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# CHAPTER FIVE

Convective transport at low & high pressure. Free convection effects in Supercritical Fluids

PARTICLE-TO-FLUID MASS & HEAT TRANSFER

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**Fernando Pessoa (1888 – 1935)
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Chapter Five

One of the most important parameters needed in the design of packed bed systems is the particle-to-fluid transport coefficients. In the past six decades, a substantial amount of work has been devoted to the study of these parameters. Particle-to-fluid mass transfer studies were first carried out by Gamson et al. (1943), and Hurt (1943). They obtained mass transfer coefficients from measurements of the rates of evaporation of water from wet porous particles. Hurt (1943) also reported mass transfer coefficients derived from the measurement of rates of naphthalene sublimation. Since their pioneering work, a large number of experimental studies have been carried out on mass transfer coefficients in packed bed systems. Theoretical work has also been in progress. Pfeffer (1964) and Pfeffer and Happel (1964) applied a free surface cell model to the creeping flow region. LeClair and Hamielec (1968, 1970) proposed a zero vorticity cell model, and El-Kaissy and Homsy (1973) applied the free surface cell model, zero vorticity cell model and distorted cell model to a multiparticle system at low Reynolds number. Nishimura and Ishii (1980) also applied the free surface cell model to the study of mass transfer at high Reynolds numbers. These models which are based on different assumptions, generally give different and inconsistent values of particle-to-fluid mass transfer coefficients. Therefore, theoretical prediction of mass transfer coefficients is far from satisfactory. For the design and analysis of packed bed catalytic reactors, it is necessary to know the temperatures of the fluid and the catalyst particles in which the chemical reactions are taking place. In general, fluid temperature is measured with little difficulty, but the measurement of the solid surface temperature is not easy. This is particularly true of packed bed reactors. The particle temperature or temperature drop at the particle surface then has to be estimated in terms of the heat transfer coefficient between the particle and the fluid. Because of the importance of the particle-to-fluid heat transfer coefficient in packed bed reactors, a considerable effort has been made to evaluate this parameter. Experimental determinations of heat transfer coefficients for a wide variety of systems have been made using various experimental techniques, under either steady-state or unsteady-state conditions. An extensive review on experimental/theoretical works on particle-to-fluid mass and heat transfer can be found in Wakao and Kaguei (1982). Although there is broad information available of published experimental data for particle-tofluid forced convection heat and mass transfer at low pressure (see e.g. Wakao and Kaguei, 1982), scarce data are available for high pressure situations or supercritical packed bed reactors. Many authors have studied catalytic reactions using a supercritical fluid as a solvent (Poliakoff et al., 1996; Ramirez et al., 2004), but main interest has been centered in kinetics of chemical reactions under supercritical conditions. Other authors have studied mass transfer in packed beds under supercritical conditions applied to supercritical extraction (Debenedetti and Reid, 1986; Stüber et al., 1996). The recent study and development of new compact packed bed supercritical nuclear reactors opens a branch for the study of heat transfer phenomena under high pressure conditions (see e.g. Oka et al., 1994). In the following sections, analytical solutions of the steady-state temperature and composition profiles in a packed bed will be shown. In addition, a CFD simulation strategy for the estimation of forced convection mass and heat transfer coefficients at low pressure is discussed. Estimated transport parameters are compared to broadly accepted correlations. Mixed convection mass and heat transfer at high pressure is modeled and analyzed, and numerical results obtained are compared to previously published experimental data (Stüber et al., 1996), and a correlation for predicting heat transfer parameters in a supercritical packed bed reactor is presented (Guardo et al., 2006). The obtained numerical results validates the idea that the modified correlation presented by Guardo et al. (2006) can be used to describe heat transfer

- 93 -

013 – 0.1. Details on the dimensionless numbers used can be found in Appendix C.5 x 10 – 7. mass.100 - Heat transfer simulations Circulating fluid Temperature at the inlet. Results of the order of magnitude of the dimensionless groups are shown in Table 5. justified in the fact that majority of experimental results shows a range of variations between 0.132 - Boundary (operating) conditions for analyzed cases In the case of particle-to-fluid transport at low pressure. In energy and species balances.75 < Prt < 2 for air and water (Kays. 1991). . mesh design and CFD modeling To properly design a mesh capable of capturing the transport mechanisms present in the study in detail. For first analysis purposes. dimensionless analysis allows identifying the problem as forced convection in laminar or turbulent flow. momentum.1.015 – 0.2 x 106 0. mol/m3 C7H8 concentration at particle surface (equilibria). mol/m3 Pressure. the convective and the diffusive term become important for the balances. 5. Boundary (operating) conditions for each analyzed situation are shown in Table 5. Yaws. Prt was assumed as a constant value within the bed. Pa Mass flow at the inlet. Poling et al.95 101325 -4 7. kg/m2· s Velocity at the inlet. Pa Mass flow at the inlet. Reynolds analogy was used to estimate values of Prt from Ret (White. Air 298 423 101325 -4 3 x 10 – 7. Inertial gravity forces increase their contribution as Re decreases.5 x 10-1 CO2 330 340 1 x 107 0. The dimensionless equations corresponding to continuity. Reynolds number was calculated using particle diameter as characteristic length. Boundary condition Circulating fluid C7H8 concentration at inlet.. m/s Low pressure High pressure Mass transfer simulations CO2 0 5.94 - .5 x 10-1 120 – 190 9 – 9.2. For both balances. and pressure drop together with turbulent forces become the most important terms in the momentum balance at high Re.Chapter Five phenomena in a supercritical packed bed reactor under mixed convection regime at high pressures. For the momentum balance it becomes clear that viscous forces decrease their contribution as Re increases. 1987. 1999. 2000). and energy balances are detailed in Chapter two. m/s Table 5. K Pressure..1. Geometry. K Temperature at the particle surface. The orders of magnitude of the dimensionless groups were estimated by taking physical-chemical property values for air from experimental data and empirical correlations available in the literature (Reid et al. steady state analysis can be used. 1994). a dimensionless analysis of Navier-Stokes equations under simulation conditions was developed. kg/m2· s Velocity at the inlet.

a 44 spheres stacking with a sphere-to-tube diameters ratio of 3. the fluid was taken to be Newtonian.x. For the high pressure simulations.100 10-1 100 10-8 .2. power law for viscosity and appropriated mixing rules were applied to the model for making these variables temperature and composition dependent. 5.10-6 100 10-1 101 103 10-1 10-3 10-1 100 10-1 100 10-6 100 10-1 100 High Pressure 100 105 10-6 106 10-10 100 100 10-16 101 10-1 103 101 104 10-5 104 10-8 100 100 10-14 100 10-1 102 Dimensionless groups’ magnitude orders for analyzed cases In order to define the computational domain. Modeled geometry was constructed following the bottom-up technique (generating surfaces and volumes from nodes and edges) in order to control mesh size around critical points (i.Chapter Five When analyzing a mass/heat transfer case at high pressure. Newtonian.10-2 10-1 100 10-10 . For further details on the geometrical model please refer to Guardo et al. air and toluene at standard conditions were chosen as the simulation fluids.95 - .5 % of their diameters with the adjacent surfaces in the geometric model. the spheres were modeled overlapping by 0. 100 102 10-6 103 . CO2. In order to couple species/energy and momentum balance.x/6.103 10-4 . Incompressible ideal gas law for density..101 10-2 . unsteady state analysis is required.10-8 100 10-1 102 102 100 10-4 10-1 . For the low pressure models the fluid was taken to be incompressible. the problem is identified as mixed (free + forced) convection in laminar or transitional flow. and its .104 10-4 10-1 100 10-10 101 10-1 103 101 101 10-5 101 . (2004) and Chapter Four of this thesis. Low Pressure Re Sr Ma Eu Fr Pr Sc Ec ReT PrT ScT Table 5. Turbulence forces contribution to all balance equations is negligible. Model setup and analysis Navier-Stokes equations together with species/energy balance were solved using commercially available finite volume code software Fluent® 5. Body forces and pressure drop become the most important terms in the momentum balance.923 was chosen for the geometrical model. and in a laminar or turbulent flow regime. in laminar flow regime and with variable density. In this study. particle-to-particle and particle-to-wall contact points). to include real contact points.2.e. CO2 and toluene were chosen in this case as the simulation fluids.

. In both mass and heat transfer simulation sets. 1982). and experimental data were selected as reference values to compare against the numerical results generated (Wakao et al. It can be noticed that for both mass and heat transfer situations.2.3. variable profiles along the bed were recorded and analyzed. under-relaxation factors for turbulent quantities were set in 0.3. the transport coefficients (kc. 1979.. then the balance equations for steady-state analysis are as shown in Table 5. 2005). in the laminar and transition flow zone (Re < 300) the results do not show dependence on the mesh density.2. 0. 0. For the modeling in the turbulent flow region (Re > 300). .4 and 0. Numerical convergence of the model was checked based on a suitable diminution of the normalized numerical residuals of all computed variables. h) were obtained from Equations [5.Chapter Five properties at high pressure were incorporated to the solver code through User Defined Functions (UDF) and User Defined Equations (UDE). and thermal excess method was used to calculate the thermal conductivity (Reid et al.2 < Re < 1800). Details on the implementation of these UDE’s and UDF’s can be found in Appendix D. Appropriate mixing rules were applied to the model for making all variables compositiondependant.96 - . the transport resistance resides only on the fluid side. Results for mass transfer are shown in Figure 5. Peng-Robinson equation of state was used to calculate fluid’s density and heat capacity.1. For a more complete convergence checking the average static temperature or average species concentration at the bed outlet were also chosen as monitors depending on the case.1. 1987). Sh) were obtained. The refinement of the mesh is expressed in terms of Vcell / Vp ratio. Standard correlations for Nu and Sh.. 5. Under-relaxation factors for pressure. With the collected numerical results. A first order discretization scheme for pressure.8. Simulations were run in a Dell Precision 380 and Hewlett Packard Proliant DL385 workstations. From the obtained values for kc and h. and the transport coefficients (Nu. momentum and energy were initially set to 0. In packed beds with constant temperature or species concentration at particle surface.3.3-2]. four meshes were used. momentum and energy equations was used until convergence was achieved. 2005). previous experience shows that the Spalart-Allmaras turbulence model is a good choice (Guardo et al. Lucas method was used to calculate the viscosity. In the case of turbulent flow simulations.2. and simulation times ranged from 1 to 240 hours depending on the studied case. and the results obtained were used as initial solution for a new simulation applying a second order discretization scheme for momentum and energy equations.4. Results for heat transfer are shown in Figure 5.1 and 0. inlet velocity was varied (0. 5. If axial dispersion is taken into consideration. Results and discussion Convective transport at low pressure The main purpose of this set of simulations was to test CFD capabilities in a particle-to-fluid transport packed bed model.3-1] and [5. Sh and Nu were computed and compared with the broadly accepted correlations and experimental data. For each simulation. respectively (Gunjal et al.05. respectively. and increased progressively after convergence until values of 0. For each simulation..

2).74 x 10-4 Vvcell/vp cell / V p = 3.3-2] dT f Boundary conditions u (C − C 0 ) = α ax at x = 0 (inlet) dC dx [5. a good accuracy for Sh and Nu values was obtained within 10 < Re < 100.1.77 x 10 = 5.3 1 1 VSerie10 cell / V p = 5. Experimentally. 1976).3-2b] at x = xL (outlet) Mass and energy balance equations applied to the packed bed model At lower Reynolds numbers (Re < 10).3-1] Energy balance d 2T f 6h ⋅ (1 − ε ) (T f − T p ) = α ax 2 u + dx d p ⋅ ε ⋅ C p ⋅ ρ dx [5.3-2a] at x = 0 (inlet) [5. For a single velocity condition. Reynolds number for the low pressure convective mass transfer packed bed model . one-shot measurements have demonstrated that no definite Nu values can be obtained at low Re (Wakao. 100 Sh 10 Sc = 1.. reinforcing the idea that a similar methodology can be applied to model mixed convection heat transfer at high pressure in the same Re range. This is particularly noticeable in the case of the heat transfer simulations (see Figure 5. particle-to-fluid heat transfer makes little contribution to the overall heat transfer in the system.3-1a] u (T f − T0 ) = α ax dT f =0 dT f dx [5.21 x 10 Ranz & Marshall (1952) 10000 -5 Re -4 VSerie11 cell / V p = 2.Chapter Five Mass balance 2 dC 6k c (1 − ε ) (C f − C ps ) = α ax d C + u dx d p ⋅ε dx 2 [5.97 - . mass and heat transfer results obtained shows that the fitting against Wakao et al. Sherwood number vs. correlations (1979. dx [5.3. The fact that any Nu value within the obtained ranges yields approximately the same value of αax suggests that at this low Re. 1982) is not good. 1981).) EXPERIMENTAL DATA (Reviewed by Experimental data Richardson & Szekely (1961) Wakao & Kaguei (1982) Figure 5. Using a laminar model. different meshes give results in a wide range of Nu and no relation with mesh density can be established in any case. which analytically has been reflected in an increased confidence range for the selected correlation at low Re (Shent et al.3-1b] dC =0 dx at x = L (outlet) Table 5.04 x 10 -4 -5 10 100 1000 Serie12 V cell / V p = 3.09 x 10 Wakao et al.

An analogy between the obtained numerical data and previously reported heat transfer data (Guardo et al.. 2006b) is also presented.3. (1996). The effects of density.Chapter Five 100 RANGE OF EXPERIMENTAL DATA (Reviewed by Wakao et al.2. for our specific study case. Convective transport at high pressure A numerical modeling of a packed bed where mixed convection mass and heat transfer phenomena appear was also made. 2005).98 - .04 x 10 V cell /V pelements 104325 elements -4 V cell /V p = 2. probably due to a better capture of the vorticity energetic scales associated effects. (1979) Figure 5. 5. The results obtained with the finer meshes fit better the prediction of Wakao et al. Shur et al.. the balance equations possess a smooth exact solution. Obtained numerical results for mass transfer were compared against the experimental results and the correlation presented by Stüber et al.. (1979) for heat transfer.1 1 Pr = 0. In RANS modeling. Reynolds number for the low pressure convective mass transfer packed bed model For higher values of Re there is a divergence between the results obtained for tested meshes in both heat and mass transfer simulations.21 x 10 Wakao et al. 2000. an accurate turbulence modeling requires a denser mesh around the particles surface in order to capture the involved turbulence phenomena and its related mixing enhancement in the boundary layer (Guardo et al. turbulent transport term in the transport equation becomes more important.) Nu 10 1 0. . 2005). and the numerical solution approaches that solution as we refine the grid.. and a novel correlation based on the convective mass transfer correlation presented by Stüber et al. 2006a). (1996) is proposed (Guardo et al. Nusselt number vs. The aim of grid refinement is numerical accuracy (Spalart. and Wakao and Kaguei (1982) for mass transfer in the turbulent flow zone (Re > 300). Therefore. The same geometrical model as the aforementioned case was used but now the circulating fluid and the values of pressure and velocity were modified.9 Re -4 10 100 1000 58933 V cell /Velements p = 5. flow rate and flow direction on mass and heat transfer are presented.77 x 10 -5 430051 = 3.09 x 10 Ranz & Marshall (1952) 348065 elements -5 V cell /V p = 3.2. Obtained numerical results for heat transfer were fitted. probably due to the fact that at higher Re.

inlet velocity was varied and Sh and Nu were obtained for 9 < Re < 100.3. and for each simulation. recirculation) caused by buoyancy effects (Benneker et al. 1964) and are shown in Figure 5. Equations [5. In order to corroborate this idea. A first order discretization scheme for momentum and energy equations and a second order discretization scheme for pressure were used until convergence was achieved. stream differentiation. local values of Gr. Obtained values were compared with Metais-Eckert maps (Metais and Eckert. the numerical results obtained for Nu for the different heat transfer situations analyzed were plotted in a flow map according to Churchill’s criteria (see Figure 5..e.3.. laminar or transitional flow could be expected. As it can be observed. Gravitational acceleration was added to the operating conditions of the model. In order to compute correctly the flow fields and the heat transfer phenomena in these zones. the optimal grid used for the prior model was locally refined for each case studied around the zones where high density gradients were found.3-2] were used to obtain the values of Sh and Nu for each studied case (see Table 5.3-1] and [5. Boundary conditions for the model are described in Table 5.4). .3). 1998). Sc and Re were calculated various points inside the boundary layer around the spheres in order to corroborate the transport mechanism present in the packed bed. The presence of high density gradients lead to the formation of hydrodynamical instabilities (i. 1E+5 Forced Convection / Laminar flow Forced Convection / Turbulent flow Free Convection / Turbulent flow 1E+4 1E+3 Re 1E+2 Free Convection / Laminar flow 1E+1 Transition: Laminar . Pr.Turbulent 1E+0 1E+2 1E+3 1E+4 1E+5 or 1E+6 1E+7 1E+8 1E+9 Gr · (Pr Figure 5.99 - . For different mass and heat transfer simulations. and the results obtained were used as initial solution for a new simulation applying a second order discretization scheme for momentum and energy equations. A laminar flow model was used as viscous model for all simulations. Under-relaxation factors were set as previously explained for the aforementioned low pressure models. countercurrent flow.Chapter Five Two simulation sets (upflow and downflow operation) were done. Sc) · (d/L) Comparison between simulation data and Metais-Eckert maps Churchill (1983) suggests that in a mixed convection heat transfer situation the transition between laminar and turbulent flow can be found at 1 × 109 < GrH < 1 × 1010. Dimensionless analysis indicated that for the studied velocity range. the main transport mechanism inside the packed bed under the different simulation conditions is the free convection in laminar/transitional flow regime.1.

