Methanation of carbon dioxide by hydrogen reduction using the Sabatier process in microchannel reactors

This paper describes the development of a microchannel-based Sabatier reactor for applications such as propellant production on Mars or space habitat air revitalization. Microchannel designs offer advantages for a compact reactor with excellent thermal control. This paper discusses the development of a Ru-TiO₂-based catalyst using powdered form and its application and testing in a microchannel reactor. The resultant catalyst and microchannel reactor demonstrates good conversion, selectivity, and longevity in a compact device. A chemically reacting flow model is used to assist experimental interpretation and to suggest microchannel design approaches. A kinetic rate expression for the global Sabatier reaction is developed and validated using computational models to interpret packed-bed experiments with catalysts in powder form. The resulting global reaction is then incorporated into a reactive plug-flow model that represents a microchannel reactor.     

Synthesis of -leucine nanoparticles via physical vapor deposition at varying saturation conditions

Preparation of L-leucine nanoparticles by a process based on physical vapor deposition has been presented. In an aerosol flow reactor method, aqueous L-leucine droplets were first dried followed by the sublimation of L-leucine to produce vapor that upon vapor deposition resulted in L-leucine nanoparticles with size ranging from 40 to 200 nm. Onset temperature for the sublimation of L-leucine at concentrations from 0.02 to increased from 135 to , respectively. The formation of nanoparticles was initiated in three different ways: (i) via droplet drying, (ii) via heterogeneous nucleation of L-leucine vapor on solid L-leucine particles, and (iii) via homogeneous nucleation of L-leucine vapor to form new-born nanoparticles. Consequently, the saturation conditions of L-leucine vapor in the reactor determined the resulting particle size, size distribution and number concentration, those depending very much on nucleation mode. In general, the both nucleation modes produced narrow size distributions, that is, geometric standard deviation (GSD) was <1.8 although the number concentration increased with the increased amount of L-leucine vapor. Upon desublimation and vapor deposition, L-leucine formed leafy crystals whose size was the largest when produced from the heated section at the vicinity of the onset temperature and the smallest far above the onset temperature. All the particles prepared in the conditions (i)–(iii) were crystalline. However, X-ray diffraction analysis showed preferential direction for crystal growth according to the way of particle formation.     

Kinetic analysis of NO-sensitized methane oxidation

The role of NO-sensitized oxidation during the product-gas entrainment of a low-NO_x, multi-jet, natural gas burner is investigated. A detailed kinetic mechanism for the NO-sensitized oxidation of CH₄, consisting of 483 reactions and 69 species, is used for the kinetic analysis. An eigenvalue-eigenvector decomposition is performed on normalized sensitivity coefficients to study the important reactions using principal component analysis (PCA), and the loadings corresponding to the largest eigenvalue are used to identify the reaction pathways of NO-sensitized oxidation. The main reaction pathway is most strongly affected by the temperature profile and equivalence ratio. Also, a reduced kinetic scheme of 110 reactions and 47 species is developed by eliminating reactions with small loadings. The temporal evolution of reactions is investigated using functional PCA, in which the functional loadings reflect the importance of reactions as a function of time. A discretization approach is used to perform the functional PCA.     

Decomposition of methane in the presence of carbon dioxide over Ni catalysts

Methane decomposition was carried out in the presence of CO₂ over the nickel catalysts. Spherical alumina and glycothermally synthesized zirconia were used as the catalyst supports. In the presence of CO₂, CH₄ was decomposed in the same fashion as pure methane decomposition, and fibrous carbons were formed. However, the formation of hydrogen, carbon monoxide, and water continued even after the apparent carbon formation ceased, and this phenomenon was observed irrespective of the support materials. These results showed a sharp contrast against the results for the pure methane decomposition where the catalyst was completely deactivated when the carbon formation ceased. Further carbon formation was observed when the feed gas containing CO₂ was replaced with pure CH₄. Mechanisms for these phenomena are discussed from the thermodynamical point of view.     

