Activated carbon for hydrogen purification by pressure swing adsorption: Multicomponent breakthrough curves and PSA performance

In this work, multicomponent breakthrough experiments (binary H₂-CO₂, ternary H₂-CO₂-CO and five-component H₂-CO₂-CO-CH₄-N₂) were performed under different operating conditions in activated carbon extrudates to validate the mathematical model. A 10 steps one-column VPSA experiment was also performed. These experiments allow experimental validation of adsorption equilibrium predicted by the multicomponent extension of the Virial isotherm and a fixed-bed mathematical model. In the VPSA experiment, a 99.981% hydrogen purity stream (with 63 ppm of CO contamination) was obtained with a hydrogen recovery of 81.6% and an adsorbent productivity of .The mathematical model was also employed to assess the effect of operating conditions and the influence of step times and pressure equalizations in the PSA unit. It was verified that high-purity hydrogen (>99.99%) can be obtained using this adsorbent with recoveries higher than 75% and unit productivities of .     

Influence of carbon dioxide partial pressure and fluidization velocity on activated carbons prepared from scrap car tyre in a fluidized bed

The effect of carbon dioxide partial pressure and fluidization velocity on activated carbons produced by carbon dioxide activation of scrap car tyre rubber in a fluidized bed has been studied. The method consisted of carbonization at under nitrogen followed by activation at . Three types of activated carbons were produced using activated gas concentrations of 20, 60 and 100% carbon dioxide by volume, the rest nitrogen, at a constant fluidization velocity (0.0393 m/s) to investigate the influence of carbon dioxide partial pressure. Within the experimental setup and activation time of 4 h, it was observed that BET surface area and total pore volume increased with carbon dioxide partial pressure reaching and , respectively, for 100% activation with carbon dioxide. Three other types of activated carbons were produced using 100% carbon dioxide at two (0.0393 m/s), three (0.0589 m/s) and four (0.0786 m/s) times the minimum fluidization velocity (U_mf). The BET surface area and total pore volume were observed to increase with fluidization velocity (which can be viewed as an indicator of the intensity of mixing in the bed), reaching and , respectively, at four times the minimum fluidization velocity.     

Kinetics and equilibrium of dissolved oxygen adsorption on activated carbon

The macroscopic adsorption behavior of dissolved oxygen on a coconut shell-derived granular activated carbon has been studied in batch mode at 301 and 313 K for initial dissolved oxygen concentrations of 10-30 mg/l and oxygen/carbon ratios of 2-180 mg/g. BET (Brunauer, Emmett, and Teller) surface area, micropore volume, and pore size distribution were determined from N₂ isotherm data for fresh and used samples of carbon. The surface groups were characterized using Boehm titrations, potentiometric titrations, and FTIR study. The material is characterized by its high specific surface area , microporocity (micropore volume ), its basic character ( total basic groups) and its high iron content (15,480 ppm Fe). BET n-layer isotherm describes adsorption equilibrium suggesting cooperative adsorption and important adsorbate-adsorbate interactions. Kinetic data suggest a process dependent on surface coverage. At low coverage a Fickian, intraparticle diffusion rate model assuming a local equilibrium isotherm (oxygen dissociation reaction) adequately describes the process. The calculated diffusion coefficients (D) vary between and for initial oxygen concentration of 10 and 20 mg/l, respectively. Sensitivity analysis shows that the oxygen dissociation equilibrium constant determines the equilibrium concentration, whereas the diffusion coefficient controls the kinetic rate of the adsorption process having no effect at the final equilibrium concentration. A combined kinetic mass transfer model with concentration-dependent diffusion (parabolic form) has been developed and successfully applied on the dissolved oxygen adsorption system at high surface coverage. For equilibrium uptake of the estimated mean mass transfer coefficient and adsorption rate constant are and , respectively.     

Measurements and modeling of high-pressure excess molar enthalpies and isothermal vapor-liquid equilibria of the carbon dioxide + N,N-dimethylformamide system