5a) the presence of high density gradients (differences up to 40 kg/m3) lead to the differentiation of two streams: heavy (cold) fluid sinking into the bed. in order to minimize the effects of flow instability on calculations. 1995).Chapter Five It can be noticed that the results obtained follow the expected behavior according to the dimensionless analysis. (1998) proved that the hydrodynamical instabilities caused by buoyancy effects in a packed bed when density increases with height lead to a significant increase in the flow axial dispersion within the bed. 1987.4. Figure 5. the presence of hydrodynamical instabilities captured by the model caused numerical instability in the results. Opposing Flow Flow map according to Churchill’s (1983) criteria 5.5b). and transition between laminar and turbulent flow shows up in the results by means of a high increase in Nu for alike values of GrH. Benneker et al.2. The presence of large density gradients may result in convergence problems when solving the momentum. there has been a growth in the literature published on hydrodynamical instabilities due to density and viscosity variations in porous media (Homsy. continuity and pressure equations (Lakshminarayana. While simulating the high pressure data sets. 1991).3. When analyzing the velocity–density profile for the low pressure situation (Figure 5.5 compares velocity fields (colored by density) for high and low pressure heat transfer situations. it becomes . the mesh was locally refined in each case trying to avoid the presence of high density and velocity gradients within a single cell. Numerical instability increased as inlet mass flow imposed as boundary condition decreased. It can be seen that for the high pressure situation (Figure 5. This fact will be important when analyzing the effects of flow direction in free convection heat transfer. Manickam and Homsy. Effect of density gradients and flow stability Density gradients control the fluid movement at low velocities. 20 Laminar Flow Transition Turbulent Flow 15 Nu 10 5 0 1E+7 1E+8 1E+9 1E+10 1E+11 Gr H Assisting Flow Figure 5. and light (hot) fluid floating out of the bed.1.100 - . As mentioned before. Since the early experiments of Hill (1952).

(B) Air at 101 325 Pa and Re = 531 . Velocity field (scale colored by density. kg/m3) in an axial cut of the packed bed.Chapter Five clear that despite the fact a small density gradient is present in the results. Figure 5. flow field is controlled by the inlet velocity.5.101 - . (A) CO2 at 1 × 107 Pa and Re = 41.

Saiz et al.102 - ..6 presents a solute mass fraction contour plot within the packed bed. This effect appears to be more pronounced at low Re. The fluid motion direction was also considered defining the fluid flowing in a direction opposite to gravity (upflow mode) or in its direction (downflow mode).. The direction of this density gradient and the direction of the flow have strong effects on the axial dispersion and the mixing of the flow (Benneker et al.8). it can be noticed that.. 2005).. Several authors have reported in experiments that under supercritical conditions. Either if the flow direction assists the transfer phenomena (when density decreases with height) or is opposed to it (when density increases with height)..6. This behavior is certainly related to the presence of free convection and has been experimentally noted by other authors (Sovová et al. 1996). Figure 5.8 illustrates the initial mass extraction rates for different flow rates and flow directions.2. 2000. flow direction have a direct effect on mass and heat transfer phenomena. two conclusions can be drawn..6 and 5. 1994. Numerical runs were performed at various flow rates.3. Sovová et al. From the figures.Chapter Five 5. flow direction affects extraction rates increasing them when flow direction assists the mass transfer (e. 1998).g.. Effect of flow rate and flow direction As mentioned before. When gravity acceleration is added to the heat transfer model. 1994. constant pressure and temperatures. (1) Regardless of flow direction. and (2) Despite the strong dependence on flow rate. flow instability zones within the bed appear if a density gradient is present along the bed.7 and 5. 1996.7). the aforementioned phenomenology is captured by CFD analysis. the extraction rate increases strongly with flow rate (see Figure 5. Figure 5. Stüber et al. When analyzing mass transfer. and Figures 5. gravity-assisting flow enhances the extraction rate significantly (see Figures 5. Stüber et al.2. Germain et al. under certain conditions. for the case of extraction of toluene from the particles surface. Toluene mass fraction contour plot in an axial cut of the packed bed for [A] opposing flow and for [B] assisting flow with Re ≈ 20 .

00E-05 1. Re = 20 Re = 36 Re = 78 Cumulative toluene extracted at the bed outlet vs.00E-06 0.50E-05 2.00E-05 C7H8 extracted [kg] 2.Chapter Five 3.00E+00 0 30 60 90 120 150 Time [s] Re = 13 Figure 5.00E-05 5.7. time for different flow directions .50E-05 1.8. Assisting flow Cumulative toluene extracted at the bed outlet vs.00E+00 0 30 60 90 120 150 C7H8 extracted [kg] Time [s] Opposing flow Figure 5.103 - .00E-05 1. time for different Re in opposing flow regime 2.00E-05 5.50E-05 3.50E-05 2.00E-06 0.50E-05 1.

This fact generates a better mixing and a greater heat transfer coefficient (see Figure 5. the obtained results indicate that despite the fact that the forced convection component of the phenomena follows this behavior. An increase on flow velocity leads to an increase on kinetic energy. Therefore. . flow velocity has a directly proportional effect over heat transfer when forced convection takes place. Independently of flow direction. free convection component is almost constant for all cases (see Figure 5.Chapter Five When analyzing heat transfer at high pressure.104 - .9). the dominant dimensionless group describing this phenomenon will be GrH rather than Re. 20 16 12 Nu 8 4 0 40 50 60 70 80 90 100 Re Assisting flow Figure 5. This increase in the overall heat transfer is due exclusively to the increase of the contribution of forced convection to the total heat transfer rate. Is clear that free convection component is intrinsically related to density and temperature fields and it is not affected by velocity. which increases flow mixing and heat transfer rates. The heat transfer rising in assisting flow is favored by the temperature gradient direction (the same as flow direction). The presence of an adverse density gradient (when temperature gradient direction is opposed to flow direction) diminishes heat transfer rates and lower coefficients are obtained.9. When analyzing a mixed convection case.9). results obtained show a similar behavior than the aforementioned. for the covered range of Re the heat transfer coefficient value increases almost linearly with velocity (see Figure 5. reflecting that heat transfer coefficient values are significantly greater in assisting flow cases than those obtained for opposing flow cases (see figure 5. Reynolds number for assisting and opposing flow simulations In a similar way. Opposing flow Nusselt number vs.2).10).

(1996). 100 Sh 10 1 10 Re CFD Experimental Stüber et al. From the obtained results for values of kc. using numerical data and substance properties at corresponding operating conditions. Reynolds number for both upflow and downflow operations.10. Reynolds number for free and forced convection in assisting flow 5.11. Validating the numerically obtained mass transfer data Values of kc were evaluated from the mass balance equation (see Table 3). a good agreement between numerical results. 100 Figure 5. Sh was computed and compared against experimental data and against the correlation presented by Stüber et al.3. (1996). Re and the aforementioned comparison are given in Figure 5. As it can be seen.11.2. The results of Sh vs. . CFD obtained Sherwood number vs.Chapter Five 100 Nu 10 1 1 10 100 Re Free Convection Forced Convection Figure 5. and comparison against experimental data and correlations presented by Stüber et al. experimental results and the correlation prediction is obtained. Nusselt number vs.105 - .3.

(1996).12 and 5. .Chapter Five The contributions of free and forced convection to mass transfer could be evaluated following the indications of Stüber et al. finding also concordance between the numerically obtained results and the experimental results reported in that paper (see Figures 5.13. Assisting flow Experimental (Stüber et al.) CFD obtained contribution of forced convection to total mass transfer vs. [(Sh .Sh0)]/Sc 0. Reynolds number and comparison against experimental data presented by Stüber et al.3 100 10 1 10 100 Re Opposing flow Figure 5. Reynolds number and comparison against experimental data presented by Stüber et al.Sh0) ± (Shfree .13). Experimental (Stüber et al. 100 Shfree/Sh (%) 10 10 Re Assisting flow 100 Opposing flow Figure 5.12.106 - . (1996). (1996).) CFD obtained contribution of free convection to total mass transfer vs.

14 and Figure 5. Figure 5. (1996) for mixed convection mass transfer under supercritical conditions in packed beds can be used to describe heat transfer phenomena in a supercritical packed bed reactor under mixed convection regime at high pressures. .15 shows a reduction of the numerical data points to a natural convection-free basis only depending on the Re numbers.3. Such correlation can be useful when designing supercritical packed bed reactors..14 shows the contribution of free convection to the total Nusselt number as a function of the Reynolds number. nowadays under study and development process. low Re numbers correspond to transport dominated by natural convection.4.Chapter Five 5. still 30% of transport is due to natural convection (for both assisting and opposing flow). CFD obtained contribution of free convection to total heat transfer as a function of Reynolds number The aforementioned idea of a high pressure mixed convection heat transfer correlation can be noticed explicitly in Figure 5. The obtained numerical results validates the idea that a modified correlation based on the one proposed by Stüber et al. particularly in the design of directcycle supercritical-water-cooled fast nuclear reactors (Oka et al. 1994). Unfortunately.2.107 - . 100 Nufree / Nu (%) 10 1 Re Assisting Flow Opposing Flow 10 100 Figure 5. leading to greater heat transfer coefficients.15. As expected. there is no experimental data available in order to validate the prior statement. Correlating the numerically obtained heat transfer data Heat transfer coefficients at high pressure were obtained using a CFD simulation procedure similar to that applied for the mass transfer simulations presented in the prior sections of this chapter. While the contribution of free convection to total heat transfer rate decreases with Re (as its value remains almost a constant). Figure 5. forced convection increases. but for Re around 100.14.

3 0. CFD obtained contribution of forced convection to total heat transfer as a function of Reynolds number After validating the numerical results obtained against experimental data and empirical correlations (see Figures 5.4-3b] Valid for the following ranges of dimensionless numbers: 9 < Re < 96. obtained Nusselt and Sherwood numbers is given in Figure 5. an analogy between mass transfer data presented in this work (CFD and experimental) and numerical heat transfer data reported (Guardo et al.2 < Pr < 3.3-3] Taking Nu0 = 2 (Wakao and Kaguei. the correlations for free and forced convection are: Nu free = Nu 0 + 0. In summary. establishing a relationship between the selected data. 5.13).001(GrH ⋅ Pr ) Nu forced = 0. because the CFD code applies the same mathematical procedure to estimate transport of any scalar quantity (such as mass or energy). It can be noticed that with a similar simulation methodology heat and mass transfer coefficients at high pressure can be obtained.88 Pr 0. 1982).12 and 5. 2.10 1 Re Assisting Flow Opposing Flow 10 100 Figure 5.00 [(Nu ..244 [5.3-3a] [5.11. 2006) can be done.Nu0 ) ± (Nufree . Results obtained for heat and mass transfer simulations show a good fitting when compared to the prediction of the aforementioned correlations for heat and mass transfer.269 Re 0.3 1. .33 Pr 0.15. The parity plot for predicted vs.00 0.16.108 - .3.Chapter Five 10.Nu0 )]/Pr 0. 1 × 108 < GrH · Pr < 4 ×1010. the correlations recommended are: Nu − Nu 0 = Nu forced m (Nu free − Nu 0 ) [5.

17.3-3] Figure 5. that showed an AARD = 18.3-3]).16. 20 Coefficient from CFD 15 10 5 0 0 5 10 15 20 Coefficient from correlations Heat transfer Figure 5. Predicted values for Nusselt number show that estimation error is within that obtained with original mass transfer correlation. Estimated error for the high pressure mixed convection correlation against simulation runs .17). Mass transfer Comparison of numerically obtained vs.Chapter Five An advantage of this correlation is that a single set of parameters predicts heat transfer for assisting flow free convection (with the minus sign in Equation [5. predicted heat and mass transfer coefficients using the proposed correlations 25 20 15 NuT 10 5 0 1 2 3 4 5 6 7 8 9 10 11 Simulation run CFD Correlation [Eq. 5.109 - .3-3]) as well as opposing flow free convection (with plus sign in Equation [5.9% (see Figure 5.

For a single velocity condition different meshes give results in a wide range of Nu and no relation with mesh density can be established in any case. 2006). It was noticed that the presence of large density gradients conditioned the mesh influence over the numerical results when computing the mixing and the mass/heat transfer within the computed domain.3. and Wakao et al. [5. At lower Reynolds numbers (Re < 10).110 - . . Free convection is independent of flow velocity and its value remains almost constant within the studied velocity range. 2. but in the turbulent flow zone a good definition of the mesh around the particles surface is of primal importance in order to capture the turbulence vorticity energetic scales associated effects. For a supercritical fluid in laminar flow regime it was possible to study the effects of the density gradient. Pr and GrH . can be used to describe heat transfer phenomena in a supercritical packed bed reactor under mixed convection regime at high pressures.3-3]) is presented for estimating the free and forced convection effects and Nu from Re. The obtained numerical results validates the idea that the modified correlation presented (Guardo et al. This situation is especially notorious when analyzing heat transfer. An adverse density gradient generates hydrodynamical instabilities that produce an increase of the axial dispersion and a diminished mass/heat transfer rates. The rising in the density along the bed height due to the adverse density gradient helps the axial dispersion to grow. greater heat transfer rates are obtained. Presented correlations are valid for 9 < Re < 96. (1979) for heat transfer. the mesh was locally refined in each case trying to avoid the presence of high density and velocity gradients along the bed. based on the one proposed by Stüber et al. flow direction and velocity over mass and heat transfer. In order to eliminate numerical instability. It allows to analyze either free or forced convection situations and the obtained results can be compared qualitatively and quantitatively against previous published data. results shows that the fitting against correlation is not good. and 1 × 108 < GrH · Pr < 4 × 1010. Flow velocity also affects the heat transfer rate. This fact caused numerical instability in the simulation process.2 < Pr < 3. The value of Sh and Nu increases almost linearly with flow velocity and this increase is due exclusively to the increase in the contribution of forced convection to the overall mass/heat transfer. (1996) for mixed convection mass transfer under supercritical conditions in packed beds. obtaining less mixing within the bed and smaller heat transfer coefficients. and the influence of velocity over mass and heat transfer could be analyzed.Chapter Five CONCLUSIONS CFD proves to be a reliable tool when modeling convective mass and heat transfer phenomena in packed beds. Mixed (free+forced) convection at high pressure in a packed bed was also analyzed. No mesh sensitivity was noticed for the laminar and transition flow zones. For values of Re > 10 it was obtained a good agreement with the correlations presented by Wakao and Kaguei (1982) for mass transfer.. Forced convection at low pressure in a packed bed was simulated. A novel correlation (Eq. Influence of flow direction over mass/heat transfer was also analyzed and it was noticed that in assisting flow regime.

Egusquiza.. AIChE Journal.. and Homsy. Hurt. M. Industrial & Engineering Chemistry. S. F. 19. Hougen. M. W.Chapter Five REFERENCES Benneker.M.. Westerterp. 35. (1986).A. Egusquiza. 284 – 295. (1994). G. 271 – 311. Coussirat. R. Recasens. 522 – 528. Escaler. (2005).. A.. Germain.. Recasens.. (Eds.. AIChE Journal.. A... 7049 – 7056. E. (2004). Escaler. USA. P. Recasens.. Influence of the turbulence model in CFD modeling of wall-to-fluid heat transfer in packed beds. A.. V. 1.. F. 2879 – 2886.M.A. 263 – 270. Channeling in packed columns. Kays. Coussirat. 82 – 90. 12.M. R. (1998).M. NY. M. (1987).10) Debenedetti. G. 365 – 378.. Industrial & Engineering Chemistry Research. 51.W. (2006a). Guardo. (1973). A theoretical study of pressure drop and transport in packed beds at intermediate Reynolds numbers. New York. 44. Where are we? Journal of Heat Transfer. Churchill. (1983). Homsy. M.. Hemisphere publishing corporation.. del Valle. 116. Viscous fingering in porous media. (2005). Coussirat. (Sections 2. B. Heat..): Heat Exchanger Design Handbook. 44. Chemical Engineering Science. 247 – 253. 39. (2005). A. Natural convection retards supercritical CO2 extraction of essential oils and lipids from vegetable substrates. Coussirat. Hill. CFD studies on particle-to-fluid mass and heat transfer in packed beds: free convection effects in supercritical fluids. Annual Reviews of Fluid Mechanics... Guardo. CFD Flow and heat transfer in nonregular packings for fixed bed equipment design.A.. F... 1733 – 1742. and Reid. Guardo.. E. El-Kaissy. . (1952). P. F. et al. Chaudhari. Computational study of a single-phase flow in packed beds of spheres..C. A. CFD study on particle-to-fluid heat transfer in fixed bed reactors: Convective heat transfer at low and high pressure. M. X... M..M. Gunjal. K.A.5.. (2006b).. Single phase convective heat transfer. M. (1943). S. Transactions of the American Institute of Chemical Engineers. 61. Larrayoz.. O.111 - .A. J.. M. 1 – 35. 60. 4341 – 4353.. de la Fuente. Kronberg. Larrayoz. G.7 to 2. Ranade. Thodos.. Larrayoz. AIChE Journal. X. 43. Recasens.. A. Diffusion and mass transfer in supercritical fluids. M.. J.. Industrial & Engineering Chemistry Fundamentals.5. Industrial & Engineering Chemistry Research. Influence of buoyancy forces on the flow of gases through packed beds at elevated pressures. In: Schlünder.. 32. (1943). Chemical Engineering Science. J. Chemical Engineering Science. Larrayoz. D.. 2034 – 2046. E. Chemical Engineering Science (submitted – in revision). Principles of reactor design.. mass and momentum transfer in the flow of gases through granular solids. Gamson. Turbulent Prandtl number.. Guardo.