The effect of specific surface area on the activity of nano-scale ceria catalysts for methanol decomposition with and without steam at SOFC operating temperatures

Nano-particulate high surface area CeO₂ was found to have a useful methanol decomposition activity producing H₂, CO, CO₂, and a small amount of CH₄ without the presence of steam being required under solid oxide fuel cell temperatures, 700-1000 °C. The catalyst provides high resistance toward carbon deposition even when no steam is present in the feed. It was observed that the conversion of methanol was close to 100% at 850 °C, and no carbon deposition was detected from the temperature programmed oxidation measurement.The reactivity toward methanol decomposition for CeO₂ is due to the redox property of this material. During the decomposition process, the gas-solid reactions between the gaseous components, which are homogeneously generated from the methanol decomposition (i.e., CH₄, CO₂, CO, H₂O, and H₂), and the lattice oxygen on ceria surface take place. The reactions of adsorbed surface hydrocarbons with the lattice oxygen ( can produce synthesis gas (CO and H₂) and also prevent the formation of carbon species from hydrocarbons decomposition reaction (C_nH_m⇔nC+m/2H₂). V_O^·· denotes an oxygen vacancy with an effective charge 2⁺. Moreover, the formation of carbon via Boudouard reaction (2CO⇔CO₂+C) is also reduced by the gas-solid reaction of carbon monoxide with the lattice oxygen .At steady state, the rate of methanol decomposition over high surface area CeO₂ was considerably higher than that over low surface area CeO₂ due to the significantly higher oxygen storage capacity of high surface area CeO₂, which also results in the high resistance toward carbon deposition for this material. In particular, it was observed that the methanol decomposition rate is proportional to the methanol partial pressure but independent of the steam partial pressure at 700-800 °C. The addition of hydrogen to the inlet stream was found to have a significant inhibitory effect on the rate of methanol decomposition.     

Assessment of a redox alkaline/iron-chelate absorption process for the removal of dilute hydrogen sulfide in air emissions

The oxidative absorption of hydrogen sulfide (H₂S) into a solution of ferric chelate of trans-1,2- diaminocyclohexanetetraacetate (CDTA) was studied in a counter-current laboratory column randomly packed with 15 mm plastic Ralu rings. The present investigation takes concern about the Kraft pulping situation where dilute H₂S concentrations are omnipresent in large-volume gas effluents. A fractional two-level factorial approach was instigated to determine the significance of six operating variables, namely the solution's alkalinity (pH; 8.5-10.5), the liquid mass flow rate (L;1.73-), the solution's ionic strength (I_C;0.01-), the gas mass flow rate (G;0.19-), the inlet H₂S concentration (C_H2S,0;70-430 ppm) and the initial ferric CDTA concentration (C_Fe,0;100 -). Initially, a Plackett-Burman design matrix of seven duplicated experiments revealed that pH is the leading factor controlling the H₂S conversion rate while the ionic strength and ferric CDTA concentration effects remained negligible within the factorial domain. Surface response analysis based on 11 duplicated factorial experiments plus 10 central composite trials revealed that the H₂S conversion significantly increases with liquid flow rate but decreases with growing H₂S load up. Further examination about the influence of ferric CDTA on H₂S absorption rate was set up over a broader concentration range (C_Fe,0;0- at pH of 9.5 and 10.5. It showed good potential at as H₂S conversion increased by a significant 25% for both pH values in comparison to pure alkaline solutions containing no ferric CDTA.     

Systematics of salt precipitation in complexes of polyethylene oxide and alkali metal iodides

Conductivity measurements in PEO₃₀MI polymer electrolytes with M=Li, Na, K, Rb, or Cs over the temperature range from about 65 to 200 °C show an increasing tendency for salt precipitation with increasing cation size. The salt precipitation in these complexes upon heating is revealed by the decrease of the dc conductivity starting at a critical temperature T_c. Whereas LiI and NaI complexes do not show precipitation effects, T_c monotonically decreases from about 140 to 65 °C when changing the salt component from KI via RbI to CsI. For the PEO-RbI system, precipitation is further investigated by nuclear magnetic resonance (NMR) and tracer diffusion experiments. NMR analysis unambiguously demonstrates the onset of RbI salt precipitation and the increase of the precipitate fraction with increasing temperature. In diffusion experiments on PEO₃₀RbI with the radiotracers and , the precipitation effect is manifested by anomalous features in the penetration profiles, however, without noticeable changes in their depth range. Combining the resulting tracer diffusion coefficients with the dc conductivity data enables us to assess crucial parameters characterizing ionic transport in PEO₃₀RbI.     

Characterization of flow phenomena induced by ultrasonic horn

Mean flow and turbulence parameters have been measured using laser Doppler anemometer (LDA) in ultrasound reactor. The effects of the ultrasonic power have been investigated over a power density (P/V) range of 15-. The liquid circulation velocities are dominant in the zone nearer to the source of energy and are substantially low at the walls and at the bottom of the reactor. The levels of turbulence kinetic energy and dissipation rate are high near the horn and decrease rapidly with increasing distance from the horn. Average turbulent normal stresses are larger than the turbulent shear stresses. However, they are much lower than stirred reactors when compared at the same power consumption per unit mass. Comparisons of LDA measurements and computational fluid dynamics (CFD) predictions have been presented. The good agreement indicates the validity of the CFD model. The flow information has been extended for the prediction of mixing time. For uniform mixing in ultrasound-assisted reactors, optimum power density and diameter of the vessel is needed, yet it is far less effective than conventional stirred vessel. The possibility of optimization has been suggested in terms of power dissipation and the vessel size.     