Mixtures of supercritical CO₂ and N,N-dimethylformamide (DMF) are very often involved in supercritical fluid applications and their thermodynamic properties are required to understand and design these processes. Excess molar enthalpies () for CO₂ + DMF mixtures were measured using an isothermal high-pressure flow calorimeter under conditions of temperature and pressure typically used in supercritical processes: 313.15 and 323.15 K at 9.00, 12.00, 15.00 and 18.00 MPa and 333.15 K at 9.00 and 15.00 MPa. The Peng-Robinson and the Soave-Redlich-Kwong equations of state were used in conjunction with the classical mixing rules to model the literature vapor-liquid equilibrium and critical data and the excess enthalpy data. In most cases, CO₂ + DMF mixtures showed very exothermic mixing and excess molar enthalpies exhibited a minimum in the CO₂-rich region. The lowest value (−4526 J mol⁻¹) was observed for a CO₂ mole fraction value of 0.713 at 9.00 MPa and 333.15 K. On the other hand, at 9.00 MPa and 323.15 and 333.15 K varies linearly with CO₂ mole fraction in the two-phase region where a gaseous and a liquid mixture of fixed composition are in equilibrium. The effects of pressure and temperature on the excess molar enthalpy are large. For a given mole fraction, mixtures become less exothermic as pressure increases or temperature decreases. These excess enthalpy data were analyzed in terms of molecular interactions, phase equilibria, density and critical parameters previously reported for CO₂ + DMF. All throughout this paper, the key concepts and modeling tools originate from the work of van der Waals: the paper is intended as a small piece of recognition of van der Waals overwhelming contributions to thermodynamics.     

Mechanism of enhanced gas absorption in presence of fine solid particles. Effect of molecular diffusivity on mass transfer coefficient in stirred cell

Desorption of oxygen and hydrogen from various liquids (water, 0.8 molar sodium sulphate solution) containing suspended particles of activated carbon at various solid loading was investigated. The desorption was used to avoid supersaturation effect which was observed during oxygen and hydrogen absorption into liquid saturated with nitrogen. Experiments were carried out in a stirred cell with flat gas-liquid interface at and atmospheric pressure. An increase of k_L upon addition of the particles was observed. Enhancement factor increases with increasing contact time of the particles with liquid reaching maximum steady-state value of approx. 3 after sufficiently long time (a few hours) regardless of solid loading , agitator frequency and solute gas (O₂,H₂). The results fit the correlation (e is specific power dissipated by agitator in liquid and D is molecular diffusivity of gas absorbed) with the exponent for liquids without and for the liquids with the particles. It indicates that the interface is rigid in absence of particles and hinders the motion of liquid along the interface forming boundary layer while in the presence of particles the interface is completely mobile and surface renewal proceeds according to the penetration model. These results confirm a finding of Kaya and Schumpe (2005) that the enhancement of mass transfer in the cell at the presence of hydrophobic solids is due to clean-up of the interface from surfactants by their adsorption on hydrophobic solids rather than by a “shuttle mechanism” exerted by particles with a high adsorption capacity for the transfer component.     

Preparation of diatomite/Ca(OH)2 sorbents and modelling their sulphation reaction

Mixtures of Ca(OH)₂ and diatomite were hydrated at different conditions to produce reactive SO₂ sorbents. Two different hydration techniques were used; namely, atmospheric and pressure hydration. The effect of the hydration temperature, time and diatomite/Ca(OH)₂ weight ratio on the physical properties of the activated sorbents were investigated. In atmospheric hydration, it was found that increasing the temperature and hydration time caused an increase in the total surface area of the sorbents. However, surface area values of the sorbents prepared from mixtures which have different diatomite/Ca(OH)₂ weight ratio were generally not changed significantly. In pressure hydration, the surface area of the activated sorbents was positively affected from the hydration temperature and pressure. Finally, Ca(OH)₂ and two diatomite/Ca(OH)₂ sorbents were sulphated at constant temperature using a synthetic gaseous mixture consisting of 5% O₂, 10% CO₂, and the balance of nitrogen with a 55% relative humidity. The sulphation reaction of these sorbents were investigated and modelled. The unreacted shrinking core model was chosen to describe this non-catalytic solid/gas (hydrated sorbent/SO₂) reaction mechanism. The experimental results were found to be correlated successfully by this model.     

Study of supercritical three-phase methanol synthesis with n-hexane at supercritical state

A process of supercritical three-phase methanol synthesis on a Cu-based catalyst C302-2, which has high activity at low temperature and low pressure, has been carried out in a mechanically agitated slurry reactor with paraffin as the inert liquid medium and n-hexane as the supercritical medium. The reaction conditions are as follows: pressure ranging from 6.0 to , temperature ranging from 235 to and mass space velocity from 450 to . The influences of these conditions on the conversion of CO and the outlet methanol mole fraction have been investigated in detail. The results show that both the conversion of CO and outlet methanol mole fraction decreased when the mass space velocity and the temperature were increased under the condition of supercritical n-hexane. In addition, we compared the three-phase slurry bed methanol synthesis with and without supercritical medium. The results show that the conversion of CO, CO₂ and H₂ as well as outlet methanol mole fraction of supercritical three-phase methanol synthesis are obviously higher than those chemical equilibrium values of gas-solid reaction under the corresponding experimental condition. That is to say, the process of supercritical three-phase methanol synthesis with n-hexane at supercritical state can remove the limitation of chemical reaction balance of the reversible exothermic methanol synthesis reaction on the conversion of reactants by introducing a supercritical medium that plays an important role in the reaction-separation coupling process in methanol synthesis, by which the conversion of reactants and outlet methanol mole fraction at supercritical condition are increased greatly. Therefore, they are higher than those of three-phase methanol synthesis without supercritical n-hexane. The advantage of supercritical three-phase methanol synthesis is self-evident. Our present study provides an experimental foundation for further engineering exploitation research on the three-phase methanol synthesis process with supercritical medium in three-phase slurry reactors.     