Fernández. P200002461.112 - . 9. Okano. 415 – 420. (2000). Howdle. Y. O’Connell.. Industrial & Engineering Chemistry Fundamentals.. 35.. McGraw-Hill. An analytical study of heat and mass transfer in multiparticle systems at low Reynolds numbers.. B.E. 50.. 75 – 102. (2000). (1987). (1996).P. Extraction of grape oil. A. 109.. Steady-state solutions for flow through assemblages of cylinders. O. P.. B. 189–218 (Chapter 5). J. Poling. Chemistry under Extreme and Non-classical Conditions. M.. Travin.E. . and Ishii. (1991). (1981). R.A. Measurements of particle-to-gas heat transfer coefficients from one-shot thermal responses in packed beds... R. 3. 380 – 383. AIChE Journal. 43. B. K. 7..W. Saiz. E. N. J. Sovová. Spain patent No. G. (2004). 1545 – 1555. Jevremovic. Spalart.. McGraw-Hill. R. Larrayoz. M...M. J. (1964). Fingering instabilities in vertical miscible displacement flows through porous media. (1970). and Homsy. pp. 1 – 10. Pfeffer. 542 – 549. S.. pp..A.1 – 10. Poling. Poliakoff.. Pfeffer.... J. George. AIAA Journal.. J. A. Trabelsi. Chemical Engineering Science. Viscous flow through particle assemblages at intermediate Reynolds numbers. 3.. Wakao.. J.. (1968). (1994). Systems design of direct-cycle supercritical-water-cooled fast reactors.. Ramírez. Y. Jež. S. Sunflower oil hydrogenation on Pd/C in SC propane in a continuous recycle reactor. Oka. Journal of Fluid Mechanics. F. New York. M. Rate of the vegetable oil extraction with supercritical CO2 – II. and Happel.. 36.. R. Reid. Recasens.. Inorganic and related chemical reactions in supercritical fluids.. 1230 – 1242. 608 – 613. (Ed. In: Van Eldik. M. Three dimensionality in Reynolds-averaged Navier–Stokes solutions around two-dimensional geometries. Strelets. T. Steady-state solutions for flow through assemblages of spheres. Nishimura. Viscous flow through particle assemblages at intermediate Reynolds numbers. Koshizuka. F. Kučera. Squires. S. Shent.M. Industrial & Engineering Chemistry Fundamentals. Procedimiento para la extracción de lanolina de la lana y planta para la realización de dicho procedimiento. M. F..P. Recasens. 605 – 611. T.. Boston. and Hamielec. Prausnitz. (1980)... 49.. Manickam. Industrial & Engineering Chemistry Fundamentals. J. (2005). (1964). (1994). M. Y. The 1990 Freeman scholar lecture.. B. Journal of Fluids Engineering... Shur. Chemical Engineering Science. pp.. An analysis of transport phenomena for multi-solid particle systems at higher Reynolds numbers by a standard Karman—Pohlhausen method—I Mass transfer.. Heat and mass transport in multiparticle systems.56.. 288.. 113.. and Hamielec. LeClair. M. Chemical Engineering Science. 10. Heidelberg.Chapter Five Lakshminarayana. A. The properties of gases and liquids. H.. 315–352. An assessment of computational fluid dynamic techniques in the analysis and design of turbomachinery.). Larrayoz. Nuclear Technology. S. The properties of gases and liquids. B. LeClair. 1283 – 1286. Prausnitz. (1995). 95 – 205. AIChE Journal. Kaguei. Spektrum.. 1205 – 1209.

. 31. F. Particle-to-fluid transfer coefficients and fluid diffusivities at low flow rate in packed beds. Chemical Engineering Science. (1999)..Chapter Five Spalart.. International Journal of Heat and Fluid Flow. Kaguei. White. 138 – 160. S. (2000).. M.. N. Wakao. 21. Yaws.. New York. New York. A..113 - . 35. 34. N. . McGraw-Hill. S. Larrayoz.. 325 – 336. F.. T. Chemical Engineering Science.R. (1976). (1991). pp. (1996). 1 – 55. McGraw-Hill. Strategies for turbulence modelling and simulations.A. Chemical properties handbook.. Recasens. C. (1979). 252 – 263. pp. pp. Vázquez. Heat and mass transfer in packed beds. 264 – 295. Gordon and Breach Science Publishers. 482 – 542. 3618–3628. F. 1115 – 1122.M. P. (1982). and Kaguei. Stüber. Supercritical fluid extraction of packed beds: external mass transfer in upflow and downflow operation. Industrial & Engineering Chemistry Research. New York. Effect of fluid dispersion coefficients on particle-tofluid heat transfer coefficients in packed beds: correlation of Nusselt numbers. Funazkri. N. Viscous fluid flow... Wakao. Wakao..

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CHAPTER SIX CFD modeling on the supercritical hydrogenation of sunflower oil HIGH–PRESSURE HETEROGENEOUS REACTIONS « Verdrink niet in je eigen inspiratie en verbeelding. « Het zonnebloemen » (1888) . wordt geen slaaf van je eigen model » Vincent van Gogh.

.

margarines or shortenings). reaction rate determined directly by measurements using a differential reactor. If. the activation energy may differ from that of the intrinsic chemical reaction. the intra-particle diffusion mechanisms of the triglycerides and hydrogen in the hydrogenation were studied using supercritical propane for 2 % Pd on activated carbon. economic and environmental friendly process. the reactant gas may diffuse deep into the pores of pellet. not the intrinsic chemical reaction rate.Chapter Six Partial hydrogenation of fats and oils is an important process in the food industry because not only increases oxidative stability of the final product when compared to raw materials. In previous work done by our research group (Ramírez et al. Satterfield (1970). 1997). If a chemical reaction is very fast. Smith (1970). according to their final application (e. 1955) made an extensive study on the role of pore diffusion in catalysis. an experimental design methodology and a response surface methodology were used to achieve optimum hydrogenation conditions for Pd catalyst in supercritical propane in a continuous well-mixed reactor. The results showed that while hydrogen is transported by bulk pore diffusion. Wheeler (1951. even to the center of the pellet. and Dullien (1979) have reviewed the subject of pore diffusion associated with chemical reaction well. Diffusivity for H2 is about 10 times greater than that for triglycerides. . the reaction is very slow. This enormous amount of surface area results mainly from the fine interconnecting pores in the catalyst pellets. In the conventional process. If we simply measure activation energy from the overall reaction rate constants.117 - . but also changes the physical characteristics of it.g. however. for example. studies applying the Hashimoto et al. The overall rate is governed not only by the chemical reaction. low reaction rates and the formation of undesirable by-products (such as trans fatty acids content about 40 wt%) are consequences of the low solubility of H2 in the oil and the high mass transfer resistance for the hydrogen in the liquid phase (Farrauto and Bartholomew. to derive the diffusivities in diffusion-limited reaction runs using larger catalyst sizes (up to 2 mm). 2004).5 mm) in the absence of diffusional limitation and then using the intrinsic kinetic constants. Petersen (1965). Porous solid catalysts used for gas catalytic reactions have specific surface areas of tens to hundreds of square meters per gram. it proceeds at the external surface of the pellet.. It also provides a clean. Supercritical technology has proven to be a reliable alternative to the conventional hydrogenation process (Härrod et al. The review article of Youngquist (1970) will also help readers understand the basic principles of diffusion and reaction in a porous catalyst. The importance of diffusion is often underestimated by some catalyst chemists. 2003) resulting increasing the rate of reaction and reduced trans isomer levels. the oil seem to diffuse by surface diffusion. Furthermore. The method of measuring the effective diffusion coefficients was first to obtain the intrinsic kinetic constants on small-size catalyst particles (≈ 0.. is the overall rate. one needs to know the overall reaction rate. External resistance to mass transfer was made negligible using a high flow velocity over the catalyst bed (Re ≈ 6000). In the laboratory. The overall rate constant does not necessarily mean the intrinsic chemical reaction rate constant.. Also.. In later studies (Ramírez et al. (1971) scheme provided information on the kinetics for the supercritical hydrogenation on a commercial-size Pd/C catalyst. but also by the diffusion rate through the pores inside the catalyst pellet as well as at the pellet’s external surface. 2006). Tacke et al. 2001. Jackson (1977). The results showed that it is possible to obtain a hydrogenated fat with 2 – 3 wt% trans C18:1 content and an iodine value (IV) of about 70 (starting from an initial value of 130). and the chemical reaction takes place everywhere uniformly in the pellet. For the design of industrial packed bed reactors.

443499 0. and conversion profiles are obtained. mm L inlet concentration. Different particle sizes are studied and external mass transfer and intra-particle diffusional effects are analyzed. mol/m3 S inlet concentration. Poling et al. Yaws.118 - .10 0. The dimensionless equations corresponding to continuity.47 0. momentum.57 242.023614 0. A 2D CFD model of a single Pd-based catalyst pellet is presented. 2000). mol/m3 H2 inlet concentration.094676 0. Intraparticle concentration profiles for all species present in the mixture (oil triglycerides and hydrogen) are obtained and compared against experimental results.32 0.. a dimensionless analysis of Navier-Stokes equations under simulation conditions was developed.00 2.13 – 1. mesh design and CFD modeling To properly design a mesh capable of capturing the transport mechanisms present in the study in detail. Boundary condition Circulating fluid Mixture proportions (wt %) Temperature. Reynolds number was calculated using particle diameter as characteristic length.171589 0.057084 0.73 13.179669 0. Single pellet model 95 : 4 : 1 457 – 473 2 x 107 Laminar. 1991). mol/m3 Table 6. Pa Flow model Velocity at the inlet.1.1.217710 0..32 0. Boundary (operating) conditions for each analyzed situation are shown in Table 6. (2006).Chapter Six The aim of the work presented in this chapter was to apply Computational Fluid Dynamics (CFD) to the study of the catalytic hydrogenation of sunflower oil in the presence of a supercritical solvent. and energy balances are detailed in Chapter Two. 6.013177 0. mol/m3 E inlet concentration.5590 1. 1999. Results of the order of magnitude of the dimensionless groups are shown in Table 6.018240 0.108529 1.. Details on the dimensionless numbers used can be found in Appendix C.28 0. mol/m3 O inlet concentration.056489 0.075731 0.450727 Boundary (operating) conditions for analyzed cases .1. Geometry. The orders of magnitude of the dimensionless groups were estimated by taking physical-chemical property values for air from experimental data and empirical correlations available in the literature (Reid et al.2. K Pressure.92 2. 1987. mass. Values for operating conditions were taken from experimental data published by Ramírez et al.120502 1. Reynolds analogy was used to estimate values of Sct and Prt from Ret (White.00 Packed bed model Propane + H2 + Sunflower oil Laminar 1 x 10-3 – 2 x 10-2 0.47 37. m/s Particle diameter. κ − ε 0. Verified kinetic constants and intra-particle diffusion coefficients were fed into a 3D packed bed reactor model.

1. 0. For both balances. In energy and species balances.3 m/s for the single sphere model).2) was selected as the base unit cell in order to simulate a packed bed reactor.2. steady state analysis can be used. 0.1.9205 and 2 mm).473 K) and in a laminar (10 < Rep < 100 for the packed bed model) or turbulent flow regime (u = 1. Inertial gravity forces increase their contribution as Re decreases. A simple cubic sphere stacking (see Figure 6.1) was built to study mass transfer and intra-particle diffusional effects.47. and pressure drop together with turbulent forces become the most important terms in the momentum balance at high Re.119 - . hydrogen and sunflower oil (95 : 4 : 1) was chosen as the simulation fluid.Chapter Six Magnitude order Re Sr Ma Eu Fr Pr Sc Ec ReT PrT ScT Table 6. 2 geometrical models were created. A 2D axisymmetric simplification of a single spherical catalyst pellet (see Figure 6. 4 different particle sizes were selected for this study (Dp = 0. Figure 6. For the simulations the fluid was taken to be Newtonian. For the momentum balance it becomes clear that viscous forces decrease their contribution as Re increases. In order to define the computational domains. dimensionless analysis allows identifying the problem as forced convection in laminar or turbulent flow. Mesh detail for the 2D single pellet geometrical model . 100 10-1 10-6 1010 10-2 100 10-1 10-10 10-3 103 102 101 10-2 10-5 108 10-1 100 10-1 10-8 10-2 103 102 102 10-3 10-4 106 100 100 10-1 10-6 10-1 103 102 103 10-4 10-3 104 101 100 10-1 10-4 100 103 102 104 10-3 10-3 104 100 100 10-1 10-4 101 103 102 Dimensionless groups’ magnitude orders for analyzed cases In the case of particle-to-fluid transport. the convective and the diffusive term become important for the balances. A mixture of propane. isothermal (457 .

1996.3. In this chapter. Harris et al.Chapter Six Figure 6. Schematic representation of the kinetic model used for the supercritical hydrogenation of sunflower oil . 1994. Model analysis and setup CFD has proven to be a reliable tool when modeling chemical reactors.. Steady state analysis was chosen for the simulations.2.. Navier-Stokes equations together with the κ . 2006) for the supercritical hydrogenation of sunflower oil were also incorporated within the equations set of the CFD solver. in order to study the transport and reaction mechanisms present in the supercritical hydrogenation of sunflower oil. Mesh detail for the 3D packed bed unit cell geometrical model 6.x. For further insight in the kinetic and diffusional model. A schematic representation of the kinetic model used is shown in Figure 6. Comsol Multiphysics 3. Figure 6.3. Several reviews on the applicability of CFD methodology to chemical reactors design have been published in the last years (Bode. Values of molecular and effective intra-particle diffusivities applied to the CFD model can be seen in Table 6.120 - .4. 2002). following the guidelines obtained with the dimensionless analysis. please refer to Ramírez (2005).2.3. Kuipers and van Swaaij. The kinetic and diffusional models proposed by our research group (Ramírez et al. Kinetic constants used for simulations can be seen in Table 6. Simulations were run under isothermal (457 – 473 K) conditions. 1998.ε turbulence model (when necessary) and a convection/diffusion mass balance were solved using a CFD commercially available finite element code software. 2004. Ranade.

47 .426 0.02 k13 mol-0.5· mol-0. Fitted parameters values for the kinetic model 457 K Oil Particle diameter.3.94 x 10-8 1.77 x 10-3 7.352 0.94 x 10-8 2.4 x 10-8 1.5· m4.5· (kg Pd)-1· s-1 (kg Pd)-1· s-1 k32 k24 mol-1· m6· (kg Pd)-1· s-1 k34 mol-1· m6· (kg Pd)-1· s-1 Table 6.8 x 10-8 5.8 x 10-8 9. m2/s 0.4 x 10-8 0.76 x 10-8 6.933 0.84 x 10-8 2 2. m2/s Molecular diffusivity.82 x 10-9 6. mm Molecular diffusivity.Chapter Six Parameter k12 mol-0.94 x 10-8 3 x 10-7 9 x 10-8 H2 Table 6.4 x 10-8 3.92 x 10-8 H2 473 K Oil Particle diameter.5· m4.2 mm) Simulations were run in a Dell Precision 380 workstation.8 x 10-7 2 9.603 6. K 457 0.8 x 10-8 2.5· m4. Concentration contour fields (see Figure 6.4) for all species present in the model were obtained and the numerical data recorded in order to analyze conversion.47 2. m2/s Effective diffusivity. .5· m4.5· (kg Pd)-1· s-1 Temperature. m2/s Effective diffusivity.88 x 10-8 3 x 10-7 1.4. m2/s Effective diffusivity.13 x 10-3 473 0. Numerical convergence of the model was checked based on a suitable diminution of the normalized numerical residuals of all computed variables. mm Molecular diffusivity.5· (kg Pd)-1· s-1 k23 mol-0.9205 9.9205 2.1 1 x 10-6 0. m2/s 0. m2/s Effective diffusivity.121 - .94 x 10-8 6. m2/s Molecular diffusivity.4 x 10-8 6. and simulation times ranged from 1 to 4 hours depending on the studied case.071 1 x 10-6 0. Fitted molecular and effective diffusion coefficients for hydrogenation species on 2% Pd/C catalyst (Dp range = 0.116 0. reaction velocities and mass transfer.8 x 10-8 3 x 10-7 3 x 10-7 0.94 x 10-8 8.47 9.

Chapter Six

Figure 6.4.

(A) Concentration contour plot for Linoleic fatty acid (C18:2) in a single 2 % Pd catalyst pellet model (Dp = 0.9205 mm); (B) Concentration contour plots for fatty acids in a 3D packed bed model (Re = 100). Concentrations expressed in mol/m3

- 122 -

Chapter Six

6.3.

6.3.1.

**RESULTS AND DISCUSSION
**

Validation of numerical results

In order to validate the numerical results obtained, a set of 2D simulations of particle-to-fluid mass transfer and reaction in a single catalyst pellet (emulating the experimental conditions proposed by Ramírez et al. (2006)) was made, and the results obtained were compared against the experimental results aforementioned. Intra-particle concentration profiles and intra-particle reaction rates were obtained for Dp = 0.47, 0.9205 and 2 mm, for which validation was possible due to the availability of experimental data. First of all, it was necessary to verify the absence of gradients in the catalyst surface, since the experimental data was obtained in a Robinson-Mahoney gradientless reactor (Ramírez et al., 2004, 2006). For all particle diameters studied, concentrations (see Figure 6.5) and reaction velocity profiles (see Figure 6.6) along the surface arc were recorded. In all cases analyzed, flat variables profiles were obtained, assuring the absence of gradients along the catalyst surface.