Wet 2,4,6-trichloro[1,3,5]triazine (TCT) an efficient catalyst for synthesis of -bis(substituted-benzylidene) cycloalkanones under solvent-free conditions

An array of aromatic aldehydes undergo crossed aldol condensation with ketones in the presence of catalytic amounts of wet-TCT under solvent-free conditions to afford the corresponding α,α^′-bis(substituted-benzylidene) cycloalkanones in excellent yields. Contrary to the existing methods, which use classical Lewis acids a new catalyst (TCT) is employed. This method is also general with respect to all types of aromatic aldehydes and is an eco friendly procedure.     

Enhanced hydrogen production from biomass with in situ carbon dioxide capture using calcium oxide sorbents

The steam gasification of biomass, in the presence of a calcium oxide (CaO) sorbent for carbon dioxide (CO₂) capture, is a promising pathway for the renewable and sustainable production of hydrogen (H₂). In this work, we demonstrate the potential of using a CaO sorbent to enhance hydrogen output from biomass gasifiers. In addition, we show that CaO materials are the most suitable sorbents reported in the literature for in situ CO₂ capture. A further advantage of the coupled gasification-CO₂ capture process is the production of a concentrated stream of CO₂ as a byproduct. The integration of CO₂ sequestration technology with H₂ production from biomass could potentially result in the net removal of CO₂ from the atmosphere.Maximum experimental H₂ concentrations reported for the steam gasification of biomass, without CO₂ capture, range between 40%-vol and 50%-vol. When CaO is used to remove CO₂ from the product gas, as soon as it is formed, we predict an increase in the H₂ concentrations from 40%-vol to 80%-vol (dry basis), based on thermodynamic modelling and previously published data.We examine the effect of key variables, with a specific focus on obtaining fundamental data relevant to the design and scale-up of novel biomass reactors. These include: (i) reaction temperature, (ii) pressure, (iii) steam-to-biomass ratio, (iv) residence time, and (v) CO₂ sorbent loading. We report on operational challenges related to in situ CO₂ capture using CaO-based sorbents. These include: (i) sorbent durability, (ii) limits to the maximum achievable conversion and (iii) decay in reactivity through multiple capture and release cycles. Strategies for enhancing the multicycle reactivity of CaO are reviewed, including: (i) optimized calcination conditions, and (ii) sorbent hydration procedures for reactivation of spent CaO. However, no CaO-based CO₂ sorbent, with demonstrated high reactivity, maintained through multiple CO₂ capture and release cycles, has been identified in the literature. Thus, we argue that the development of a CO₂ sorbent, which is resistant to physical deterioration and maintains high chemical reactivity through multiple CO₂ capture and release cycles, is the limiting step in the scale-up and commercial operation of the coupled gasification-CO₂ capture process.     

Gas mass transfer to AOT-based microemulsions

The present paper analyses the gas/liquid mass transfer process employing carbon dioxide as gas phase and ternary water in oil microemulsions as absorbent liquid phases. The liquid phases were obtained by a direct mixing of water, 2,2,4-trimethylpentane and sodium bis(2-ethylhexyl)sulfosuccinate (Aerosol OT). The characteristics of the microemulsions employed as liquid phase have been analysed to interpret the experimental results observed in the absorption process. More specifically, they have been analysed in relation to the percolation phenomenon and the effects produced by this phenomenon upon the different physical properties. Characteristic results have been observed for the gas/liquid mass transfer using microemulsions, because ternary microemulsions with high viscosity values in relation to pure water show a faster absorption process than the carbon dioxide/water system. This characteristic behaviour has been explained on the basis of the microemulsions internal dynamics.     