Surfactant adsorption rather than “shuttle effect”?

In the absence of chemical reaction, mass transfer enhancement by suspended particles (mostly activated carbon) at the gas/liquid interface has been frequently reported and is usually explained by a “shuttle mechanism” exerted by particles with a high adsorption capacity for the transfer component. A major problem of this model is that unrealistic enrichment of the solids at the interface as compared to the bulk concentration has to be assumed. A comprehensive study has been carried out in a stirred tank in a wide range of the stirring speed (0-) with 9 different powdered solids suspended in water. With a flat gas/liquid interface, moderately hydrophobic solids significantly increased the mass transfer rates at low solid loadings (0.1-). However, the effect is not limited to particles with a high adsorption capacity for the gas (e.g. activated carbon) but it is observed also for non-porous particles (e.g. graphite or sulphur). When the particles are removed by rinsing, the absorption rates remain high. When the system is kept very clean (surfactant free), the enhancement effect is not observed. Based on these findings, it is concluded that adsorption of surfactants on hydrophobic solids cleans the interface resulting in higher mass transfer coefficients k_L.     

Gas-solid adsorption of selected volatile organic compounds on titanium dioxide Degussa P25

This paper focuses on the adsorption of gaseous trichloroethylene, toluene and chlorobenzene on the photocatalyst TiO₂ Degussa P25. An optimized EPICS (Equilibrium Partitioning In Closed Systems) methodology was used to study equilibrium partitioning. For the three compounds investigated, equilibrium adsorption was reached within of incubation. Adsorption isotherms, determined at a temperature (T) of and relative humidities (RH) of 0.0% and 57.8% were found to be linear (R²>0.993,n=5), indicating that no monolayer surface coverage was reached in the concentration interval studied ). Within the linear part of the isotherm, the influence of both relative humidity and temperature was investigated in a systematic way and discussed from a thermodynamic point of view. Data analysis resulted in a double linear regression for 22% ?RH?90% and . The equilibrium adsorption coefficient represents the equilibrium concentration ratio and ΔU_ads is the internal energy of adsorption . At RH=0.0%, experimental K values were a factor 5-10 higher than those expected from the regression equation, indicating that another adsorption mechanism becomes important below monolayer surface coverage of TiO₂ by water vapour molecules. Since surface interactions are of primary importance in photocatalytic reactions, this paper contributes to a better understanding of the basic mechanisms of TiO₂ mediated heterogeneous photocatalysis and is an interesting tool for developing optimized mathematical models.     

Adsorption of zinc(II) from water with purified carbon nanotubes

Commercial single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) were purified by sodium hypochlorite solutions and were employed as adsorbents to study the adsorption characteristics of zinc from water. The properties of CNTs such as purity, structure and nature of the surface were greatly improved after purification which made CNTs become more hydrophilic and suitable for adsorption of Zn²⁺. In general, the adsorption capacity of Zn²⁺ onto CNTs increased with the increase of pH in the pH range of 1-8, fluctuated very little and reached maximum in the pH range of 8-11 and decreased at a pH of 12. A comparative study on the adsorption of Zn²⁺ between CNTs and commercial powdered activated carbon (PAC) was also conducted. The maximum adsorption capacities of Zn²⁺ calculated by the Langmuir model are 43.66, 32.68, and with SWCNTs, MWCNTs and PAC, respectively, at an initial Zn²⁺ concentration range of 10-. The short contact time needed to reach equilibrium as well as the high adsorption capacity suggests that SWCNTs and MWCNTs possess highly potential applications for the removal of Zn²⁺ from water.     