0.24

1.6

Coil, surface [mol/m3]

0.18

1.2

0.12

0.8

0.06

0.4

Dp = 0.47 mm

0 -1.00 -0.50 0.00 0.50 0 1.00

**Surface arc length [dimensionless] Linoleic
**

Figure 6.5.

Oleic

Elaidic

Stearic

Hydrogen

Verification of the gradientless condition at the catalyst surface. Species concentration on catalyst surface for Dp = 0.47 mm

Once verified the aforementioned, intra-particle concentration profiles and intra-particle reaction rates were obtained and compared against experimental data previously published by our research group (Ramírez et al., 2006), obtaining for all cases a good agreement between the numerical and the experimental data (see Figures 6.7 and 6.8). Magnitude of relative errors was evaluated for the developed simulations, finding that this value was within the magnitude order of the experimental error previously reported by our research group. A trial for minimizing the relative error by means of optimizing the kinetic constants of the model and the effective diffusivities was also made, but an appreciable change was not observed in the concentration profiles obtained, remaining the magnitude order of the relative errors similar to those obtained when the original kinetic and diffusional model was used (Guardo et al., 2006).

- 123 -

CH2, surface [mol/m3]

Chapter Six

0.03

-0.08

roil, surface [mol/m3·s]

0.015

-0.11

0

-0.14

-0.015

-0.17

Dp = 2 mm

-0.03 -1 -0.5 0 0.5 1 -0.2

**Surface arc length [dimensionless] Linoleic
**

Figure 6.6.

Oleic

Elaidic

Stearic

Hydrogen

Verification of the gradientless condition at the catalyst surface. Reaction rates on catalyst surface for Dp = 2 mm

0.25 0.2

1.6 1.4 1.2 1 0.8

[mol/m ]

0.15 0.1 0.05

Coil

0.4

Dp = 0.47 mm

0 -1 -0.5 0 0.5 [dimensionless]

Elaidic Elaidic - EXP

0.2 0 1

Particle radius

Linoleic Linoleic - EXP Hydrogen Oleic Oleic - EXP Hydrogen - EXP

Stearic Stearic - EXP

Figure 6.7.

Validation of numerical data obtained. Intra-particle species concentration profile for Dp = 0.47 mm. Experimental data taken from Ramírez et al. (2006)

- 124 -

CH 2

0.6

[mol/m ]

3

3

rH2, surface [mol/m3·s]

4 1.125 - CH 2 r H2 [mol/m ·s] -0.0015 -0.2 0.EXP Figure 6.2 1.25 0. Comparison of the intra-particle concentration profiles for Dp = 0.8.1mm Linoleic 0.0045 0.3 1.47mm Stearic 0.47mm Figure 6.003 -0. Intra-particle reaction rates for Dp = 2 mm.47 mm (experimental – Ramírez et al.05 0 Particle radius [dimensionless] Linoleic 0.15 1.1 0.5 1.5 0 0.EXP Stearic Stearic .03 roil Dp = 2 mm -0.2 0.0015 0 -0.6 0.8 1 Coil 0.1 mm (numerical) and Dp = 0.035 -0.5 [dimensionless] Elaidic Elaidic .EXP Hydrogen .4 0.02 -0.005 -0. Experimental data taken from Ramírez et al..1mm Oleic 0.47mm Hydrogen 0. Validation of numerical data obtained. 2006) in a single 2 % Pd catalyst pellet .1 1 0 0.Chapter Six 0.1mm Stearic 0.025 -0.003 -1 Linoleic Linoleic . (2006) 0.015 3 3 .1mm Elaidic 0.01 [mol/m ·s] 0.EXP Hydrogen -0.47mm Elaidic 0.EXP 1 Particle radius Oleic Oleic .9.47mm Hydrogen 0.1mm Oleic 0.

05 0.11 shows the surface local mass transfer for H2 obtained by means of the CFD simulations.47 mm (Ramírez et al.50 0.Chapter Six 6. a CFD simulation extrapolating the catalyst evaluation for Dp = 0. surface − C i .03 0. It can be seen in Figure 6.1 mm.00 Surface arc length [dimensionless] Figure 6.∞ ) [6. 2006).00 0. species concentration contour plots (Figure 6. the effectiveness factor of the catalyst is close to the unity.47 mm koil.10 shows the surface local mass transfer coefficients for oil and Figure 6.2. Particle-to-fluid mass transfer coefficients estimation For each simulation.01 2 mm 0 -1. 0. reassuring the idea that for a particle diameter of 0. This fact must be related with the formation of an stagnation/recirculation flow point downstream the catalyst pellet.126 - . 6. local 0. and mass flux through the particle surface was recorded. numerically obtained concentration profiles were almost identical to those reported experimentally for Dp = 0. It can be seen that the obtained mass transfer coefficient values are almost constant in the upstream surface sector.10 mm 0.3.3-1] Figure 6.4) were analyzed.3.04 [m/s] 0..02 0.9 that for a particle with Dp = 0.3.9205 mm 0.1 mm was also made in order to corroborate the catalyst effectiveness.00 -0. Verification of catalyst effectiveness at low particle sizes Due to the difficulty for obtaining experimental data at very low particle sizes. while in the downstream surface sector the mass transfer coefficient value is strongly diminished. affecting specially the mass fluxes over the catalyst surface.50 1.47 mm or lower. Surface local mass transfer coefficients for oil fatty acids for the supercritical hydrogenation of sunflower oil at 20 MPa and 473 K .10. With this data the surface local mass transfer coefficients (k) could be determined: J i = k i ⋅ Ae ⋅ (C i .

1985).04 0.02 2 mm 0.00 Surface arc length [dimensionless] Figure 6.00 Table 6.10 0. mm 0.47 0. the obtained numerical data suggests that the particle-to-fluid mass transfer coefficients for the supercritical hydrogenation of sunflower oil lie within the values for a gas (Ranz and Marshall.10 mm kH2.127 - .5.00 -1.5) and compared with the theoretical solution proposed by Ranz and Marshall (1952) for particle-to-fluid mass transfer in a single sphere (gas at low pressure). it can be noticed that the obtained values are lower than the extrapolation predictions.18 44.43 113.28 119.9205 mm 0. When comparing the obtained results with an extrapolation for the correlation proposed by Tan et al.50 0.47 mm 0.14 208. Nevertheless.Chapter Six 0. Dp.11. 1952) and a liquid (Brunner.79 620.55 622.11 209.32 207. the Sherwood number (Sh) was computed (see Table 6.12).61 3044 113.00 -0. which is coherent with the definition of a supercritical fluid (Guardo et al.18 27. local [m/s] 0.94 621.16 44.85 12954 628.09 0. Surface local mass transfer coefficients for hydrogen for the supercritical hydrogenation of sunflower oil at 20 MPa and 473 K From the values of k.50 1.35 360. The absence of experimental data at such high Reynolds numbers difficult the validation tasks of the obtained numerical data.05 0.16 44. Re L Sherwood number O E S H 647 44.41 Computed values for Sherwood number for oil fatty acids and hydrogen in the supercritical hydrogenation of sunflower oil at 20 MPa and 473 K at different particle sizes .56 113.07 0.47 113. (1988) for supercritical extraction in packed beds or with an extrapolation of the experimental results obtained by Brunner (1985) for a high pressure bubble column..78 64. 2006).11 5962 208.00 0. finding that obtained values for the Sherwood number are higher than those predicted by the aforementioned theoretical correlation (see Figure 6.9205 2.

47 113.6.128 - .80 139.30 3044 113. following a procedure similar to that explained priory on this chapter. Re L Sherwood number O E S H 3972 202.56 113. From the numerical results obtained. When expressing these numerically obtained mass transfer coefficients in a dimensionless way. as proven with the diffusional model and the intra-particle concentration profiles described in prior sections of this chapter.4 (for the diffusional model). a simulation set at two different temperatures (457 and 473 K) was done. (1988) 100 10 Ranz & Marshall (1952) 1 10 100 1000 10000 100000 Brunner (1985) Sh THIS WORK Re p HYDROGEN OIL Figure 6. it can also be noticed that mass transfer coefficients increase with Reynolds. Particle size of Dp = 0.3. It can be noticed that a temperature increase is reflected in a direct increase of the surface local mass transfer coefficients.86 196.12. Dp = 0.4.Chapter Six 100000 10000 1000 Tan et al. surface local mass transfer coefficients (see Figure 6.6) for the temperatures selected were estimated. Temperature.13) and Sherwood numbers (see Table 6. K 457 473 Table 6.11 Computed values for Sherwood number for oil fatty acids and hydrogen in the supercritical hydrogenation of sunflower oil at different temperatures (particle size.47 mm) .47 mm was chosen for the simulations because of being considered the optimal particle size for the hydrogenation reaction.78 64.41 202.43 113.24 198. Temperature effects on external mass transfer coefficients In order to evaluate the temperature effects on the external mass transfer coefficients for the supercritical hydrogenation of sunflower oil. Sherwood number vs. Values for the kinetic parameters and the values for the diffusion coefficients were set as show in Table 6.3 (for the kinetic model) and Table 6. Reynolds number for different particle diameters on the supercritical hydrogenation of sunflower oil at 20 MPa and 473 K 6.

0075 H2 OIL 0.69 3044 113.0132715 0.56 113.73 12.47 113.045 473 K 0. Superficial velocity. a simulation set at six different inlet flow velocities (u = 2.129 - kH2.132.0225 koil.89 30 8.75 8. Temperature effects over the surface local mass transfer coefficients for the supercritical hydrogenation of sunflower oil 6.43 114.0132 m/s) was done.00 -0.54 63.24 30.54 19. local [m/s] H2 0.0663575 0. Dp = 0.1327150 0.78 111.3271500 2.75 8.50 0 1. m/s 0.40 30.43 30.03 0. as explained in prior sections of this chapter.72 17. local [m/s] OIL 0.47 mm 0 -1.78 6077 114.32.13.66.54 Computed values for Sherwood number for oil fatty acids and hydrogen in the supercritical hydrogenation of sunflower oil at different inlet flow velocities (particle size. 0. Superficial velocity effects on external mass transfer coefficients In order to evaluate the superficial velocity effects on the external mass transfer coefficients for the supercritical hydrogenation of sunflower oil.75 152 19.50 0. 0. Values for the kinetic parameters and the values for the diffusion coefficients were set as show in Table 6.68 114. 1. Particle size of Dp = 0.01125 Dp = 0.00 Surface arc length [dimensionless] Figure 6.5.00 0.6635750 1.33 1522 111.54 304 30.03375 .6500000 Table 6.54 19.7.3.Chapter Six 0.066 and 0.61 111.54 19.4 (for the diffusional model).76 111.65.47 mm was chosen for the simulations because of being considered the optimal particle size for the hydrogenation reaction.43 113. Re L Sherwood number O E S H 5.3 (for the kinetic model) and Table 6.015 0.47 mm) .75 8.0225 457 K 0.11 64.63 114.89 64. 0.

v = 1. surface local mass transfer coefficients (see Figures 6.066 m/s v = 0.5 0 0.5 0 0.14 and 6.7) for the temperatures selected were estimated. following a procedure similar to that explained priory on this chapter.Chapter Six From the numerical results obtained.65 m/s v = 0. 0.13 m/s Figure 6.013 m/s Surface velocity effects on the hydrogen local mass transfer coefficients for the supercritical hydrogenation of sunflower oil. local [m/s] 0.66 m/s v = 0.5 1 Surface arc length [dimensionless] v = 2.5 1 Figure 6.15) and Sherwood numbers (see Table 6. Surface velocity effects on the oil fatty acids local mass transfer coefficients for the supercritical hydrogenation of sunflower oil .32 m/s v = 0.045 kH2.025 0. 0. local [m/s] 0.13 m/s v = 1.005 0 -1 Surface arc length [dimensionless] v = 2.03 0.015 0 -1 -0.15.65 m/s v = 0.02 koil.01 0.015 0.130 - .013 m/s -0.32 m/s v = 0.66 m/s v = 0.14.066 m/s v = 0.

6 and 6. Figure 6.. Obtained mass transfer coefficients are significantly lower than those obtained for a well-stirred reactor.3. 6. in order to present a simple set of equations capable to predict mass transfer coefficients in the supercritical hydrogenation of sunflower oil. numerically obtained Sherwood numbers (shown in Tables 6.33 Valid for the following range of dimensionless numbers: 30 < Re < 12954 0.66 m/s).33 ShH 2 = 0.14. an increase in superficial velocity) from 52 rad/s to 262 rad/s produces no significant increase in the reaction rates of the hydrogenation. 6. Correlating the numerically obtained mass transfer data Tan et al. (1988) correlated experimentally obtained mass transfer data for a fluid-solid system in a supercritical extractor. The diminution of the surface reaction rates and the increase of the surface mass fluxes can significantly affect the surface mass transfer coefficients.15 and the numerical data shown in Table 6. A similar situation has been studied experimentally by Ramírez et al.69 ⋅ Sc 0.Chapter Six From Figures 6.15 and Table 6..7 it can be concluded that for high superficial velocities (u > 0.3-4] .16 shows the obtained correlations for the numerically obtained mass transfer data.7) at low superficial velocities (similar velocities to those used in supercritical packed bed reactors) it can be noticed that there is a clear effect of velocity over mass transfer. suggested correlations for predicting the oil fatty acids and hydrogen mass transfer coefficients in the supercritical hydrogenation of sunflower oil are as follows: Shoil = 0.3-2] Following the aforementioned model. It was noticed that surface reaction velocities decreased with surface velocity.7) were correlated as a function of Reynolds and Schmidt numbers.6.5.14 and 6. there is no significant effect of the superficial velocity over mass transfer phenomena.8 % [6.3-3] [6. When taking a look at the surface local mass transfer coefficients (shown in Figures 6. (2004) and Ramírez (2005). fitting their data with an equation of the type: Sh = a ⋅ Re x ⋅ Sc y [6. 6. and that the total mass flux over particle surface increased with the surface velocity.131 - .5192 ⋅ Re 0. who reported for a CSTR supercritical hydrogenation reactor that an increase in operating stirrer speed (and in consequence.6765 ⋅ Sc 0. This behavior is in complete agree with the expected behavior for a well-stirred reactor.4796 ⋅ Re 0.7 < Sc < 2.1 AARD = 2. In summary.

For every simulation stage. Figure 6.47 mm was chosen for the simulations because of being considered the optimal particle size for the hydrogenation reaction. but it guaranteed that the computational size of the CFD model was kept in reasonable sizes. it can be noticed that there is a fast conversion in the first sector of the packed bed reactor. (2004. The high reaction rates obtained at the bed inlet are reflected in the small reactor sizes obtained (less than 10 cm length for Re = 200). approximately 1000 times higher than for the traditional biphasic hydrogenation process (Tacke et al.17 shows an example of the obtained concentration profiles at different simulation stages along the packed bed reactor.4796 · Re 1 1 10 100 1000 0.33 [6.3-3] Figure 6.132 - . obtained contour fields for all computed variables (velocity and species concentration) were recorded at the model flow outlet. For all cases analyzed. 2006) allowed to create a fullyheterogeneous 3D packed bed reactor model in order to study the supercritical hydrogenation process in a semi-industrial scale.3. This simulation strategy is highly timedemanding. and fed as inlet boundary conditions for the following stage. Particle size of Dp = 0. as explained in prior sections of this chapter.33 [6.69 · Sc 0. Hydrogen Equation [6. Packed bed model The validation of the intra-particle concentration profiles and the verification of the kinetic and diffusional models proposed by Ramírez et al. The packed bed model was created using a unit cell approach (a repetitive geometrical model) and simulations were carried by stages until full conversion was achieved for every case analyzed. This fact can be clearly noticed when analyzing the conversion profiles along the packed bed length (see Figure 6.3-3] Sh 10 Sh H 2 = 0..5192 · Re 0.3-4] Re 10000 100000 Oil Equation [6.16. This fact is related to the extremely high reaction rates achieved in this zone of the reactor.7.18).Chapter Six 1000 100 Sh oil = 0.3-4] Correlations for the numerically obtained mass transfer data 6. .6765 · Sc 0. 1996).

1 Reactor length [m] Re = 10 Figure 6.06 0.08 0.Chapter Six Figure 6.17. Re = 40 Re = 70 Re = 100 Re = 150 Re = 200 Conversion profile along the packed bed length for different inlet velocities at 457 K . Re = 100) 150 Iodine Value (IV) 100 50 0 0 0.18. Linoleic fatty acid concentration contour fields for different stages of the packed bed reactor model (T= 473 K.04 0.02 0.133 - .