Dynamic modeling and simulation of absorption of carbon dioxide into seawater

In order to elucidate the dynamic performance of the CO₂ ocean disposal process, effects of operating parameters, such as gas flow rate, salinity and temperature, on the absorption of CO₂ into seawater were examined. The rate-based model consisting of the rates of chemical reaction and gas-liquid mass transfer was developed for simulating dynamic process of CO₂ ocean disposal. In modeling, non-ideal mixing characteristics in the gas and liquid phases are described using a tanks-in-series model with backflow. Experiments were performed to verify dynamic CO₂ absorption prediction capability of the proposed model in a cylindrical bubble column. The operation was batch and continuous with respect to liquid phase and gas phase, respectively. Experimental results indicate that the CO₂ gas injection rate increased the absorption rate but the increase in salinity concentration caused inhibition of the absorption of CO₂. The proposed model could describe the present experimental results for the dynamic changes and the steady-state values of dissolved CO₂ concentration and hydrogen ion concentration. The proposed model might effectively handle the prediction of the absorption of CO₂ into seawater in the CO₂ ocean disposal.     

Intrinsic kinetics of the oxidative reaction of dichloroacetic acid employing hydrogen peroxide and ultraviolet radiation

In a previous work it has been shown that the combination of H₂O₂ and low wavelength UV radiation is a suitable process for degrading dichloroacetic acid (DCA). The final result provided a validated and complete reaction scheme. That proposal included two possible ways for the hydroxyl radical to react with DCA [Zalazar, C., Labas, M., Brandi, R., Cassano, A., 2007. Dichloroacetic acid degradation employing hydrogen peroxide and UV radiation. Chemosphere 66, 808-815].This work was directed to a single objective: to derive, from the previous reaction sequence, a mathematical model able to represent the kinetics of DCA oxidation and validate its predictive quality with experiments. This representation of the reaction must include all the required variables for an ulterior reactor design and scale-up and, consequently, the kinetic model parameters must be independent of the shape, size and configuration of the laboratory reactor.Working with a complete set of experimental runs that included all the involved variables, the unknown kinetics parameters of the DCA degradation were obtained by comparing predicted concentrations by the model (represented by a set of two ordinary differential equations and two algebraic equations coupled with a mass and a radiation balance inside the reactor) with the experimental values, employing a multi-parameter non-linear regression analysis. Experimental values confirmed the validity of the proposed mechanism. Additionally, an optimal concentration ratio of hydrogen peroxide with respect to DCA was obtained (r=CH₂O₂/C_DCA≈8).The intermediate results of the numerical solution of the complete system of differential and algebraic equations representing the proposed complete reaction mechanism were useful to find simplified, analytical expressions for the reaction rates of DCA and H₂O₂. The obtained rates resulting from these simplifications were compared with those of the complete system showing a very satisfactory concordance. This outcome is, at the same time, a clear indication of the significant influence of the radical in the reaction evolution.     

Optimization of the cathode geometry in polymer electrolyte membrane (PEM) fuel cells

A nonlinear constrained optimization procedure is used in the cathode design in order to maximize the average current density at a fixed voltage in a polymer electrolyte membrane (PEM) fuel cell with interdigitated fuel/air distributors. The operation of the PEM fuel cell is studied using a steady-state, two-phase, two-dimensional electro-chemical model. The following geometrical parameters of the cathode are considered: the thickness, and length per one shoulder of the interdigitated air distributor and the length of the shoulder. The optimization results obtained show that within manufacturability controlled lower and the space-limitation controlled upper bounds of these parameters, the optimal-cathode design corresponds to the lower bounds in the cathode length per one shoulder of the interdigitated air distributor and the fraction of the length associated with the shoulders and at a low (but larger than the lower bound) value of the cathode thickness. These findings are explained using an analogy with the effect of pipe dimensions on the fluid flow through a pipe and by considering the role of forced convection on the oxygen transport to the membrane/cathode interface.     

Formation and behavior of composite CO2 hydrate particles in a high-pressure water tunnel facility

Sinking CO₂ composite particles consisting of seawater, liquid CO₂, and CO₂ hydrate were produced by a coaxial flow injector fed with liquid CO₂ and artificial seawater. The particles were injected into a high-pressure water tunnel facility to permit determination of their settling velocities and dissolution rates. Injections were performed at fixed pressures approximately equivalent to 1200-m, 1500-m, and 1800-m depths and at temperatures varying from approximately 2 to 5 °C. Immediately after injection, the cylindrical particles were observed to break away from the injector tip and often aggregated into sinking clusters. The seawater flow in the tunnel was then adjusted in a countercurrent flow mode to suspend the particles in an observation window so that images of the particles could be recorded for later analysis. The flow would often break or cause rearrangement of some of the clusters. Selected individual particles and some clusters were studied until they became too hydrodynamically unstable to follow. In general, the flow required to suspend clusters or individual particles decreased with time as the particles dissolved. For example, one particle was produced and observed for over 6 min at an average pressure of 15.022 MPa and an average temperature of 5.1 °C. Its sinking rate, determined from the flow required for stabilization, changed from 37.2 to 3.3 mm/s over this time. Particle sinking rates were compared to correlations from the literature for uniform cylindrical objects. Reasonable agreement was observed for short times; however, the observed decrease in sinking velocity with time was greater than that predicted by the correlations for longer times. Particle dissolution rates, based on changes in diameter, were also determined and varied from 5 to . A pseudo-homogeneous mass transfer model was used to predict single-particle dissolution rates. Good agreement was achieved between experimental dissolution data and the modeling results.     

