatalytic processes. A net increase in oxygen occurs up to 200-250 °C; at higher temperatures, oxygen is lost. Spectroscopic analyses revealed the oxidation of susceptible groups within the lignin macromolecule to ketones, phenols and possibly carboxylic acids in the early stage of the reaction; the later stage involving the loss of CO₂ and water and the formation of anhydrides and possibly esters. Slower heating rates favored oxygen gain and, consequently, higher glass transition temperatures (T_g) as opposed to faster heating rates.     

Synthesis of nanoporous carbide-derived carbon by chlorination of titanium silicon carbide

Synthesis of nanoporous carbide-derived carbon, CDC, by extraction of titanium and silicon from Ti₃SiC₂ by chlorine is discussed in this work. Thermodynamic simulations using a Gibbs free energy minimization program provided general guidelines to the experimental design. Raman spectroscopy, X-ray diffraction, and electron microscopy studies showed that the structure of CDC depends on the chlorination temperature. The low temperature synthesis resulted in an amorphous CDC structure. Noticeable graphite formation starts above 800 °C and well ordered graphite ribbons of 1-3 nm in thickness form at 1200 °C. The macroscopic volume and shape of Ti₃SiC₂ preform were preserved during the transformation. However, the chlorination resulted in the formation of cracks between the former grains of the polycrystalline Ti₃SiC₂ preform. These cracks are believed to be caused by a contraction in the direction perpendicular to the basal planes of Ti₃SiC₂. The synthesized nanoporous carbon demonstrated excellent sorption properties. Energy dispersive X-ray spectroscopy studies showed that Ti₃SiC₂ material chlorinated at 400 °C is capable of trapping over 40 wt.% of Cl₂.     

Hollow porous carbon microspheres obtained by the pyrolysis of TiO2/poly(furfuryl alcohol) composite precursors

Disordered carbon materials with high porosity were prepared through the pyrolysis of TiO₂/poly(furfuryl alcohol) composites, obtained by the sol-gel method. The composites were prepared starting from titanium tetra-isopropoxide (TTIP) and furfuryl alcohol (FA) as precursors. Two different synthetic procedures for our composites were carried out, based on the addition of furfuryl alcohol (FA) before or after the TiO₂ nanoparticles formation. Also, different TTIP/FA ratio was tested. The hybrid materials obtained by both synthetic routes were pyrolyzed, under argon flow, at 900 °C producing novel TiO₂/carbon composites. All samples were characterized by XRD, FT-IR, DR-FTIR, Raman spectroscopy and TEM. Results indicated the effective FA polymerization on TiO₂ (anatase) nanoparticles, and polymer conversion to disordered carbon after the pyrolysis, simultaneously with TiO₂ anatase-rutile phase transition. The resulting TiO₂/carbon composites were treated with HF solution aiming the oxide dissolution, yielding an extremely porous carbon material as insoluble fraction. The morphology of these porous carbon materials is strongly dependent on the synthetic route adopted for the composite precursor, varying from carbon foam to highly ordered hollow microspheres.     

Polyfurfuryl alcohol derived activated carbons for high power electrical double layer capacitors

Polyfurfuryl alcohol (PFA) derived activated carbons were prepared by the acid catalysed polymerization of furfuryl alcohol, followed by potassium hydroxide activation. Activated carbons with apparent BET surface areas ranging from 1070 to 2600 m² g⁻¹, and corresponding average micropore sizes between 0.6 and 1.6 nm were obtained. The porosity of these carbons can be carefully controlled during activation and their performance as electrode materials in electric double layer capacitors (EDLCs) in a non-aqueous electrolyte (1 M Et₄NBF₄/ACN) is investigated.Carbon materials with a low average pore size (<∼0.6 nm) exhibited electrolyte accessibility issues and an associated decrease in capacitance at high charging rates. PFA carbons with larger average pore sizes exhibited greatly improved performance, with specific electrode capacitances of 150 F g⁻¹ at an operating voltage window of 0-2.5 V; which corresponds to 32 Wh kg⁻¹ and 38 kW kg⁻¹ on an active material basis. These carbons also displayed an outstanding performance at high current densities delivering up to 100 F g⁻¹ at current densities as high as 250 A g⁻¹. The exceptionally high capacitance and power of this electrode material is attributed to its good electronic conductivity and a highly effective combination of micro- and fine mesoporosity.     