1 mm.473 K Figure 6.9 that for a particle with Dp = 0.2 O S E 100 0 120 Iodine value (IV) 80 60 E .473 K O .6 L Mass fraction 0. This computational technique allows to obtain in a fast and economical way information that otherwise is extremely complicated and expensive to obtain experimentally. obtaining a good agreement in every case analyzed. the effectiveness factor of the catalyst is close to the unity.473 K Oil fatty acids mass fraction in the hydrogenated product (Re = 200) CONCLUSIONS Computational Fluid Dynamics proves to be a useful tool when applied to the study of the catalytic hydrogenation of sunflower oil in the presence of a supercritical solvent. L .19. An increase in the reaction temperature produces an increase of the reaction rates.Chapter Six As it is important to minimize the presence of trans C18:1 (elaidic fatty acid) in the hydrogenation product due to its health implications (Ramírez.457 K E .1 mm was also made in order to corroborate the catalyst effectiveness. It can be seen that an increase in the reaction temperature makes the reaction move primarily to the formation of stearic fatty acid. reassuring the idea that for a particle diameter of 0.4 0.457 K L . 2006). numerically obtained concentration profiles were almost identical to those reported experimentally for Dp = 0. a CFD simulation extrapolating the catalyst evaluation for Dp = 0. reducing the formation of elaidic fatty acid. . Magnitude of relative errors was evaluated for the developed simulations.457 K S .19). 2006). oil fatty acids mass fraction in the hydrogenated product was also obtained (see Figure 6. Numerical simulations for the supercritical hydrogenation of sunflower oil were validated against experimental data previously published by this research group (Ramírez et al. 0.473 K S . 2005). favoring the formation of stearic fatty acid. It can be seen in Figure 6.47 mm or lower..47 mm (Ramírez et al. finding that this value was within the magnitude order of the experimental error previously reported by our research group.134 - ..457 K O . Due to the difficulty for obtaining experimental data at very low particle sizes.

Guardo. New York. Further work must be done in the study of a packed bed reactor configuration in order to find optimal design and operation conditions for the industrial development of the supercritical hydrogenation process. Daskopoulos. Fundamentals of Industrial Catalytic Processes. Chemical Engineering Science (submitted).A. I. Chemical Engineering Science. (1985). M...J.. M.).. Larrayoz.A.... P. London. Computational fluid dynamics for chemical reactor engineering. Wang.J. Sherwood number for the process was also evaluated.Chapter Six Obtained numerical data allowed analyzing local mass transfer coefficients over the catalyst surface.8 %. (1996). Penninger. Correlations presented are valid for predicting mass transfer in a range of 30 < Re < 12954 and 0. D. it was found that for high superficial velocities the system shows the behavior of a well-stirred reactor. G. E. J.. A. New York.. . Applications of computational fluid dynamics in the chemical industry.. In: Bertucco. (1979). H. 1569 – 1594. 51..1. Buitendijk. It was found that mass transfer coefficients increased with an increase in temperature and in particle size. and it was found that its value lies in between those expected for a gas and those expected for a liquid. Casanovas. G. 17. Mass transfer in gas extraction. (2006). Hydrogenation at supercritical single-phase conditions. Rosendal.J..H.J.. Amsterdam. Vreenegoor. Porous media: Fluid transport and pore structure. Harris. F. 145 – 148.. Moller. Reaction rates obtained in the first 10 % of the length of the reactor are extremely high in every case analyzed (approximately 1000 times higher than for the traditional biphasic hydrogenation process). Elsevier Science Publishers.N. obtaining concentration and conversion profiles along the packed bed. Macher. Farrauto R..K.7 < Sc < 2. and Bartholomew C. (Eds.135 - . F. McHugh (Eds.. REFERENCES Bode. F. Academic Press. Van den Hark. (2001). Particle size..... and Vetter. a supercritical fluid technology. (1994). Recasens... High Pressure Process Technology: Fundamentals and Applications.). Martínez. When analyzing the effects of the superficial velocity over the mass transfer coefficients. UK: Chapman & Hall. Dullien... Numerically obtained Sherwood numbers were correlated as a function of Reynolds and Schmidt numbers. A.L.M.B. Chemical Engineering & Technology. M. Brunner. F. A. in order to present a simple set of equations capable to predict mass transfer coefficients in the supercritical hydrogenation of sunflower oil. Roekaerts. In: J. whit an AARD = 2. It was observed that at high superficial velocities there is no effect over mass transfer coefficients. M. M. Elsevier Science Publishers. Härröd. C. The validation of a single particle model allowed creating a 3D heterogeneous packed bed model in order to study the hydrogenation reaction in a semi-industrial scale.J.L. D. S. CFD modeling on external mass transfer and intra-particle diffusional effects on the supercritical hydrogenation of sunflower oil..G.A. Radosz and M. (1997). temperature and superficial velocity effects on external mass transfer were analyzed. Ramírez. Ph. Magaña.

173 – 180. UK: Oxford Univ. New York. 291 – 295. The properties of gases and liquids. J. Contribution to the study of heterogeneous catalytic reactions in SCFs: Hydrogenation of sunflower oil in Pd catalysts at single-phase conditions. Denn..D. In: De Simone.. 48. Evaporation from drops. (1970). Poling. Advances in Chemical Engineering 24. 2.). M. Panster. S... 1545 – 1555. . McGraw-Hill.. J. D. Ranz. M. Bischoff. W. M.. Prausnitz. New York. Transport in porous catalysts. Tacke. Ramírez. Intraparticle diffusion mechanisms in SC sunflower oil hydrogenation on Pd. New York. W. S. 2nd ed.. Elsevier Science Publishers. F. McGraw-Hill.. S.1 – 10. (2002).E. Selective and complete hydrogenation of vegetable oils and free fatty acids in supercritical fluids. Wieland. White. Ranade.. In: Wei. (Eds. New York. Journal of the America Oil Chemists’ Society. Ramírez. E. 48.. pp.. Kuipers. Liang... (2004). Ph.22.... (1987). Prentice-Hall. (1977). Stephanopoulos. W. B. Catalysis. Jackson. McGraw-Hill. Boston. G.. 38. Chemical Engineering Progress. P.. M.-C. 95 – 205. 1539 – 1553. Liou. Larrayoz. J. New York. 50.. Satterfield. Universitat Politècnica de Catalunya.. Elsevier.. Tan. Reinhold. Fernández.. pp. pp. Press.A. F. CA. The properties of gases and liquids. Panster.... 227 – 328. 3. Proceedings of the 3rd International Symposium on High-Pressure Chemical Engineering. Thesis. Mass transfer in heterogeneous catalysis. B. Muroyama. (Eds.. Seinfield. E. C. A.H. and Van Swaaij. J.56. 52.. Wheeler. Oxford.. Vol. Academic press. (1991). (1951). J. K. (1955). In: P. Zurich. R.. Hardening of fats and oils. and Trepp. AIChE Journal. Poling... In: Rudolf von Rohr. New York. Chemical Engineering Department. Kinetics of the hydrogenation of fatty oils.. pp. O’Connell. C.. E.-S. Sunflower oil hydrogenation in Pd/C in SC propane in a continuous recycle reactor. T. New York. (1952).. R. Anderson.. Switzerland.). McGraw-Hill. Chemical Engineering Journal. (2006). 482 – 542. pp.A. A.. New Jersey. J. Computational flow modeling for chemical reactor engineering. Ch.136 - . Emmett (Ed. P. Advances in catalysis.. Computational fluid dynamics applied to chemical reaction engineering. K. J. (2005). M. 17 – 22. Academic Press: San Diego.) Green Chemistry Using Liquid and Supercritical Carbon Dioxide. E. Ramírez. Nagata. (1998).). 244 – 422.Chapter Six Hashimoto.-K. Wheeler.E.N. part 1. Petersen. (2003). Recasens.. 3.. Vol. A. pp. Barcelona. S.. Tacke. AIChE Journal. Academic Press. Recasens.. Reid. P... (Ed. T. Viscous fluid flow. Prausnitz.. (1971). (1988).. J. M.. (1965). (1996). 17 ..M. F. (2000). Fluid-solid mass transfer in a supercritical fluid extractor. Larrayoz. Wieland. and Marshall Jr. K. Chemical reaction analysis.. V. P.R.

Chapter Six

Yaws, C., (1999). Chemical properties handbook. McGraw-Hill, New York. pp. 1 – 55. Youngquist, G.R., (1970). SYMPOSIUM ON FLOW THROUGH POROUS MEDIA: Diffusion and flow of gases in porous solids. Industrial & Engineering Chemistry, 62 (8), 52 – 63.

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CHAPTER SEVEN

conclusions

and future work

.

and also for calculation of pressure drop along the bed in packed bed equipment. Drag coefficient over particle surface was recorded and compared against the Stokes’ law and the graphical correlation presented by Lapple and Shepherd (1940). and a neglectable mesh dependency on the results. In the case of the prediction of heat transfer parameters. Numerical results obtained were compared against the theoretical answer for estimating the heat transfer coefficient obtained by Ranz and Marshall (1952). Fluent 5. stagnant points. and a Finite Volume code. wall channeling. Mesh sensitivity was established and optimal average mesh density for flow problems could be obtained.. For the flow validation test.Conclusions CFD proves to be a useful tool when modeling mass and heat transfer and chemical reactions in packed bed equipment. reaching information almost impossible to get by means of experimental work. flow around a simple cubic stack of spheres was used as validation model to test the capabilities of the solver reproducing experimental data.x) allowed us to simulate and validate velocity and temperature profiles around simple geometries. and optimal average mesh density over the heat transfer surface was established. and to study mass and heat transfer phenomena and heterogeneous reaction at low and high pressure in packed beds. It allows obtaining velocity. Validation models Two computational flow models were developed to validate flow and heat transfer around spheres (single or stacked). The calculated velocity profiles fitted qualitatively the expected results.e. a sphere suspended in an infinite fluid was used as validation tool to test the capabilities of the solver reproducing an analytical solution. Wall-to-fluid heat transfer CFD proves to be useful in the wall to fluid heat transfer parameter estimation. Using CFD commercially available codes (a Finite Element code.1.. A summary of the conclusions reached in each section of this thesis work is presented in this chapter.141 - .x/6. Predicted results showed excellent agreement with the experimental data of Suekane et al. This can be explained by the similarity in the . obtaining an overall good agreement between the compared sets of data. For the heat transfer validation test. and the calculated values of pressure drop along the bed adjust quite well with previously published and accepted correlations. The results obtained for all of the cases studied (laminar and turbulent) agree among themselves and with the selected empirical and semi-empirical correlations when analyzing pressure drop and effective radial conductivity. Comsol 3. (2003). eddy flows) were easily identifiable.2.x. pressure. Obtained temperature profiles inside the bed allowed estimating wall heat transfer parameters such as Nuw and kr/kf . 7. Flow structures within the bed (i. 7. mesh sensitivity tests were performed. temperature and species concentration contour plots inside the bed. It was possible to model a realistic case of a packed bed of spheres including contact points within the surfaces involved in the geometry. The model predictions were verified by comparing the simulation results with the published experimental and computational results. obtaining a good agreement between numerical and theoretical answers.

Therefore. 7. A good near-wall modeling is fundamental to obtain more accurate results in pressure drop and heat transfer calculations and the selection of the right turbulent model will depend on the geometry proposed and the values obtained for y+ in the wall. (1979) for heat transfer. and the influence of velocity over mass and heat transfer could be analyzed. κ or µt can lead to differences in flow and temperature profiles that can be translated into miscalculation of heat transfer parameters. results shows that the fitting against correlation is not good.g. and turbulent solutions tend to underestimate the value of the coefficient in the laminar transition zone.3. Results obtained with the Spalart–Allmaras turbulence model show better agreement than the two-equation RANS models for pressure drop and heat transfer parameter estimation. For a single velocity condition different meshes give results in a wide range of Nu and no relation with mesh density can be established in any case. Turbulence models used for simulations do not predict the transition regime well. This situation is especially notorious when analyzing heat transfer. Factors such as the misestimating of ε. To define an adequate y+ for a correct coupling for the two-equation models at the near-wall treatment is not an easy task. Therefore. the Spalart – Allmaras model could be a good tool for these kinds of flows because the y+ problem is solved automatically in spite of the necessity of checking the upper values of y+ (less than 120). Particle-to-fluid convective mass and heat transfer at low and high pressure CFD proves to be a reliable tool when modeling convective mass and heat transfer phenomena in packed beds. It allows to analyze either free or forced convection situations and the obtained results can be compared qualitatively and quantitatively against previous published data. This could be due to the fact that this model uses a coupling between wall functions and damping functions for near-wall treatment. Results present slower ratios of convergence at low Re than at high Re. No mesh sensitivity was .Conclusions velocity field obtained for each simulation. and this can be seen in the discrepancy between numerically obtained results and correlations in the low Re and transition range. The calculation of these parameters is more closely related to velocity fields than to mixing parameters. the y+ parameter is crucial during the selection of the appropriate turbulence model to apply within the simulation. A laminar solution overestimates the value of this coefficient in the turbulent flow zone. For values of Re > 10 it was obtained a good agreement with the correlations presented by Wakao and Kaguei (1982) for mass transfer. the κ − ε family models). Flow regime zones can be identified using the heat transfer coefficient estimate. and this fact affects the definition of an appropriate y+ parameter in order to apply a correct near-wall treatment for certain turbulence models (e. The definition of a good mesh allows calculations of fluid dynamics variables.142 - . At lower Reynolds numbers (Re < 10). the proposed geometry governs mesh density and element size in the near-wall area. and Wakao et al. Forced convection at low pressure in a packed bed was simulated. as velocity and pressure. Turbulence models used for simulations do not properly predict the transition regime and this can be observed in the discrepancy between numerically obtained results and correlations in the low Re and transition range. does not include additional diffusion or dissipation terms in its formulation and does not present the stagnation point anomaly. in our case. However. The prediction of the mixing rate within the bed along with the near-wall treatment appreciably affects the estimate of Nuw.

Conclusions

noticed for the laminar and transition flow zones, but in the turbulent flow zone a good definition of the mesh around the particles surface is of primal importance in order to capture the turbulence vorticity energetic scales associated effects. Mixed (free+forced) convection at high pressure in a packed bed was also analyzed. For a supercritical fluid in laminar flow regime it was possible to study the effects of the density gradient, flow direction and velocity over mass and heat transfer. It was noticed that the presence of large density gradients conditioned the mesh influence over the numerical results when computing the mixing and the mass/heat transfer within the computed domain. An adverse density gradient generates hydrodynamical instabilities that produce an increase of the axial dispersion and a diminished mass/heat transfer rates. This fact caused numerical instability in the simulation process. In order to eliminate numerical instability, the mesh was locally refined in each case trying to avoid the presence of high density and velocity gradients along the bed. Influence of flow direction over mass/heat transfer was also analyzed and it was noticed that in assisting flow regime, greater heat transfer rates are obtained. The rising in the density along the bed height due to the adverse density gradient helps the axial dispersion to grow, obtaining less mixing within the bed and smaller heat transfer coefficients. Flow velocity also affects the heat transfer rate. The value of Sh and Nu increases almost linearly with flow velocity and this increase is due exclusively to the increase in the contribution of forced convection to the overall mass/heat transfer. Free convection is independent of flow velocity and its value remains almost constant within the studied velocity range. A novel correlation (Eq. [5.3-3]) is presented for estimating the free and forced convection effects and Nu from Re, Pr and GrH . Presented correlations are valid for 9 < Re < 96, 2.2 < Pr < 3.3, and 1 × 108 < GrH · Pr < 4 × 1010. The obtained numerical results validates the idea that the modified correlation presented (Guardo et al., 2006), based on the one proposed by Stüber et al. (1996) for mixed convection mass transfer under supercritical conditions in packed beds, can be used to describe heat transfer phenomena in a supercritical packed bed reactor under mixed convection regime at high pressures.

7.4.

High pressure heterogeneous reaction

Computational Fluid Dynamics proves to be a useful tool when applied to the study of the catalytic hydrogenation of sunflower oil in the presence of a supercritical solvent. This computational technique allows to obtain in a fast and economical way information that otherwise is extremely complicated and expensive to obtain experimentally. Numerical simulations for the supercritical hydrogenation of sunflower oil were validated against experimental data previously published by this research group (Ramírez et al., 2006), obtaining a good agreement in every case analyzed. Magnitude of relative errors was evaluated for the developed simulations, finding that this value was within the magnitude order of the experimental error previously reported by our research group. Due to the difficulty for obtaining experimental data at very low particle sizes, a CFD simulation extrapolating the catalyst evaluation for Dp = 0.1 mm was also made in order to corroborate the catalyst effectiveness. It can be seen in Figure 6.9 that for a particle with Dp = 0.1 mm, numerically obtained concentration profiles were almost identical to those reported

- 143 -

Conclusions

experimentally for Dp = 0.47 mm (Ramírez et al., 2006), reassuring the idea that for a particle diameter of 0.47 mm or lower, the effectiveness factor of the catalyst is close to the unity. Obtained numerical data allowed analyzing local mass transfer coefficients over the catalyst surface. Sherwood number for the process was also evaluated, and it was found that its value lies in between those expected for a gas and those expected for a liquid. Particle size, temperature and superficial velocity effects on external mass transfer were analyzed. It was found that mass transfer coefficients increased with an increase in temperature and in particle size. When analyzing the effects of the superficial velocity over the mass transfer coefficients, it was found that for high superficial velocities the system shows the behavior of a well-stirred reactor. It was observed that at high superficial velocities there is no effect over mass transfer coefficients. Numerically obtained Sherwood numbers were correlated as a function of Reynolds and Schmidt numbers, in order to present a simple set of equations capable to predict mass transfer coefficients in the supercritical hydrogenation of sunflower oil. Correlations presented are valid for predicting mass transfer in a range of 30 < Re < 12954 and 0.7 < Sc < 2.1, whit an AARD = 2.8 %. The validation of a single particle model allowed creating a 3D heterogeneous packed bed model in order to study the hydrogenation reaction in a semi-industrial scale, obtaining concentration and conversion profiles along the packed bed. Reaction rates obtained in the first 10 % of the length of the reactor are extremely high in every case analyzed (approximately 1000 times higher than for the traditional biphasic hydrogenation process). Further work must be done in the study of a packed bed reactor configuration in order to find optimal design and operation conditions for the industrial development of the supercritical hydrogenation process.

