José P.B. Mota

Thermodynamics of adsorption of light alkanes and alkenes in single-walled carbon nanotube bundles

The thermodynamics of adsorption of light alkanes and alkenes (CH4, C2H6, C2H4, C3H8, and C3H6) in single-walled carbon nanotube bundles is studied by configurational-bias grand canonical Monte Carlo simulation. The bundles consist of uniform nanotubes with diameters in the range 11.0 < D (A) < 18.1, arranged in the usual close-packed hexagonal lattice. The phase space is systematically analyzed with calculations for adsorption at room temperature and reduced pressure range of 8.7 x 10-9 < (p/p0) < 0.9. The simulation results are interpreted in terms of the molecular nature of the adsorbate and the corresponding solid-fluid interactions. It is shown that confinement in the internal volume of the bundle (interstitial and intratubular) is energetically more favorable than physisorption on the external surface (grooves and exposed surfaces of peripheral tubes), as indicated by the curves of isosteric heat as a function of reduced pressure. However, the zero-loading properties suggest a crossover point to this behavior for D = 18 - 19 A. When interstitial confinement is not inhibited by geometrical considerations, it is possible to establish the following ordering of the zero-loading isosteric heat by type of adsorption site.

Natural convection heat transfer in horizontal eccentric elliptic annuli containing saturated porous media

The two-dimensional Darcy‐Boussinesq equations, governing natural convection heat transfer in a saturated porous medium, are solved in generalised orthogonal coordinates, using high-order compact finites diAerences on a very fine grid. The mesh is generated numerically using the orthogonal trajectory method. The code is thoroughly validated against results reported in the literature for concentric and eccentric cylinders, obtained using diAerent numerical techniques. The code is applied to horizontal eccentric elliptic annuli containing saturated porous media. The judicious stretching of one of the annular walls in the horizontal direction reduces the heat losses with respect to a concentric cylindrical annulus with the same amount of insulating material. The savings in heat transfer can be further improved if the elliptic annular shape is made eccentric. Previous studies show that, under certain conditions, eccentric cylinders may lead to a more eAective insulation than concentric ones. The results presented here provide an alternative approach to optimising the heat transfer rate by a proper choice of the annular shape. The energy savings are of the order of 10%. 7 2000 Elsevier Science Ltd. All rights reserved.

Simulation of a new hybrid membrane/pressure swing adsorption process for gas separation☆

A new hybrid gas separation process combining membrane permeation and pressure swing adsorption (PSA) is presented. An integrated model was formulated which successfully predicts all process characteristics. Our modeling work shows that the coupled process increases the efficiency of the pressurization and high-pressure adsorption steps, thereby improving the separation performance as compared to a standalone PSA. The new process has been applied successfully to the bulk separation of a mixture of 50/50 H 2 /CH 4 and preliminary results have been obtained for CO 2/ CH 4 and H 2 /CO 2 /CH 4 mixtures.

Dynamic modelling of an adsorption storage tank using a hybrid approach combining computational fluid dynamics and process simulation

Abstract A computational fluid dynamics (CFD) software package has been coupled with the dynamic process simulator of an adsorption storage tank for methane fuelled vehicles. The two solvers run as independent processes and handle non-overlapping portions of the computational domain. The codes exchange data on the boundary interface of the two domains to ensure continuity of the solution and of its gradient. A software interface was developed to dynamically suspend and activate each process as necessary, and be responsible for data exchange and process synchronization. This hybrid computational tool has been successfully employed to accurately simulate the discharge of a new tank design and evaluate its performance. The case study presented here shows that CFD and process simulation are highly complementary computational tools, and that there are clear benefits to be gained from a close integration of the two.

Regioselective competitive adsorption of water and organic vapor mixtures on pristine single-walled carbon nanotube bundles.