Kinetics of absorption of carbon dioxide into aqueous blends of 2-(1-piperazinyl)-ethylamine and N-methyldiethanolamine

The kinetics absorption of CO₂ into aqueous blends of 2-(1-piperazinyl)-ethylamine (PZEA) and N-methyldiethanolamine (MDEA) were studied at 303, 313, and 323 K using a wetted wall column absorber. The PZEA concentrations in the blends with MDEA varied from 0 to to see the effect of PZEA as an activator in the blends with two different total amine concentrations (1.0 and ). Based on the pseudo-first-order condition for the CO₂ absorption, the overall second-order reaction rate constants were determined from the kinetic measurements. The kinetic rate parameters were calculated and presented at each experimental condition.     

Hydrodynamics characterization of the Maxblend impeller

The hydrodynamic characteristics of the Maxblend^TM impeller have been investigated in the case of viscous Newtonian fluids. Both laboratory experiments and 3D finite element based computational fluid dynamics (CFD) simulations have been carried out. The power consumption, the mixing evolution yielding the mixing time, and the effect of baffles in the laminar and transition flow regimes have been determined. It was found that the limit Reynolds number between the laminar and transition regimes is approximately 25 and 38 for the unbaffled and baffled configurations, respectively. Based on the range of Reynolds numbers studied in this work, the best window performance of the Maxblend^TM mixer where fast and homogenous mixing is achieved is the end of the laminar regime and the early transition regime with baffles.     

Modeling of a 120 kW chemical looping combustion reactor system using a Ni-based oxygen carrier

A modeling tool for the investigation of chemical looping combustion (CLC) in a dual circulating fluidized bed (DCFB) reactor system is introduced. CLC is a novel combustion process with inherent CO₂ separation, consisting of two fluidized bed reactors, an air reactor (AR) and a fuel reactor (FR). A solid oxygen carrier (OC) that circulates between the reactors, transports the necessary oxygen for the combustion. In the DCFB concept both AR and FR are designed as circulating fluidized beds (CFBs). Each CFB is modeled using a very simple structure in which the reacting gas is only in contact with a defined fraction of the well mixed solids. The solids distribution along the height axis is defined by a void fraction profile. Different parameters that characterize the gas-solids contact are merged into only one parameter: the fraction of solids exposed to the gas passing in plug flow (φ_s,core). Using this model, the performance of the 120 kW DCFB chemical looping combustor at Vienna University of Technology is investigated. This pilot rig is designed for a Ni-based OC and natural gas as fuel. The influence of the reactor temperatures, solids circulation rate, air/fuel ratio and fuel power are determined. Furthermore, it is shown that with the applied kinetics data, the OC is only fully oxidized in the AR when the AR solids inventory is much larger than the FR solids inventory or when both reactors are very large. To compare different reactor systems, the effect of the solids distribution between AR and FR is studied and both gas and solids conversions are reported.     

Robust control of a reverse-flow reactor

This paper is focused on the design of a robust controller for a catalytic fixed-bed reactor with periodical inversion of the flow direction (reverse-flow reactor, RFR). The analogy between the RFR operated at infinite switching frequency and the countercurrent reactor is the basis of the simplified mathematical model of the reactor.The control system uses dilution and internal electric heating to ensure complete conversion of the reactants and to prevent overheating of the catalyst. As the state of the system is not fully available, apart from some temperature measurements, an observer is designed and used in the control algorithm. This is a typical case of nonlinear system with uncertainties. Following the procedure described in detail by Fissore [2008. Robust control in presence of parametric uncertainties: observer-based feedback controller design. Chemical Engineering Science, in press, doi:10.1016/j.ces.2007.12.019.], the extended model for the process is setup, thus taking into account all the simplifications of the model and linking performance and robustness to the control law, which is a simple state feedback. Simulations with randomly varying feeding concentration have been carried out in order to demonstrate the effectiveness of the proposed control system.