Computational study of B- or N-doped single-walled carbon nanotubes as NH3 and NO2 sensors

The adsorption of NH₃ and NO₂ in B- or N-doped (10, 0) single-walled carbon nanotubes (SWCNTs) was investigated by using density functional computations to exploit their potential applications as gas sensors. NH₃ can be chemisorbed only in B-doped SWCNTs with apparent charge transfer, so B-doped SWCNTs can be used as NH₃ sensors. Both B- and N-doping make NO₂ chemisorption feasible in SWCNTs, but the binding of NO₂ with B is too strong, indicating an impractical recovery time as gas sensors. Due to the medium (optimal) adsorption energy and the conductance reduction accompanied with the charge transfer between SWCNTs and gas molecules, N-doped SWCNTs are potentially good NO₂ sensors.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.     

Selective transport of CO2, CH4, and N2 in coals: insights from modeling of experimental gas adsorption data

Selective adsorption and transport of gases in coal are important for natural gas recovery and carbon sequestration in depleted coal seams for environmental remediation. Gases are stored in coal mainly in the adsorbed state. In this study, the interaction energies of adsorbates (CO₂, CH₄, and N₂) and micropores with various widths are investigated using a slit-shape pore model. The experimental adsorption rate data of the three gases conducted on the same coal sample are numerically simulated using a bidisperse model and apparent diffusivities of each adsorbate in the macropore and micropore are determined. The results indicate that the relative adsorbate molecule size and pore structure play an important role in selective gas adsorption and diffusion in micropores. Generally, the microporous coals diffusion is activated and the apparent micropore diffusivities of gases in coal decrease strongly with increase in gas kinetic diameters. Apparent micropore diffusivity of CO₂ is generally one or two order of magnitude higher than those of CH₄ and N₂ because their kinetic diameters have the relation: CO₂ (0.33 nm)<N₂ (0.36 nm)<CH₄ (0.38 nm). In contrast to theoretical values, apparent macropore diffusivity of CO₂ is also larger than those of CH₄ and N₂, suggesting that coal has an interconnected pore network but highly constricted by ultra micropores with width <∼0.6 nm. It is also found that the apparent diffusivity strongly decreases with an increase in gas pressure, which may be attributed to coal matrix swelling caused by gas adsorption. Therefore, rigorous modeling of gas recovery and production requires consideration of specific interaction of gas and coal matrix.     

Enhancement of H2 and CH4 adsorptivities of single wall carbon nanotubes produced by mixed acid treatment

Single wall carbon nanotubes (SWCNTs) were treated with a HNO₃/H₂SO₄ mixed solution to increase the number of narrow micropores. The mixed acid treatment increased the micropore volume from 0.13 to 0.35 mL g⁻¹ as measured by N₂ adsorption at 77 K. The micropore volume evaluated with CO₂ adsorption at 273 K increased from 0.06 to 0.27 mL g⁻¹. This remarkable micropore volume increase was ascribed to the formation of a highly packed and ordered SWCNT assembly with the acid treatment, which was confirmed by field emission scanning electron microscopy. The adsorption amount of supercritical H₂ at 77 K under 5 MPa pressure increased twofold as a result of the acid treatment, while the supercritical CH₄ adsorption amount at 303 K and 5 MPa pressure increased by 40%. These remarkable increases were caused by increased amount of narrow micropores as a result of the acid treatment.     

Synthesis of radially aligned single-walled carbon nanotubes on a SiO2/Si substrate by introducing sodium chloride

Radially aligned single-walled carbon nanotubes (SWCNTs) were synthesized on a SiO₂/Si substrate with thermal chemical vapor deposition by introducing sodium chloride (NaCl) onto the substrate surface. The growth of such SWCNTs was sensitive to the thickness of the SiO₂ layer on the Si substrate and the speed of the reactive gas flow. Cristobalite crystals were found to be formed on the substrate after the SWCNT growth process and were significant for the growth of radially aligned SWCNTs. The SWCNTs were assumed to be directed by the cristobalite crystals along a certain crystal direction on the (1 0 1) crystal face.     