Control of mesoporous properties of carbon cryogels prepared from wattle tannin and furfural

Wattle tannin–furfural (TFu) carbon cryogels are synthesized by sol–gel polycondensation of wattle tannin with furfural by using sodium hydroxide (NaOH) as a catalyst, dried by freeze-drying technique and then pyrolyzed under inert atmosphere, respectively. The amounts of wattle tannin (T), furfural (Fu), NaOH (C) and distilled water (W) are changed for preparing the mesoporous TFu carbon cryogels. The mole ratio of tannin to catalyst T/C plays a crucial role for the synthesis of TFu organic and carbon cryogels. The results suggest that the T/C ratio should be above 0.25 but <1.0 to prepare the mesoporous and homogeneous cryogels. Although TFu carbon cryogels have the broad mesopore size distribution, the mesoporous structure is controllable by the synthesis conditions. The carbon cryogels possess the mesopore volume less than 0.56 cm³/g and the BET surface area less than 600 m²/g. Moreover, the ratio of catalyst to water C/W can be used to prepare the homogeneous and mesoporous carbon cryogels, and to control the mesopore radius of carbon cryogels in the range of 1.6–9.6 nm.     

Structure of nanoporous carbon produced from boron carbide

The structure of nanoporous carbon produced by chlorination of powdered boron carbide at 600, 800, 1000, 1300, 1500, and 1800 °C has been studied by scanning electron microscopy, X-ray diffraction analysis, helium pycnometry, and low-temperature adsorption of nitrogen. On the basis of the results obtained, suggestions are made concerning the type of organization of the nanoporous structure of these materials. The evolution of the structure of nanoporous carbon is analyzed in relation to the synthesis temperature of nanoporous carbon. It is shown that, as the chlorination temperature increases, the structure of nanoporous carbon becomes more perfect: it changes from paracrystalline to turbostratic. The specific surface area decreases from 2200 to 36 m²/g, the volume of micropores decreases from 0.93 to 0.01 cm³/g, and that of mesopores first increases from 0.15 cm³/g (600 °C) to 0.57 cm³/g (1000 °C) and then decreases to 0.19 cm³/g (1800 °C). The total pore volume decreases from 1.08 to 0.20 cm³/g.     

SAXS investigation of nanoporous structure of thermal-modified carbon materials

The article investigates the effect of thermal modification of porous carbon material (PCM), obtained from plant feedstock, on its morphology and fractal structure by small-angle X-ray scattering (SAXS) method. The analysis of the scattering intensity curves serve the basis for calculating the parameters of the PCM porous structure: the Porod constant, the Porod invariant, average pore radius, specific surface area, and mass and surface fractal dimensions. It has been found out that the PCMs obtained have fractal structure, formed from mass and surface fractals, the sizes of which increase at the growth of temperature and modification time.

PACS

81.05.Uw; 61.05.cf; 82.47.Aa     

Preparation of porous carbon derived from mixtures of furfuryl resin and glycol with controlled pore size distribution

This paper describes the preparation and properties of porous carbon by a technique which consists of mixing a carbon precursor (furfuryl resin and furfural alcohol), a pore-forming agent and a solvent (glycol), polymerizing the resin mixture, and pyrolyzing the hybrid of resin and glycol. The properties of porous carbons have been systematically investigated as a function of composition and heat treatment, with emphasis on understanding and controlling their morphology and pore size distribution. The results seem to indicate that by varying the ratios of the constituents in the polymer system, porous carbons with a wide variation in pore size distribution and morphology can be obtained. Three types of morphologies were observed: interconnected carbon with secondary spherical pores, discrete carbon particulates, and a crosslinked carbon network. Porous carbons with a very narrow pore size distribution have been obtained and the average pore size was controlled between 5 and 0.008 μm. The microstructure of porous carbon formed as a result of phase separation of resin-rich phase and glycol-rich phase, rather than a result of the pyrolysis process. Heat treatment had little effect on the properties of the porous carbons.