7.5.

Future work

Further work on the study of heat and mass transfer phenomena in packed beds can be done applying a CFD methodology, especially when dealing with supercritical fluids. The advantages of CFD simulations (low cost, fast and reliable information) can be applied to situations where obtaining experimental data is technically complex and not cost effective. When dealing with supercritical fluids, materials and equipment needed to deal with the high pressures and high temperatures required for the experimentation are extremely expensive, limiting sometimes the experimentation possibilities. Further work can be done in this subject, using CFD to simulate complex situations involving supercritical fluids, as radial effects in packed beds or axial dispersion studies when natural convection is involved into the heat/mass transfer phenomena. Further research can be done for studying the effects of the configuration of the packing structure in the efficiency of the transport process, and the effects of the geometrical configuration (particle size, pore size and pore distribution) on transport and reaction parameters.

REFERENCES

Guardo, A., Coussirat, M., Recasens, F., Larrayoz, M.A., Escaler, X., (2006). CFD study on particle-to-fluid heat transfer in fixed bed reactors: Convective heat transfer at low and high pressure. Chemical Engineering Science, 61, 4341 – 4353.

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Conclusions

Lapple, C.E., and Shepherd, C.B., (1940). Calculation of particle trajectories. Industrial & Engineering Chemistry, 32, 605 – 617. Ramírez, E., Larrayoz, M.A., Recasens, F., (2006). Intraparticle diffusion mechanisms in SC sunflower oil hydrogenation on Pd. AIChE Journal, 52, 1539 – 1553. Ranz, W.E., and Marshall Jr., W.R., (1952). Evaporation from drops, part 1. Chemical Engineering Progress, 48, 173 – 180. Suekane, T., Yokouchi, Y., Hirai, S., (2003). Inertial flow structures in a simple-packed bed of spheres. AIChE Journal, 49, 10 – 17. Stüber, F., Vázquez, A.M., Larrayoz, M.A., Recasens, F., (1996). Supercritical fluid extraction of packed beds: external mass transfer in upflow and downflow operation. Industrial & Engineering Chemistry Research, 35, 3618–3628. Wakao, N., Kaguei, S., Funazkri, T., (1979). Effect of fluid dispersion coefficients on particle-tofluid heat transfer coefficients in packed beds: correlation of Nusselt numbers. Chemical Engineering Science, 34, 325 – 336. Wakao, N., and Kaguei, S., (1982). Heat and mass transfer in packed beds. Gordon and Breach Science Publishers, New York. pp. 138 – 160; 264 – 295.

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APPENDICES .

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« Open book » .APPENDIX A on CFD design issues. supercritical fluids extraction and reaction BIBLIOGRAPHIC REVIEW Luke Andrews.

« Turbulence » .Michael Graf.

2000 Rónyai et al..5 – 12 8 – 35 9 10 – 40 6. 1999 Daukšas et al. 2001 Daukšas et al. 1998 Ferreira et al. 2002 Monteiro et al. and there is a growing interest in developing such processes..5 – 30 20 – 30 30 25 – 35 15 – 45 8 – 28 25 – 30 7 – 30 20 – 30 20 – 30 10 – 20 25 20 – 25 Solvent CO2 CO2 + ethanol CO2 CO2 + caprylic acid methyl ester CO2 CO2 CO2 + ethyl alcohol CO2 Ethane CO2 CO2 CO2 CO2 + ethanol CO2 + ethanol CO2 + ethanol CO2 CO2 CO2 + ethanol CO2 + propanol CO2 CO2 CO2 + H2O CO2 Propane CO2 CO2 CO2 CO2 CO2 CO2 Propane CO2 + ethanol CO2 + ethanol CO2 References Doneanu and Anitescu. 1997 del Valle et al.) seeds Caraway (Carum carvi L.Brazilian fruit Dandelion leaves Dehydrated orange peel Dried Saw Palmetto berries St. 2002 Total extract β . 1999 Esquível et al... 1999 Daood et al. 2002 Ginkgo leaves Ground pyrethrum flowers Guaraná seeds Hiprose fruit Jalapeño peppers (Capiscum annuum L.) seeds Coriander seed Corn germ Cupuaçu (Theobroma grandiflorum). root Australian ginger root Black pepper (Piper nigrun L.3 – 20 16 – 69 12 – 18 Chiu et al. 1999 Table A-1...) Nutmeg (Myristica fragans Houttuyn) Pungent spice paprika powder Shells of the bacuri fruit (Platonia insignis Mart) Soybeans Summer savory (Satureja hortensis L. 2002 Baysal and Starmans.) 333 – 393 293 – 313 313 – 343 298 – 308 313 308 – 313 296 – 323 313 – 323 296 308 – 328 289 – 323 333 – 353 313 24 – 31 7 – 25 10 – 40 5 – 25 12 – 32 10 – 18 8. Limonene Oil Oil Total extract β . 2003 Saldaña et al.Amyrin β .151 - . Raw material Angelica archangelica L. 2001 Carlson et al. 1998 Badalyan et al..] Rauschert) Freeze dried carrots Ginger (Zingiber officinale Roscoe) Extract Oil Oil Essential oil Total extract Carvone... Vegetal products extractions carried out in SCF ..Appendix A A-1. animal and wood/fibre material can be carried out with a supercritical solvent (see Tables A-1 to A-3). 1999 Catchpole at al.) Borage (Borago officinalis L.. 2002 Mira et al.. 2003 Ribeiro et al.. 1998 Zancan et al.... 2001 Subra et al. specially for the food. 1999 Illés et al..Sitosterol Oil Limonene Total extract T [K] 313 282 – 308 303 – 323 313 305 – 348 308 315 323 – 343 308 – 338 293 – 323 313 – 323 295 – 323 311 – 323 313 – 333 303 – 313 330 303 – 313 P [M Pa] 12 6 – 10 15 – 30 10 – 35 7. 2002 Illés et al. 2002 Kiriamiti et al.carotene Oleoresin Terpene lactones and flavonoids Pyrethrins Caffeine Total extract Oleoresin Total extract Antioxidants Essential oil Essential oil Oil Oleoresin Total extract Oil Oil Povh et al. Extraction of natural products A wide range of extractions of natural products from vegetal.) prepelletised Lemon balm (Melissa Officinalis L. 1999 Spricigo et al... cosmetics and pharmaceutical industries.) Lemongrass (Cymbopogon citratus) Lovage (Levisticum officinale Koch. John’s Wort flowers Echinacea purpurea (aerial parts) Kava roots and stems Flowers of chamomile (Chamomilla recutita [L... 1998 de Azevedo et al.... 1997 Montanari et al.. 2003 Simándi et al..

Tributyl phosphate CO2 + ethanol/water CO2 + methanol References Cellulose-based filter papers Uranyl nitrate Shamsipur et al.Appendix A Raw material Atlantic mackerel (Scomber scombrus) Black scabbardfish (Aphanopus carbo) Cow brain Dried egg yolk Pigskin Raw wool Sheepskin Wool scour wastes Extract Oil PCB..20 10 – 24 10. Wood and fiber material extractions carried out in SCF A-2. the removal of typical industrial wastes (PAH. chlorinated pesticides Cholesterol Phospolipids Fat Natural wax Fat Wax T [K] 308 309 – 337 323 . 2006 Eychenne et al. Fish and animal material extractions carried out in SCF Raw material Extract T [K] 333 P [M Pa] 25 Solvent CO2 + methanol. 2003 Vedaraman et al. 2000a Marsal et al. 1987 Polycyclic aromatic hydrocarbons (PAH) ~ 100 % 313 – 423 40 Barnabas et al. 2005 Carbamate pesticides Gasoline Diesel 39.343 313 293 – 313 303 . Contaminant PCB 1.5 10 .7 10 ....6 – 91. 1995 Table A-4.353 318 313 353 P [M Pa] 34. Soil remediation Decontamination of soils using SCF is an attractive process compared to extraction with liquid solvents because no toxic residue is left in the remediated soil and in contrast to thermal desorption soils are not burned. 1998 Antunes et al..1-trichloroethane (DDT) Toxaphene Removal efficiency 70 – 90 % T [K] 313 P [M Pa] 10 Solvent CO2 CO2 CO2 + methanol Acetone Hexane Methanol Toluene CO2 CO2 + methanol CO2 References Brady et al. 2001 Marsal et al.152 - . 2005 McDaniel et al. 2000 Vaquero et al. 2001 Sugar cane bagasse Pinus Taeda wood chips Wood pulp Lignine Total extract 415 – 471 353 14..23 51.1. Examples of applications of SCE to soil remediation .7 % > 88 % 327 353 37. Specially. 2000b López-Mesas et al. 2005 Boselli and Caboni. 2005 Table A-2.60 7 . acetyl acetone.6 Pasquini et al.... 1996 Yang et al. 2001 Table A-3. fuels) can be easily achieved through SCE (see T able A-4)...7 ... 1995 Lojková et al. PCB..8 34 Izquierdo et al. methylisobutyl ketone.4 – 24 25 Solvent CO2 CO2 CO2 CO2 CO2 CO2 + ethanol CO2 CO2 + toluene References Dunford et al..24 23 – 27 51.

pirene Palm oil Soybean oil Sunflower oil Pt/Al2O3 Pt/Al2O3 CO2+n-pentane CO2+n-hexane 291 300.7 18 27. 1995 Dooley and Knopf. 2002) . 2001 Bertucco et al. 1999. 1990.6 20 5 Collins et al.4 Dardas et al. 1987 Fan et al.488 8 – 16 6 – 12 13.413 428 .5-triisopropylbenzene Ethylbenzene to benzene and diethylbenzene Oleic acid and methanol Catalyst type Zeolite Zeolite Deloxan Solvent T [K] ALKYLATION 323 – 473 323 – 413 433 – 573 P [MPa] 3.. Heterogeneous catalysis The use of SCF as a reaction media can be a real advantage when using heterogeneous catalysts. 1998 Hitzler et al. 1997 van den Hark et al.. since the diffusion rates are enhanced compared to reactions in the liquid phase..408 393 .Propane CO2 .Propane CO2 CO2 Propane CO2 Propane CO2 Propane Dimethyleter 323 – 433 313 – 593 343 323 – 493 473 – 573 323 338 .. 2001 King et al. Ramirez et al. 1991a. 2001 Macher and Holmqvist. 1991b Snavely and Subramaniam.36 – 5.95 – 1. 1996 McCoy and Subramaniam. 1999.4 HYDROGENATION Deloxan Deloxan Pd/C Pd/Al2O3 Cu Pd/C Pd/C Ni Pd/C CO2 .4 – 5. 2003 Hitzler and Poliakoff. 2004 Ramirez. 1998 CRACKING Zeolite 598 3. 1984 Tiltscher and Hofmann. 2001 Ramirez et al.4-diisopropylbenzene to cumene and 1.3 FISHER – TROPSCH SYNTHESIS CO and H2 to liquid hydrocarbons n-hexane n-hexane 313 – 341 513 4.. See Table A-5 for further details on chemical reactions carried out in SCF.5 15 – 20 References Isopentane Isobutane CO2 Propene CO2 Heptane Fan et al.6 12 – 17. 1996 DISPROPORTIONATION Zeolite Zeolite Zeolite Benzene n-pentane Butane Pentane CO2 593 – 598 533 573 – 673 3. 1997a Clark and Subramaniam.3. 1997 Arunajatesan et al.7 OXIDATION Co/Al2O3 Pd/C CO2 281 426 8 4. 2005 Table A-5.153 - . 1997 Vieville et al. 1986 Niu and Hoffmann. 1998 Tiltscher et al. Reaction Isopentane and isobutene Isobutane and isobutene 1-butene and isobutane Mesytilene and propene Mesytilene and propan-2-ol Heptane Toluene to p-xylene and benzene 1.... 1997b ESTERIFICATION Sulfonic Ru/Al2O3 Co/SiO2 Fe > 823 0. Survey of heterogeneous catalytic reactions carried out under supercritical conditions (Baiker.. 1997 Clark and Subramaniam. 1995.5 – 5 3.4 – 15...... 2000. 1993 Yokota et al. 2001 Chouchi et al...5 15 14 15 14 20 Tacke et al.Appendix A A-3.5 7–8 ISOMERIZATION 1-hexene 1-hexene to olefinic oligomers Toluene to benzaldehyde Isobutane to tert-butyl alcohol Fats and oils Acetophenone Cyclohexene Cyclohexene Unsaturated ketones Fatty acid methyl esters α .

Turbulence models for non-Newtonian fluids are not well developed. transport rates near walls. key design issues. Constitutive equations for complex fluids are not well developed. Reasonable for turbulent flow of simple fluids. flow meters. Experiments Influence of small-scale features performance (Liou et al. 2003). 2003) .. end effects.. extrapolation to non-standard configurations. CFD codes / design applicability PATH FORWARD Limitation of current models Geometrical complexity: grid quality. (Joshi and Ranade. closure models. key design issues. 2002).Appendix A A-4. Typical process equipment.. Development needed for overcoming the limitations Behavior of complex fluids in nonrheometric flows (Rothstein and McKinley. CFD in chemical engineering process equipment design and Typical process equipment. Measurement of local concentration and segregation profiles (Verschuren et al. Table A-6. computing resources. Constitutive equations based on molecular structure (van Ruymbeke et al. CURRENT STATUS Knowledge of physics Excellent for laminar flow of simple fluids. constitutive equations and turbulence models control the quality of simulations. Turbulence: transition regime. Commercial CFD codes/models allow implementation of different constitutive equations/non-uniform material properties. T mixers. Turbulence models adaptable to the resolution requirements (Speziale..154 - . and perspectives on the current status of CFD for simulating flows of practical interest in chemical engineering are summarized in Tables A-6 to A-11. Applicability is generally excellent for laminar flows of Newtonian and simple nonNewtonian fluids. and perspectives on the current status of CFD for simulating single-phase flows through conduits/channels (Joshi and Ranade. 1994). pipe fittings. reasonable guidelines for such a selection are available. Reactive mixing: computing resources. identification of hot spots/dead regions. 2001). membrane modules. mixing. Data at the onset of turbulence (Palikaras et al.. curvature effects. CFD simulations are widely used for addressing key design issues. 2003). on Physical models Influence of curvature and severe changes in flow direction on turbulence or complex fluids (Suga. residence time distribution. heat transfer coefficient. monoliths. Grid quality. limited for viscoelastic/structured fluids. Typical equipment Design issues / applications Pipes. Pressure drop. influence of non-uniform material properties. 1984). heat exchangers. valves. etc. Measurement of wall transport rates for model discrimination (Vogel. Rheological complexity: constitutive equations. 2002). 2002). It is essential to ensure that the appropriate turbulence model is selected for simulating complex turbulent flows even for qualitative screening of configurations. 2002). 1998). solvers/algorithms. Understanding the role of unsteady flows (spatially or temporally) in mixing and other transport processes (Jana et al.

spray coating. multiphase flow through monoliths. curvature effects. in some instances. non-uniform material properties. Quantitative prediction of instabilities and regime transitions is not yet adequately possible. Flow regimes: grid quality. Experiments Physical models Characterization of wetting and drop Models for wetting characteristics dynamics on different surfaces (Ted (Fukai et al. etc. 2003) Table A-7. calibrated models may be used for design. heat/mass transfer coefficients. Transport at interface: capturing small-scale features of the interface. Typical process equipment. Characterization of film flows and Capturing small-scale structures on associated instabilities (Ambrosini et al. contact angle. 2002). the interface. and wetting and wall adhesion is not adequate. learning tool for developing macroscopic closure models. fiber spinning. Demands on grid resolution/computing resources are high: usually threedimensional simulations are needed. CFD simulations are used more as a learning tool than as a design tool. White et al. computational resources.. Prediction of “die-swell” and other peculiar characteristics of viscoleastic fluids.. computation of gradients at the interface.155 - . grid quality. Data on the influence of viscoelasticity Interface models to capture regime on evolution of free surfaces (Coopertransitions. transport of the interface. key design issues. small time step and several iterations per time step are needed for simulating transients accurately. hot spots. simulations require expert intervention. CURRENT STATUS Basic models to capture the role of surface forces on the shape of the interface between immiscible phases are available. Shape of free surface/film thickness.. influence of surface characteristics (roughness/wetting). Constitutive equations suitable for practical flows of interest. 2002). .. 1995) Mao et al. 2002). Commercial CFD codes allow simulating free surface flows with the “volume of fluid” (VOF) approach or other front tracking methods.Appendix A Typical equipment Design issues / applications Knowledge of physics CFD codes / design applicability Limitation of current models Development needed for overcoming the limitations Falling film evaporators. Influence of gradients of surface Data on mass and heat transfer through tension on transport rates the interface (Gulawani. convergence behavior is sensitive to the grid quality VOF-based codes are relatively robust compared to those with surface tracking. 1997). PATH FORWARD Wetting and wall adhesion: hysteresis in contact angle. and perspectives on the current status of CFD for simulating free surface flows (Joshi and Ranade. Understanding of surface characteristics.