Comparison of the adsorption performance of compound adsorbent in a refrigeration cycle with and without mass recovery

Adsorption and desorption were performed on a compound adsorbent composed of CaCl₂ and activated carbon in cycles both with and without mass recovery and the performances obtained were compared with those of equilibrium adsorption. Experimental results of the cycles without mass recovery carried out on an adsorption refrigeration unit yielded performances that were slightly less than those of equilibrium adsorption. The adsorption performances of the cycle with mass recovery were measured to be much better than those of the cycle without mass recovery. At of evaporating temperature, the cycle adsorption capacity was as high as 0.78 kg/kg for the cycle with mass recovery while it was only 0.55 kg/kg for the cycle without mass recovery. The average adsorption/desorption rate of the cycle with mass recovery, which was 0.031 (kg/kg)/min, has been improved by 47.6% compared with that of the cycle without mass recovery. Research on the cycle adsorption capacity at different evaporating temperatures showed that the improvement of cycle adsorption capacity, with mass recovery, was higher under the condition of lower evaporating temperature. At evaporating temperature, the mass recovery operation had improved the adsorption capacity by 78% compared with the cycle without mass recovery. In addition, refrigeration performances for the cycles with and without mass recovery at an evaporating temperature of were studied. Compared with the results of the cycle without mass recovery, SCP (specific cooling power) and COP (coefficient of refrigeration performance) have been improved by 48.6% and 54.5%, respectively, when mass recovery is performed.     

Particle diameter prediction in supercritical nanoparticle synthesis using three-dimensional CFD simulations. Validation for anatase titanium dioxide production

A mathematical model is proposed and validated with experimental data for the estimation of the average diameter attained by the particles that are generated by decomposition of an organometallic precursor in supercritical CO₂ (scCO₂). Experiments have been performed for the synthesis of TiO₂ anatase nanoparticles, using diisopropoxititanium bis(acetilacetonate) (DIPBAT) as precursor, ethanol as reactant and scCO₂ as solvent. The model is solved by using computational fluid dynamics (CFD) for the experimental geometry: a tee piece as mixer followed by a cylindrical reactor. Peng-Robinson EOS with Huron-Vidal mixing rule has been used to predict density variations within hydrodynamic equations. A pseudo-first order kinetic (r_TiO2=kC_DIPBAT, with ) has been proposed for mass and population balances. The CFD simulations predict a reduction on particle diameter from 400 to 200 nm when the Reynolds number is increased from 280 to 1500. In this range, deviations with experimental data are lower than 15%. A parametric study of the kinetic constant reveals that for faster reactions (Da?10^-3) the trend of particle size with the Reynolds number is inverse, and particle diameter increases when the Reynolds number is increased.     

Flashback propensity of syngas fuels

This paper presents experimental measurements of the critical velocity gradient and flashback behavior of H₂-CO and H₂-CH₄ mixtures. Effects of H₂ concentration, external excitation, and swirl on the flashback behavior for flames of these fuel mixtures are discussed. For H₂ concentration burner and scaling studies the critical velocity gradient (g_F), defined as the ratio of the square of the laminar burning velocity to the thermal diffusivity of the mixture , was used to quantify the flashback propensity of the flames. The critical velocity gradient of both H₂-CH₄ and H₂-CO flames changed nonlinearly with the increase in H₂ contents in the mixture. The critical velocity gradient (g_F) of 5-95% and 15-85% H₂-CO mixtures somewhat agreed with the scaling relation and yielded an average c value of 0.04. Similarly, values of a 25%H₂-75%CH₄ for different burner diameters were also fitted using the scaling relation yielding an average c value of 0.044. The g_F values of 25-75% H₂-CO mixture showed non-linear variation with the ratio (especially for ), and at a lower ratios burner diameter had small effect on critical velocity gradient measurements. The opposite trend was observed for a 25-75% H₂-CH₄ mixture showing non-linear variation at a lower ratios (for ) and having less effect at higher ratios. It was also determined that the effect of external excitation on the flashback propensity of H₂-CO flames with more than 5% H₂ was not significant. Flashback through two mechanisms and their dependence on combustor parameters were also identified for swirl stabilized H₂-CO flames.     

Diffusion coefficients of diesel fuel and surrogate compounds in supercritical carbon dioxide

Facilitating a new concept of clean diesel combustion using supercritical fluids requires a better understanding of thermophysical properties of the diesel fuel/diluent system. Mass diffusivity is one such property that is important to understand diesel fuel/diluent mixing and spray and combustion of supercritical fuel mixtures. In this work, diffusion coefficients of diesel fuel and surrogate compounds in supercritical carbon dioxide were experimentally determined by the Taylor dispersion method at temperatures from 313.15 to 373.15 K and pressures up to 30 MPa. Difficulties were encountered to measure diffusion coefficients using the Taylor dispersion method near the critical region of CO₂ which resulted in curve-fitting errors greater than 5%. Predictive correlations including Wilke-Chang, Scheibel, and He-Yu were examined. Diffusivity data were also fitted by D₁₂/T − η and correlations. Results showed that the He-Yu correlation has the best prediction performance while the D₁₂/T − η correlation best fits the data with AAD% < 8%.