Sequential adsorption of water and organic vapor mixtures onto single-walled carbon nanotube (SWNT) bundles is studied experimentally and by grand canonical Monte Carlo (GCMC) simulation to elucidate the distinct interactions between select adsorbates and the nanoporous structure of SWNTs. Experimental adsorption isotherms on SWNT bundles for hexane, methyl ethyl ketone, cyclohexane, and toluene individually mixed in carrier gases that were nearly saturated with water vapor are compared with the GCMC-simulated isotherms for hexane, as a representative organic, on the external surface of the heterogeneous SWNT bundles. From the nearly perfect overlap between the experimental and simulated isotherms, it is concluded that until near saturation only the internal pore volume of pristine SWNT bundles fills with water. The adsorption of water vapor on the peripheral surface of the bundles remains insignificant, if not negligible, in comparison to the adsorption of water in the internal volume of the bundles. This is in contrast with the adsorption of pure hexane, which exhibits appreciable adsorption both inside the bundles and on their external surface. It is also suggested that during competitive adsorption, water molecules take precedence over small nonpolar and polar organic molecules for adsorption inside SWNTs and leave unoccupied the hydrophobic external surface of the bundles for other more compatible adsorbates.

Streamlined, two-column, simulated countercurrent chromatography for binary separation

We report on a numerical and experimental study of two-column versions of streamlined, multicolumn, semi-continuous chromatography for binary separation. The systems combine a flexible node design, cyclic flow-rate modulation, and relayed operation of the inlet/outlet ports to extend the mass-transfer zone over the largest possible length, while keeping it inside the system at all times. One advantage of these streamlined designs is the simplicity of their physical realization: regardless of the number of columns, they only require two pumps to supply feed and desorbent into the system, while the flow rates of liquid withdrawn from the system are controlled by material balance using simple two-way valves. In one case, an extra pump is needed to recirculate the fluid in closed-loop. A rigorous model-based optimization approach is employed in the optimal design of the cycles to generate solutions that are physically realizable in the experimental set-ups. The optimized schemes for two-column operation supply fresh feed into the middle of the system where the composition of the circulating fluid is closest to that of the feedstock fluid, and recover the purified products, extract and raffinate, alternately at the downstream end of the unit, while desorbent is continuously supplied into the upstream end of the system. By internally recycling part of the non-pure cut fraction, the scheme with a step of closed-loop recycling significantly reduces its solvent consumption. The feasibility and effectiveness of the reported two-column processes have been verified experimentally on the linear separation of nucleosides by reversed phase subject to 99% purity constraints on both products. It is shown that our processes compare favorably against single-column batch chromatography, steady-state recycling, and four-column, open-loop SMB, for the same amount of adsorbent; they are also better than the four-column, closed-loop SMB at high feed throughputs.

Adenovirus purification by two-column, size-exclusion, simulated countercurrent chromatography.

Adenovirus serotype 5 (Ad5) was successfully separated by size-exclusion chromatography (SEC) using a simple, yet efficient, two-column, quasi-continuous, simulated moving-bed process operated in an open-loop configuration. The operating cycle is divided into two identical half-cycles, each of them consisting of the following sequence of sub-steps: (i) elution of the upstream column and direction of the effluent of the downstream column to waste; (ii) elution of the upstream column and redirection of its effluent to waste while the downstream column is fed with the clarified bioreaction bulk and its effluent collected as purified product; (iii) operation of the system as in step (i) but collecting the effluent of the downstream column as product; (iv) elution of the upstream column and direction of its effluent to waste while the flow through the downstream column is temporarily halted. Clearance of impurities, namely DNA and host cell protein (HCP), were experimentally assessed. The pilot-scale run yielded a virus recovery of 86%, and a clearance of 90% and 89% for DNA and HCP, respectively, without any fine tunning of the predetermined operating parameters. These figures compare very favorably against single-column batch chromatography for the same volume of size-exclusion resin. However, and most importantly, the virus yield was increased from 57% for the batch system to 86% for the two-column SEC process because of internal recycling of the mixed fractions of contaminated Ad5, even though the two-column process was operated strictly in an open-loop configuration. And last, but not least, the productivity was increased by 6-fold with the two-column process. In conclusion, the main drawbacks of size-exclusion chromatography, namely low productivity and low product titer, were overcome to a considerable extent by an innovative two-column configuration that keeps the mixed fractions inside the system at all times.