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.     

Porous structure and adsorptive properties of pineapple peel based activated carbons prepared via microwave assisted KOH and K2CO3 activation

The present research explores the feasibility of microwave irradiation for preparation of high surface area activated carbon from pineapple peel (PPAC), an agricultural effluent emitted from the food can processing industries via KOH and K₂CO₃ activation. The activation process was performed at the microwave power of 600 W and irradiation time of 6 min. The equilibrium behavior of PPAC was investigated by performing batch adsorption experiments using methylene blue as adsorbate. Nonlinear adsorption isotherm models, Langmuir, Freundlich and Temkin were used to simulate the equilibrium data. KOH activated sample demonstrated a better development of pore structure, with the BET surface area, total pore volume and average pore size of 1006 m²/g, 0.59 m³/g and 23.44 Å, respectively, while the monolayer adsorption capacity of methylene blue was determined to be 462.10 mg/g. The findings support the potential use of microwave assisted KOH and K₂CO₃ activation as a promising activation technique.     

Generation of H2 gas from polystyrene and poly(vinyl alcohol) by milling and heating with Ni(OH)2 and Ca(OH)2

A two-step process to generate H₂ gas; first by milling polystyrene (PS) or poly(vinyl alcohol) (PVA) with Ni(OH)₂ and Ca(OH)₂, followed by heating of the milled product in the second-step was performed in this work. Polymer and hydroxide mixtures obtained after milling for 60 min and heating to 700 °C showed H₂, CH₄, H₂O, CO, and CO₂ as the main gaseous products with H₂ as the dominant gas generated between 350 and 500 °C. Analysis of the gaseous products by TG-MS and gas-chromatography, and solid products by TG-DTA and XRD shows that CO₂ gas was fixed as CaCO₃ at temperatures between 350 to 600 °C allowing generation of H₂ gas with concentrations over 95% for PS and over 98% for PVA. The results in this study show that milling of solid based hydrocarbon compounds with nickel and calcium hydroxides allows dispersion of nickel to hydrocarbon surfaces and facilitates C-C bond rupture in polymer(s) during heating at temperatures below 500 °C, at the same time calcium adsorbs CO₂. This process could be developed to treat hydrocarbon based wastes such as plastics, biomass or combinations at low temperatures avoiding syngas purification and separation steps.     

CO oxidation and CO2 reduction on carbon supported PtWO3 catalyst

The activity of a carbon supported PtWO₃ (PtWO₃/C) catalyst in the CO oxidation and CO₂ reduction reactions was evaluated in sulfuric acid solution at room temperature.Cyclic voltammetry combined with on-line mass spectrometry shows that the oxidation of both saturated CO adlayer and dissolved CO on PtWO₃/C material commences at rather low potentials, ca. 0.18 and 0.12 V vs. RHE, respectively. However, the low-potential process seems to involve only a minor fraction of the CO adlayer, the major part of the adsorbed CO layer being oxidised at the potentials as high as those for pure Pt catalysts—ca. 0.7 V vs. RHE. PtWO₃/C material was found to reversibly de-activate upon a prolonged exposure to the CO-saturated solution due to the inhibition of the hydrogen tungsten bronze formation.The reduction of CO₂ on PtWO₃/C leads to the formation of an adsorbate - presumably CO - on the Pt sites of the catalyst. Although the rate of the adsorbate build-up on PtWO₃/C at 0.1 V is lower than that on pure Pt/C, our results indicate that upon a prolonged exposure of the PtWO₃/C electrode to a CO₂-saturated solution a complete poisoning of the Pt sites with the adsorbate is likely to occur at room temperature.     