break-up. CFD simulations are used for understanding different design configurations mainly to assist engineering decision making. CFD codes / design applicability Prediction of mean flow is reasonably good. Models for granular flows in kilns/ball mills are inadequate. Commercial CFD codes/models allow simulations of rotating elements with either quasi-steady or sliding mesh approaches. and temperature for solidliquid flows. PATH FORWARD Limitation of current models Free surface at the top/vortex/gas entrainment. size. etc.Appendix A Typical equipment Design issues / applications Rotating disk contactors. Physical models Calibration of parameters of the turbulence models. non-Newtonian fluids. Experiments Data near the top free surface (Desai and Joshi. A priori prediction of multiphase flows in stirred vessels or rotary kiln is not possible. screw extruders. Measurement of turbulence kinetic energy. Modified wall functions to capture heat transfer near walls with complex curvatures (Churchill and Zajic. 2002). Fine resolution is needed to capture vortices around rotating elements. 1996). Turbulence: transition regime. Local measurements of heat transfer coefficients at different coil/jacket configurations (Karcz. and particle sizes at higher phase fractions (Bombač et al. accumulation behind rotating elements. 1997). 2002). coefficient of restitution. Quantitative prediction of turbulence characteristics is still not good. Models for simulating formation of gas cavities behind the blades Development needed for overcoming the limitations Table A-8. mixing/residence time distribution.. 1993). Interface closures and coalescence/breakup models for high phase factions. 1996) Turbulence models/wall functions for nonNewtonian fluids (Son and Singh. ball mills. stresses and energy dissipation rate (Joshi et al. Multiphase flows: coalescence/agglomeration. Measurements of angle of internal friction. Local measurements of phase fractions. 1999). key design issues. phase velocities. granular pressure.. Typical process equipment. Ways of capturing low-frequency flow structures. full transient simulations based on the sliding mesh approach are very computation intensive. centrifuges. scale-up/scale-down CURRENT STATUS Adequate for single-phase flows in stirred vessels. 2003) . location and speed of impellers or rotating walls. 2001) Characterization of unsteady flow and its impact on the performance (Kresta and Wood.156 - . regime-specific models with calibrated parameters may provide useful design information. Improved models for estimating the frictional viscosity of solid particles sliding on each other. heat and mass transfer. Number. 1989).. pumps/turbines. Knowledge of physics Models for simulating dispersion or suspension of multiphase flows are inadequate. stirred reactors/mixers. and perspectives on the current status of CFD for simulating stirred or rotating vessels (Joshi and Ranade. Low-frequency unsteady flows. shape. Characterization of cavities formed behind rotating blades (Lu and Ju. rotary kilns/dryers. Influence of the free surface/vortex on flow in the stirred vessels (Ciofalo et al. heat and mass transfer.

condensers/evaporators. lift and virtual mass coefficients under different conditions (Tomiyama et al. closures for interface coupling for turbulent. Measurement of the interfacial area and local mass transfer coefficients (Sun et al. sensitivity with hardware changes. Distributor design..Appendix A Typical equipment Design issues / applications Bubble/slurry columns fluidized beds. Though basic solvers for Eulerian-Lagrangian and Eulerian-Eulerian approaches are available in commercial CFD codes. turbulent dispersion of particles. CFD codes / design applicability A priori prediction of flow regimes is still not possible. Eulerian-Lagrangian and Eulerian-Eulerian approaches are used for simulating diluted and dense flows respectively. Typical process equipment. scale-up. distillation trays. 2002). Use in practical design is often indirect: for qualitative screening and for assisting engineering decision making rather than for quantitative simulations. user-defined functions are needed to implement problem-specific sub-models and closures. 2003). 2002). Local measurements of size distribution to track evolution of it within the vessel (Buwa and Ranade. Data on Lagrangian quantities (Cassanello et al. 2002). several particle trajectories need to be simulated for an adequate picture. Knowledge of physics Inadequate for dense multiphase flows. flow regime.. Models are often calibrated without obtaining grid-independent results. and perspectives on the current status of CFD for simulating multiphase flows (Joshi and Ranade. CURRENT STATUS Reasonable for dilute multiphase flows. lift and virtual mass transfer coefficients (Sankaranarayanan and Sundaresan. Experiments to quantify the fraction of energy dissipated in the bulk of the continuous phase (away from the interface). dense dispersions are not adequate. mass and heat transfer.157 - . Turbulence caused by dispersed particles.. Guidelines to select appropriate coalescence/break-up kernels. ad hoc models to simulate the influence of turbulence or other particles are used. Better understanding of the formation of agglomeration/clusters and their influence of transport rates (Harris et al. cyclones. which have to be obtained from experimental data. Experiments Unambiguous experimental data to determine drag. Phase change (evaporation/condensation). furnace/boilers. spray columns/extraction columns. crystallizers/precipitators. lift coefficient and virtual mass coefficient. Models to ensure correct Lagrangian correlations (Gouesbet and Berlemont. 2003) . settling tanks. Momentum transport between different dispersed phases. 1999). Agglomeration/coalescence/break-up process. Experiments allowing separation of dispersion effects from lift and other effects. Models to estimate the effective dispersion coefficients as a function of particle size and local turbulence length scales. erosion. minimal fluidization/suspension velocity. key design issues. mist eliminators. energy and mass transfer. 2002). Development needed for overcoming the limitations Table A-9. PATH FORWARD Limitation of current models Trajectory simulations in turbulent flows: drag coefficient. Physical models Direct numerical simulation (lattice Boltzmann or surface tracking) of multiphase flows to provide theoretical basis to empirical correlations of drag. 2001). Models involve several parameters. Improved models for the interface momentum.. distribution of dispersed phase and interfacial area. entrainment.

Table A-10. etc. CFD simulations are used to address design issues of equipment involving single phase or dilute multiphase reactive flows. 2001).. Models of cluster formation and to predict their influence on reaction rates. Selectivity and yield. Knowledge of physics Closures for turbulent reactive mixing are available only for simple reaction schemes. burners. 2000). Turbulent reactive mixing in liquids. Inadequate models for interfacial area limit modeling of multiphase reactive flows. Single phase reactive mixing models may be solved using the existing framework with additional closure models (probability density function/phenomenological approaches). 2003) . PATH FORWARD Limitation of current models Laminar reactive mixing in complex fluids. Typical process equipment. and perspectives on the current status of CFD for simulating reactive flows (Joshi and Ranade.Appendix A Typical equipment Design issues / applications Reactors for fast reactions (comparable time scales of mixing and reactions). CURRENT STATUS Reasonable for single phase laminar flow. etc. Single particle combustion data under controlled flow situations. complete combustion and energy efficiency. NOx formation. nozzle designs. 1998). Simulations of reactive flows are computationally very demanding.158 - . and it is difficult to eliminate the influence of numerical issues completely. Quantification of the role of complex rheology on stretching and folding to create large interfacial areas. combustors. 2001). key design issues. Development needed for overcoming the limitations Experiments to quantitatively measure the reduction in scale of mixing and intensity of mixing (Buchmann and Mewes. Dilute/dense multiphase reactive flows. Models/correlations for interface transport rates from drops/particles with phase change. Physical models Better understanding of interaction between turbulent. mixing and reaction for cases with one of the reactants or products existing in a different immiscible phase (Marchisio et al. Measurements of local interfacial area and transport coefficients from agglomerated particle clusters (van der Bosch. Measurements of cross correlations of concentrations for improved closures. CFD codes / design applicability Particle level reactions may be simulated with the Eulerian-Lagrangian approach. Closure models for simulating complex reaction schemes.. Capability of simulating multiphase reactive systems with the Eulerian-Eulerian or VOF approach is still in the primitive stages. user defined functions are needed for implementing specific phenomenological closures. Experiments Measurements of reduction in striation thickness with time under wellcharacterized flows for complex fluids (Fourcade et al. Measurements of transport coefficients under evaporation or condensation.

and perspectives on the current status of CFD for simulating flow through packed beds (Joshi and Ranade.. Pressure drop. Pressure drop measurements along with local turbulence characteristics (Niven.159 - . CURRENT STATUS Knowledge of physics Lumped models with or without isotropic porosity are used. gas-liquid and liquid-solid phases under different flow regimes (Jiang et al. 2002). 1995). 2002). closure models suitable for multiphase flows through packed beds are not adequate. Models to represent transient or low Re turbulent flow through complex geometry with severe curvature. bypass and channelling (Tsochatzidis et al. 2003) . drag. Reasonable results for single phase flows. Table A-11. axially averaged. Quantitative representation of the role of wetting and hysteresis on contact angle. mixing and residence time distribution. Detailed modeling of a packed bed.. is being explored in recent studies. packed columns. use for designing multiphase flow through a packed bed is in the primitive stage. Capability of simulating multiphase flow through packed beds is almost nonexistent except via user defined functions based on empirically calibrated closure models.. standard deviation and so on) with quantification of the way of packing (Sharma et al. Experiments Measurements of porosity distribution (with different length scales) within a packed bed (mean. 2002). Simulation of flow regimes/transition and unsteady flows. 2000). Commercial CFD codes/models allow simulations of single phase flows through porous media with isotropic or non-isotropic permeability and inertial resistance coefficients. Local phase distributions and velocity measurements for gas-liquid flow through well-characterized packed beds (Gladden et al. 2001). Mixing and liquid dispersion: role of capillary forces/wetting. heat/mass transfer coefficients. Quantification of the role of gradients of porosity and capillary forces on liquid dispersion (Yin et al. Used for designing equipment with single phase flow through a porous medium. 2002)... key design issues. etc. Interface closure models for estimating gassolid. which is very computational intensive. Limitation of current models Closures for multiphase flow through packed beds: interfacial area. Experimental data (global as well as local measurements) on liquid dispersion. Development needed for overcoming the limitations Models to simulate different packing possibilities (Spedding and Spencer. CFD codes / design applicability PATH FORWARD Representing void space in packed beds: grid quality. computing resources. Detailed measurements of unsteady flow regimes (quantification of key spatial and temporal scales). flow maldistribution and channelling. scale-up. filters. trickle-bed reactors. Typical process equipment. Physical models Direct numerical simulations or VOF simulations are needed to guide the development of closures.Appendix A Typical equipment Design issues / applications Monoliths. fixed beds.

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APPENDIX B Transport equations. turbulent quantities and convective heat and mass transfer modeling TURBULENCE MODELS Michael Graf. « Turbulence » .

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ν ~ is viscosity except in the near-wall (viscous-affected) region. Sν Note that since the turbulence kinetic energy is not calculated in the Spalart-Allmaras model. The Spalart-Allmaras model B-1.1. Gν . the last term in Eq. is computed from ~f µ t = ρν v1 where the viscous damping function. is identical to the turbulent kinematic transported variable in the Spalart-Allmaras model.3.Appendix B B-1. µ t . [2. σ ν ~ is a user-defined source term. The model proposed by Spalart and Allmaras (1992) solves a transport equation for a quantity that is a modified form of the turbulent kinematic viscosity. Transport equation In turbulence models that employ the Boussinesq approach.2. The transport equation for ν ~⎫ ~ ⎞2 ⎤ ⎧ ⎛ ∂ν ∂ ∂ 1 ⎡ ∂ ∂ ν ⎪ ⎪ ~ ~ ~ ⎟ ⎥ − Y + Sν~ (ρ ν ) + (ρ ν u i ) = Gν + ⎢ ⎨(µ + ρ ν ) ⎬ + C b 2 ρ ⎜ ⎜ ∂x ⎟ ⎥ ν ∂t ∂x i ∂ x σ ν~ ⎢ ∂x j ⎪ ⎪ j ⎭ ⎩ ⎝ j⎠ ⎦ ⎣ [B-1] where Gν is the production of turbulent viscosity and Yν is the destruction of turbulent ~ and viscosity that occurs in the near-wall region due to wall blocking and viscous damping. B-1.171 - . f v1 . is modeled as ~~ Gν = C b1 ρ S ν [B-5] ~ ν ~ Θ ≡ Θ + 2 2 f v2 κ d [B-6] . the central issue is how the eddy viscosity is computed.1-8] is ignored when estimating the Reynolds stresses. is given by [B-2] f v1 = Χ3 Χ 3 + C v31 [B-3] Χ≡ ~ ν ν [B-4] B-1. Modeling the turbulent viscosity The turbulent viscosity. Modeling the turbulent production The production term. C b 2 are constants and ν is the molecular kinematic viscosity. The ~ .

[B-14] . [B-6].622.4187.1. Model constants The model constants have the following default values (Spalart and Allmaras.172 - . C w 2 = 0.3.4. κ = 0. 1992): C b1 = 0. 2 3 C v1 = 7. and Θ is given by Eq. C w1 = C b1 C b 2 = 0. Modeling the turbulent destruction The destruction term is modeled as ~⎞ ⎛ν Yν = C w1 ρ f w ⎜ ⎟ ⎝d ⎠ 2 [B-10] 1 ⎡ 1+ C6 ⎤ f w = g ⎢ 6 w3 6 ⎥ ⎣ g + C w3 ⎦ 6 [B-11] g = r + C w2 r 6 − r ( ) [B-12] ~ ν r≡ ~ 2 2 Θκ d C w1 .Appendix B f v2 = 1 − Χ 1 + Χ f v1 [B-7] C b1 and κ are constants. C w2 and C w3 are constants.1355.0. By default. κ2 + 1 + Cv 2 σ ν~ . σ ν~ = . [B-13] ~ B-1.5. C w3 = 2. Θ is based on the magnitude of the vorticity: Θ ≡ 2Ω ij Ω ij where Ω ij is the mean rate-of-rotation tensor and is defined by [B-8] Ω ij = ∂u 1⎛ ⎜ ∂u i − j 2⎜ ⎝ ∂x j ∂xi ⎞ ⎟ ⎟ ⎠ [B-9] B-1. d is the distance from the wall. and Θ is a scalar measure of the deformation tensor.

All three models have similar forms. is set to zero.793⎜ ⎜ µ ⎟ ⎟ u t 0. and the law-of-thewall is employed: ⎛ ρ ut d ⎞ 1 u = ln 9.7. defined as ⎤ ⎞ ∂T ⎟ ⎟ ∂x + u i (τ ij )eff ⎥ + S h ⎥ ⎠ j ⎦ [B-17] E is the total energy.173 - . B-1. Wall boundary conditions ~ . Convective heat and mass transfer modeling Turbulent heat transport is modeled using the concept of Reynolds' analogy to turbulent momentum transfer. RNG. At walls. it is assumed that the centroid of the wall-adjacent cell falls within the logarithmic region of the boundary layer. using the appropriate "law-of-the-wall''. the wall shear stress is obtained from the laminar stress-strain relationship: u ρ ut d = ut µ [B-15] If the mesh is too coarse to resolve the laminar sublayer. B-2. tensor. the modified turbulent kinematic viscosity. with a default turbulent Schmidt number of 0.4187 ⎝ ⎠ where u is the velocity parallel to the wall and [B-16] u t is the shear velocity.Appendix B B-1. Turbulent mass transfer is treated similarly.6. and realizable κ − ε models. The major differences in the models are as follows: .85.7. Wall boundary conditions for scalar transport are handled analogously to momentum. The default value of the turbulent Prandtl number is 0. with transport equations for κ and ε . ν When the mesh is fine enough to resolve the laminar sublayer. and (τ ij )eff is the deviatoric stress (τ ) ij eff ⎛ ∂u j ∂u i = µ eff ⎜ + ⎜ ∂x ⎝ i ∂x j ⎞ 2 ⎟ − µ eff ∂u i δ ij ⎟ 3 ∂xi ⎠ [B-18] The term involving τ ij ( )eff represents the viscous heating. The "modeled'' energy equation is thus given by the following: ⎡⎛ C p µt ∂ (ρE ) + ∂ [ui (ρE + p )] = ∂ ⎢⎜ k+ ⎜ ∂t ∂xi ∂x j ⎢ Prt ⎣⎝ where k is the thermal conductivity. The κ − ε family models This section presents the standard.

accounting for the effects of compressibility. Transport equations The turbulence kinetic energy. including turbulent production.1. and the effects of molecular viscosity are negligible. C1ε . Ym represents the contribution of the fluctuating dilatation in compressible turbulence to the overall dissipation rate. µ t . The transport equations. C 2ε . The model transport equation for κ is derived from the exact equation. is computed by combining κ and ε as follows: . κ . generation due to buoyancy. ε . methods of calculating turbulent viscosity.1.174 - . 1972) is a semi-empirical model based on model transport equations for the turbulence kinetic energy ( κ ) and its dissipation rate ( ε ). In the derivation of the κ − ε model. and its rate of dissipation. are obtained from the following transport equations: ⎡⎛ µt ∂ (ρ κ ) + ∂ (ρ κ u i ) = ∂ ⎢⎜ µ+ ⎜ (Prt )κ ∂t ∂xi ∂x j ⎣ ⎢⎝ ⎡⎛ µt ∂ (ρε ) + ∂ (ρε u i ) = ∂ ⎢⎜ + µ ⎜ (Prt )ε ∂t ∂xi ∂x j ⎢ ⎣⎝ ⎞ ∂κ ⎤ ⎟ ⎟ ∂x ⎥ + Gκ − ρε + S κ ⎥ ⎠ j⎦ [B-19] ⎞ ∂ε ⎤ ε ε2 ⎟ ( ) + C G + C G − C + Sε ρ 1ε 3ε b 2ε k ⎟ ∂x ⎥ κ κ ⎥ j ⎠ ⎦ [B-20] In these equations. the generation and destruction terms in the equation. The features that are essentially common to all models follow. B-2. B-2. and modeling heat and mass transfer. Gκ represents the generation of turbulence kinetic energy due to the mean velocity gradients.Appendix B • • • the method of calculating turbulent viscosity the turbulent Prandtl numbers governing the turbulent diffusion of κ and ε . Modeling the turbulent viscosity The turbulent (or eddy) viscosity . and C 3ε are constants.2. B-2. The standard κ − ε model is therefore valid only for fully turbulent flows. and model constants are presented separately for each model.1. while the model transport equation for ε was obtained using physical reasoning and bears little resemblance to its mathematically exact counterpart. The standard κ − ε model The standard κ − ε model (Launder and Spalding. and S κ and S ε are user-defined source terms. Gb is the generation of turbulence kinetic energy due to buoyancy. it was assumed that the flow is fully turbulent.1.