Chiral separation by two-column, semi-continuous, open-loop simulated moving-bed chromatography.

A two-column version of a multicolumn, semi-continuous, open-loop chromatograph for chiral separation is presented and validated experimentally. The heart of the process is a flexible node design and cyclic flow-rate modulation that succeed at keeping the mass-transfer zone inside the system without resorting to any recycling technique. One advantage of this streamlined design is the simplicity of its physical realization: regardless of the number of columns, it only requires two pumps to supply feed and desorbent into the system, while the flow rates of liquid withdrawn from the system are controlled by material balance using simple two-way valves. A rigorous model-based optimization approach is employed in the optimal cycle design to generate a solution that is physically realizable in the experimental apparatus. The optimized scheme for two-column operation supplies fresh feed into the system where the composition of the circulating fluid is closest to that of the feedstock fluid, and recovers the purified products, extract and raffinate, alternately at the downstream end of the unit while desorbent is supplied into the upstream end of the system. The feasibility and effectiveness of the two-column process are verified experimentally on the separation of reboxetine racemate, a norepinephrine re-uptake inhibitor, under overloaded conditions. Our set-up employs an automated on-line enantiomeric analysis system, comprising an analytical HPLC set-up with two UV detectors to monitor the composition profile at the downstream end of one of the columns; this monitoring system does not use a polarimeter.

A new multicolumn, open-loop process for center-cut separation by solvent-gradient chromatography.

A comprehensive description of a new process--the GSSR (Gradient with Steady State Recycle) process--for center-cut separation by solvent-gradient chromatography is provided, highlighting its versatility, flexibility, and ease of operation. The GSSR process is particularly suited for ternary separation of bioproducts: it provides three main fractions or cuts, with a target product contained in the intermediate fraction. The process comprises a multicolumn, open-loop system, with cyclic steady state operation, that simulates a solvent gradient moving countercurrently with respect to the solid phase. However, the feed is always injected into the same column and the product always collected from the same column as in a batch process; moreover, both steps occur only once per cycle. The GSSR process was experimentally validated in a pilot unit, using the purification of a crude peptide mixture by reversed phase as a proof of concept; the crude mixture is roughly 50% pure and some of its impurities have isocratic retention times very close to that of the target peptide. Experimental results are reported in terms of cyclic steady-state profiles and process performance indicators, which include product purity and yield. A simplified model-based approach, which uses only a few key components of the crude mixture, is employed to assist in the explanation of the process operation. By dynamically adjusting the switching interval while the process is running, to correctly position the composition profile with respect to the outlet ports, pure product satisfying the target specifications--98% purity and 95% recovery--was obtained under stable operation in the pilot unit.

On the optimization of mixing protocol in a certain class of three-dimensional Stokes flows

Mixing in a special class of three-dimensional, non-inertial periodic flows is studied numerically. In the type of flow considered here, the cross-sectional velocity components are independent of the axial flow and the axial flow is independent of the axial coordinate. Using the eccentric helical annular mixer as a prototype, we consider the counter-rotating case with steady rotation of the outer cylinder and sinusoidal modulation of the inner one. Apart from the mixer geometry, the behavior of the system is governed by two dimensionless parameters obtained by scaling the cross-sectional stirring protocol with respect to the characteristic residence time of the fluid in the mixer. The first parameter is related to the average number of turns of the outer cylinder and the second one is related to the average number of modulation periods of the inner cylinder. The convection-diffusion equation is solved numerically, with temperature as a passive scalar, at high Peclet number. For a given three-dimensional mixer geometry and axial flow rate we show that there is an optimum modulation frequency for which the exit standard deviation of the temperature field is a minimum. Lagrangian simulations at infinite Peclet number and the use of other tools to study mixing, such as stretching calculations and tracer tracking methods, confirm that the optimized protocol does result in very effective mixing.