Crystallinity, morphology, mechanical properties and conductivity study of in situ formed PVdF/LiClO4/TiO2 nanocomposite polymer electrolytes

Nanocomposite polymer electrolytes composed of poly(vinylidene fluoride) (PVdF), lithium perchlorate (LiClO₄) and TiO₂ nanoparticles were prepared by a solution-cast method. The nanosized ceramic filler, TiO₂, was synthesized in situ by a sol-gel process. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis revealed that the crystalline phase and crystallinity were slightly decreased with the addition of TiO₂ to the PVdF/LiClO₄ system. Scanning electron microscopy (SEM) micrographs showed that the PVdF/LiClO₄/TiO₂ solid polymer electrolyte (SPE) membranes had a porous structure to a certain extent, and that the pore size decreased with increasing TiO₂ content. The overfull nanoparticles tended to aggregate on the surface and inside the pores at TiO₂ content above 15 wt.% so that the porosity decreased. Regarding mechanical properties, the strength of the PVdF/LiClO₄/TiO₂ electrolytes decreased after the uptake of EC/PC solution. In contrast to the conductive behavior of wet PVdF/LiClO₄/TiO₂ membranes relative to the uptake of EC/PC solution, the conductive mechanism of the solid membranes, after the lithium ion of LiClO₄ had already been installed in the PVdF solid polymer network, was mainly influenced by the TiO₂ nanoparticles. At a TiO₂ content of 10 wt.%, the solid and wet PVdF/LiClO₄/TiO₂ systems had the maximum conductivity values of 7.1 × 10⁻⁴ and 1.8 × 10⁻³ S/cm, respectively.     

ZrO2 removing reactions of Groups IV-VI transition metal carbides in ZrB2 based composites

In this paper, ZrO₂ removing reactions of Groups IV-VI transition metal carbides (MCs, M = Hf, Nb, Ta, W, Ti and V) in ZrB₂ based ultra-high temperature ceramics (UHTCs) are investigated. Distinct roles of various MCs were observed during this process. According to thermodynamic analysis and experiment verifications, the sequence for oxide removing ability of different MCs is WC > VC > NbC > TaC > HfC > TiC. The importance of this study concerns the establishment of a map of reactivity of the transition metal carbides against ZrO₂, in order to choose the proper additive for the densification of ZrB₂-composites.Utilizing right reactions and controlling proper sintering atmospheres, high density ZrB₂-SiC ceramic could be eventually obtained by pressureless sintering at temperatures (around 2000-2200 °C).     

Efficiency of C60 incorporation in and release from single-wall carbon nanotubes depending on their diameters

We show that the efficiency of incorporating C₆₀ in single-wall carbon nanotubes (SWCNTs) and that of the incorporated C₆₀’s release from the SWCNTs depend on the SWCNT diameter. Through transmission electron microscopy, we found that the C₆₀ incorporation efficiency reached its maximum at diameters of 1-2 nm, while the efficiency of C₆₀ release from SWCNTs in toluene was maximized at 3-5 nm. The difficulty of C₆₀ release from SWCNTs with diameters of 5-6 nm might reflect either the effective packing of C₆₀ inside SWCNTs or a flattened SWCNT structure. We occasionally observed C₆₀ molecules arranged in a line along the sidewall inside SWCNTs with large diameters/width (>7 nm), indicating that large diameter SWCNTs were sometimes flattened.     

Methanol synthesis from CO2 and H2 in multi-tubular fixed-bed reactor and multi-tubular reactor filled with monoliths

This work investigates the impact of catalyst structuring into particles or monoliths on methanol production from only CO₂ and H₂ at a large scale. Methanol synthesis in multi-tubular reactors is evaluated using packed-bed and monolithic reactors by modeling heat and mass transfer in each reactor. The obtained simulation results show that, at low gas hourly space velocity (GHSV = 10,000 h⁻¹), the performances of both reactor technologies are similar. In this case, the packed-bed reactor technology is the most appropriate technology due to its simplicity of installation and operation. At high GHSV (25,000 h⁻¹), the packed-bed reactor technology is limited by a considerable pressure drop that causes an important loss in productivity due to thermodynamic equilibrium, whereas the monolithic reactors exhibit negligible pressure drop and achieve far better performances.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

Thermodynamic modeling of CO2 solubility in aqueous solutions of NaCl and Na2SO4

A thermodynamic model based on the electrolyte NRTL activity coefficient equation and PC-SAFT equation-of-state is developed for CO₂ solubility in aqueous solutions of NaCl and Na₂SO₄ with temperature up to 473.15 K, pressure up to 150 MPa, and salt concentrations up to saturation. The Henry's constant parameters of CO₂ in H₂O and the characteristic volume parameters for CO₂ required for pressure correction of Henry's constant are identified from fitting the experimental gas solubility of CO₂ in pure water with temperature up to 473.15 K and pressure up to 150 MPa. The NRTL binary parameters for the CO₂-(Na⁺, Cl⁻) pair and the CO₂-(Na⁺, SO₄²⁻) pair are regressed against the experimental VLE data for the CO₂-NaCl-H₂O ternary system up to 373.15 K and 20 MPa and the CO₂-Na₂SO₄-H₂O ternary system up to 433.15 K and 13 MPa, respectively. Model calculations on solubility and heat of solution of CO₂ in pure water and aqueous solutions of NaCl and Na₂SO₄ are compared to the available experimental data of the CO₂-H₂O binary, CO₂-NaCl-H₂O ternary and CO₂-Na₂SO₄-H₂O ternary systems with excellent results.     

Synthesis, characterization and performance of CuO/La2O3 composite catalyst for ammonia catalytic oxidation

This work considers the oxidation of ammonia (NH₃) by selective catalytic oxidation (SCO) over a CuO/La₂O₃ composite catalyst at temperatures between 150 and 400 °C. A CuO/La₂O₃ composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH₃ (C₀ = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O₂ = 4%) affect the operational stability and the capacity for removing NH₃. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La₂O₃ composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La₂O₃ composite catalyst, and around 93.0% NH₃ reduction was achieved during catalytic oxidation over the CuO/La₂O₃ (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH₃ in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h^− 1.     

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.     

An investigation of the causes of the difference in coal particle ignition temperature between combustion in air and in O2/CO2

The ignition temperatures of a Loy Yang brown coal and a Datong bituminous coal were investigated in a wire-mesh reactor where the secondary reactions of the evolved volatiles were minimised. An increase in the average particle ignition temperature of 21 °C was observed for the brown coal when air (21% O₂ + 79% N₂) was replaced with a mixture of 21% O₂ + 79% CO₂. Combustion was also carried out in the mixtures of 21% O₂ + 79% argon and 21%O₂ + 79% helium in order to determine the effects of heat transfer on the observed particle ignition temperature. It is concluded that the thermal conductivity of gas atmosphere surrounding the particles greatly influences the observed particle ignition temperature while the effects of the heat capacity of the gas atmosphere was very minor under our experimental conditions. The structure of char and the reactions involving the char (char-O₂ and char-CO₂) can greatly affect the observed particle ignition temperature. In particular, the char-CO₂ reactions were largely responsible for the observed difference in particle ignition temperature in air and in 21% O₂ + 79% CO₂. Alkali and alkaline earth metallic (AAEM) species in the brown coal also significantly affect the observed particle ignition temperature.     

Kinetic modeling of oxidative coupling of methane over Mn/Na2WO4/SiO2 catalyst

A comprehensive kinetic model for oxidative coupling of methane (OCM) on Mn/Na₂WO₄/SiO₂ catalyst was developed based on a microcatalytic reactor data. The methane conversion and ethylene, ethane, carbon monoxide and carbon dioxide selectivities were obtained in a wide range of operating conditions including 750 < T < 875 °C, 4 < CH₄/O₂ < 7.5 and space time between 30 and 160 kg · s/m³ at P = 657 mmHg. The reaction networks of five kinetic models with appropriate rate equation type were compared together. The kinetics rates parameters of each reaction network were estimated using genetic algorithm optimization method. After comparing the reaction networks, the reaction network presented by Stansch et al. was found to best represent the OCM reaction network and was further used in this work. This kinetic network considers both catalytic and gas-phase as well as primary and consecutive reaction steps to predict the performance of the OCM. Comparing the experimental and predicted data showed that presented model has a reasonable fit between the experimental data and the predicted values with average absolute relative deviation of ± 9.1%.