Gb is the generation of turbulence kinetic energy due to buoyancy.3.2.175 - . The analytical derivation results in a model with constants different from those in the standard κ − ε model. . The RNG κ − ε model The RNG-based κ − ε turbulence model (Choudhury et al. respectively. S κ and S ε are user-defined source terms. Model constants The model constants have the following default values (Launder and Spalding.3. C µ = 0. and Ym represents the contribution of the fluctuating dilatation in compressible turbulence to the overall dissipation rate.44. [B-22] These default values have been determined from experiments with air and water for fundamental turbulent shear flows including homogeneous shear flows and decaying isotropic grid turbulence. B-2. Transport equations The RNG κ − ε model has a similar form to the standard κ − ε model: ⎛ ∂ ∂κ ⎞ ⎟ + Gκ + Gb − ρε − YM + S κ (ρκ ) + ∂ (ρκ ui ) = ∂ ⎜ α µ κ eff ⎟ ∂t ∂xi ∂x j ⎜ ∂ x j ⎝ ⎠ [B-23] ⎛ ∂ ∂ε ⎞ ε ε2 ⎟ (ρε ) + ∂ (ρε u i ) = ∂ ⎜ ( ) + C G + C G − C − Rε + S ε α µ ρ 1ε 3ε b 2ε ε eff κ ⎟ ∂t ∂xi ∂x j ⎜ ∂ κ κ x j ⎠ ⎝ [B-24] In these equations. and additional terms and functions in the transport equations for κ and ε . B-2. They have been found to work fairly well for a wide range of wall-bounded and free shear flows. C 2ε = 1.2.1.0. using a mathematical technique called “renormalization group” (RNG) methods. Gκ represents the generation of turbulence kinetic energy due to the mean velocity gradients. 1993) is derived from the instantaneous Navier-Stokes equations. The quantities α κ and α ε are the inverse effective Prandtl numbers for κ and ε .1.09.92. (Prt )ε = 1. B-2. 1972): C1ε = 1.Appendix B µt = ρ Cµ κ2 ε [B-21] where C µ is a constant. (Prt )κ = 1..

4. Modeling the effective viscosity The scale elimination procedure in RNG theory results in a differential equation for turbulent viscosity: ⎛ ρ 2κ d⎜ ⎜ εµ ⎝ ⎞ νˆ ⎟ = 1.6321 α + 2.09 used in the standard κ − ε model.0.393 B-2.3929 0. are computed using the following formula derived analytically by the RNG theory: α − 1.2. B-2. α κ and α ε . In the high-Reynolds-number limit. α κ = α ε ≈ 1. It is interesting to note that this value of C µ is very close to the empirically-determined value of 0. Equation [B-25] gives µt = ρ Cµ κ2 ε [B-28] with C µ = 0.3929 0.3929 α 0 + 2. In the high-Reynolds-number limit ( µ mol / µ eff << 1).3679 = µ mol µ eff [B-29] where α 0 = 1. Calculating the inverse effective Prandtl numbers The inverse effective Prandtl numbers. derived using RNG theory.2.Appendix B B-2.0845. allowing the model to better handle low-Reynolds-number and near-wall flows . The Rε term in the ε equation The main difference between the RNG and standard κ − ε models lies in the additional term in the ε equation given by η ⎞ C µ ρη 3 ⎛ ⎜1 − η ⎟ ε 2 0⎠ ⎝ Rε = 3 κ 1 + βη [B-30] .3929 α 0 − 1.3. [B-25] is integrated to obtain an accurate description of how the effective turbulent transport varies with the effective Reynolds number (or eddy scale).176 - .72 dνˆ ⎟ νˆ 3 − 1 + C v ⎠ [B-25] νˆ = µ eff µ [B-26] Cν ≈ 100 [B-27] Eq.2.2.

the third and fourth terms on the right-hand side of Eq. (1995) proposed the socalled realizable κ − ε model. * making the value of C 2 ε less than C 2ε . eventually. The term “realizable” means that the model satisfies certain mathematical constraints on the normal stresses. As a result. which explains the superior performance of the RNG model for certain classes of flows. In the logarithmic layer. however. for weakly to moderately strained flows.177 - .5.1-8]) and the eddy viscosity definition (Eq. reducing κ and. To understand this. the RNG model tends to give results largely comparable to the standard κ − ε model. [B-31] The effects of this term in the RNG ε equation can be seen more clearly by rearranging Eq. which is close in magnitude to the value of C 2ε in the standard κ − ε model (1. Shih et al. the RNG model is more responsive to the effects of rapid strain and streamline curvature than the standard κ − ε model. β = 0.92). The realizable κ − ε model In addition to the standard and RNG-based κ − ε models. As a result. [B-24] can be merged. the Rε term makes a positive contribution. Thus. the Rε term makes a negative contribution. C 2ε = 1. These values are: C1ε = 1. [2. and the resulting ε equation can be rewritten as ⎛ ∂ε ⎞ ∂ ε ε2 * ⎟ (ρε ) + ∂ (ρε u i ) = ∂ ⎜ ( ) + C G + C G − C α µ ρ 1ε 3ε b 2ε ε eff κ ∂t ∂xi ∂x j ⎜ ∂x j ⎟ κ κ ⎝ ⎠ [B-32] * C2 ε ≡ C 2ε η ⎞ C µη 3 ⎛ ⎜1 − η ⎟ 0⎠ ⎝ + 3 1 + βη [B-33] * In regions where η < η 0 . [B-21]) to obtain the following expression for the normal Reynolds stress in an incompressible strained mean flow: ∂U 2 u 2 = κ − 2ν t ∂x 3 [B-35] . consistent with the physics of turbulent flows. η 0 = 4. the smaller destruction of ε augments ε .42. In regions of large strain rate ( η > η 0 ).012.0. the RNG model yields a lower turbulent viscosity than the standard κ − ε model. it can be shown that η ≈ 3. In comparison with the standard κ − ε model.Appendix B η ≡ Vκ / ε . the effective viscosity. giving C 2 ε ≈ 2. in rapidly strained flows. [B-34] B-2. Using Eq. for instance. [B-30].38.0. Model constants The model constants have values derived analytically by the RNG theory. and C 2 ε becomes larger * than C 2ε .68. consider combining the Boussinesq relationship (Eq. [B24].2. B-2.3.

which by definition is a positive quantity. The notion of variable C µ is suggested by many modelers including Reynolds (1987). Transport equations The modeled transport equations for κ and ε in the realizable κ − ε model are ⎡⎛ µt ∂ (ρκ ) + ∂ (ρκ u j ) = ∂ ⎢⎜ µ+ ⎜ (Prt )k ∂t ∂x j ∂x j ⎣ ⎢⎝ ⎡⎛ µt ∂ (ρε ) + ∂ (ρε u j ) = ∂ ⎢⎜ + µ ⎜ (Prt )ε ∂t ∂x j ∂x j ⎢ ⎣⎝ ⎡ η ⎤ C1 = max ⎢0.09 in the inertial sublayer of equilibrium boundary layers. η + 5⎥ ⎣ ⎦ ⎞ ∂κ ⎤ ⎟ ⎟ ∂x ⎥ + Gκ + Gb − ρε − YM + S κ ⎥ ⎠ j⎦ [B-37] ⎞ ∂ε ⎤ ε2 ε ⎟ ρ ε ρ + C V − C + C C 3ε Gb + S ε ⎥ 1 2 1 ε ⎟ ∂x κ κ νε + ⎥ j ⎠ ⎦ [B-38] [B-39] η =V κ .Appendix B Using Eq.7 ε ∂x 3C µ Similarly. u 2 . The most straightforward way to ensure the realizability (positivity of normal stresses and Schwarz inequality for shear stresses) is to make C µ variable by sensitizing it to the mean flow (mean deformation) and the turbulence ( κ . but prediction of the spreading rate for axisymmetric jets is unexpectedly poor) is considered to be mainly due to the modeled dissipation equation. For example.3. “non-realizable”. when the strain is large enough to satisfy κ ∂U 1 ≥ ≈ 3 . ε ). .. a new model equation for dissipation based on the dynamic equation of the meansquare vorticity fluctuation. [B-21] for ν t ≡ µ t / ρ .178 - .05 in a strong homogeneous shear flow. no summation over α and β ) can be violated when the mean strain rate is large. one obtains the result that the normal stress. it can also be shown that the Schwarz inequality for shear stresses ( u α u β 2 [B-36] 2 2 ≤ uα u β . The well-known round-jet anomaly (named based on the finding that the spreading rate in planar jets is predicted reasonably well.e. Another weakness of the standard κ − ε model or other traditional κ − ε models lies with the modeled equation for the dissipation rate.1. • B-2. The realizable κ − ε model was intended to address these deficiencies of traditional κ − ε models by adopting the following: • a new eddy-viscosity formula involving a variable originally proposed by Reynolds (1987). i. ε V = 2VijVij . and 0. C µ is found to be around 0. becomes negative. and is well substantiated by experimental evidence.43.

However. [B19]) and the RNG κ − ε model (Eq.3. even if κ vanishes or becomes smaller than zero. S κ and S ε are user-defined source terms.Appendix B In these equations. [B-38]) does not involve the production of κ .. the form of the ε equation is quite different from those in the standard and RNG-based κ − ε models (Eqs. i. i. which have a singularity due to κ in the denominator.. W = 1 3 ( ) VijV jk Vki ~ ∂u 1⎛ ⎜ j + ∂u i V V V V . As = 6 cos φ [B-45] φ = cos −1 6W . [B-23]).179 - . The model constants A0 and As are given by Ao = 4. Another desirable feature is that the destruction term (the next to last term on the right-hand side of Eq. It is believed that the present form better represents the spectral energy transfer. [B-37]) is the same as that in the standard κ − ε model (Eq. Note that the κ equation (Eq. the turbulent viscosity is computed from: κ2 µ t = ρC µ ε [B-40] The difference between the realizable κ − ε model and the standard and RNG κ − ε models is that C µ is no longer constant. except for the model constants.2. it does not contain the same Gκ term as the other κ − ε models. Modeling the turbulent viscosity As in other κ − ε models. Gκ represents the generation of turbulence kinetic energy due to the mean velocity gradients. [B-38]) does not have any singularity. .04. its denominator never vanishes.e. B-2. Gb is the generation of turbulence kinetic energy due to buoyancy. [B-20] and [B-24]). = = ~3 ij ij ij ⎜ 2 ⎝ ∂xi ∂x j V ⎞ ⎟ ⎟ ⎠ [B-46] . It is computed from Cµ = 1 κU * Ao + As ε [B-41] ~ ~ U * ≡ VijVij + Ω ij Ω ij ~ Ω ij = Ω ij − 2ε ijk ω k Ω ij = Ω ij − ε ijk ω k [B-42] [B-43] [B-44] where Ω ij is the mean rate-of-rotation tensor viewed in a rotating reference frame with the angular velocity ω k .e. This feature is contrasted with traditional κ − ε models. One of the noteworthy features is that the production term in the equation (the second term on the right-hand side of Eq. and Ym represents the contribution of the fluctuating dilatation in compressible turbulence to the overall dissipation rate.

Standard wall functions Wall functions are a collection of semi-empirical formulas and functions that in effect "bridge'' or "link'' the solution variables at the near-wall cells and the corresponding quantities on the wall.Appendix B It can be seen that C µ is a function of the mean strain and rotation rates. defined by Eqs.180 - [B-50] . B-2. B-2. The wall functions comprise: • • laws-of-the-wall for mean velocity and temperature (or other scalars) formulas for near-wall turbulent quantities The standard wall functions are based on the proposal of Launder and Spalding (1974).5. Modeling the turbulent production in the κ − ε models The term Gκ .3. this term may be defined as Gκ = − ρ u i′u ′j ∂u j ∂xi [B-48] To evaluate Gκ in a manner consistent with the Boussinesq hypothesis.2.793 y * 0.4.0.1. (Prt )κ = 1. The model constants are: C 1ε = 1. (Prt )ε = 1. and realizable κ − ε models.4187 ( ) . Gκ = µ tV 2 [B-49] where V is the modulus of the mean rate-of-strain tensor. Model constants The model constants have been established to ensure that the model performs well for certain canonical flows. [B-39] and [B-46]. the angular velocity of the system rotation.5. B-2. and the turbulence fields. representing the production of turbulence kinetic energy. RNG.3. is modeled identically for the standard. From the exact equation for the transport of . [B-47] B-2.44.9. C 2 = 1. Momentum The law-of-the-wall for mean velocity yields U* = 1 ln 9. and have been most widely used for industrial flows.

in the FV code. In the FV code.g. y * . the log-law is employed when y * > 11. it is much larger than the momentum sublayer thickness. For fluids of low Prandtl numbers (e. the FV code applies the laminar stress-strain relationship that can be written as U * = y* [B-53] It should be noted that.225 at the wall-adjacent cells..181 - . For example.5. and changes from fluid to fluid. different from the thickness of the (momentum) viscous sublayer.Appendix B U ≡ * U P C µ 4κ P 2 1 1 τw / ρ 1 1 [B-51] ρC µ 4κ P 2 y P y ≡ µ * [B-52] The logarithmic law for mean velocity is known to be valid for 30 < y * < 300. When the mesh is such that y * < 11. The law-of-the-wall implemented in the FV code has the following composite form: . oil) is much less than its momentum sublayer thickness. y + is defined as: y+ = ρuτ y µ [B-54] B-2. liquid metal). the laws-of-the-wall for mean velocity and temperature are based on the wall unit. As in the law-of-the-wall for mean velocity.. in general.2. the law-of-the-wall for temperature comprises the following two different laws: • • linear law for the thermal conduction sublayer where conduction is important logarithmic law for the turbulent region where effects of turbulence dominate conduction The thickness of the thermal conduction layer is. the thickness of the thermal sublayer for a high-Prandtl-number fluid (e.g. Energy Reynolds' analogy between momentum and energy transport gives a similar logarithmic law for mean temperature. on the contrary.225. These quantities are approximately equal in equilibrium turbulent boundary layers. rather than y + .

Once the physical properties of the fluid being modeled are specified.793 y + P ⎥ + κ ⎦ ⎪ ⎣ 1 1 ⎪ C 4κ 2 2 ⎪ 1 ρ µ P Prt U P + (Pr − Prt )U c2 ⎪ & 2 q ⎩ (y * * < yT ) [B-55] ( ) { } (y * * > yT ) where P is computed by using the formula given by Jayatilleke (1969): ⎞ ⎟ ⎟ ⎠ 3 4 ⎡⎛ Pr P = 9.182 - .w ⎧Sc y * ⎪ =⎨ ⎡ 1 ⎤ ln 9.793 y * + Pc ⎥ ⎪Sc t ⎢ ⎦ ⎩ ⎣ 0.007 Pr ⎡ Prt ⎤ − 1⎥ ⎢1 + 0.4187 ( ) (y (y * * * < yc ) >y ) * c [B-57] where Yi is the local species mass fraction.5. Similarly to Eq. with the difference being that the Prandtl numbers are always replaced by the corresponding Schmidt numbers. [B-54]. [B-56]). Note that Pc and y c are * calculated in a similar way as P and y T (Eq. * Then. B-2. the FV code assumes that species transport behaves analogously to heat transfer.28e ⎥ ⎥⎣ ⎦ ⎦ [B-56] * The non-dimensional thermal sublayer thickness. [B-55] is applied to compute the wall temperature or heat flux (depending on the type of the thermal boundary conditions). y T .Appendix B T* = (Tw − TP )ρC p C µ 4κ P 2 1 1 & q 1 1 ⎧ C µ 4κ P 2 2 1 * ⎪Pr y + ρ Pr UP & 2 q ⎪ ⎪ ⎤ * ⎪ ⎡1 = ⎨ Prt ⎢ ln 9. given the molecular Prandtl number.w − Yi )ρC µ 4 κ P 2 1 1 J i. depending on the y * value at the near-wall cell. . its molecular Prandtl number is computed. The procedure of applying the law-of-the-wall for temperature is as follows. and stored. [B-54] is computed as the y * value at which the linear law and the logarithmic law intersect. is computed from the intersection of the linear and logarithmic profiles. y T . Sc and Sct are molecular and turbulent Schmidt * numbers. and J i .3. the thermal sublayer thickness. given the molecular Prandtl number of the fluid being modeled. the law-of-the-wall for species can be expressed for constant property flow with no viscous dissipation as Y ≡ * (Y i. Species When using wall functions for species transport.24⎢⎜ ⎜ ⎢⎝ Prt ⎣ ⎤ − 0. either the linear or the logarithmic profile in Eq. w is the diffusion flux of species i at the wall. During the iteration. in Eq.

6. and its dissipation rate. the quality of the predictions is likely to be compromised.Appendix B B-2.5. are computed on the basis of the local equilibrium hypothesis. the wall boundary conditions for the solution variables. you do not need to be concerned about the boundary conditions at the walls. which are the source terms in the κ equation.4187 ρC µ 4 κ P 2 y P [B-59] and ε is computed from εP = C µ 4κ P 2 0. However. the production of κ is computed from Gκ ≈ τ w τw ∂U =τw 1 1 ∂y 0. when the near-wall flows are subjected to severe pressure gradients. [B60].4187 y P 3 3 [B-60] The ε equation is not solved at the wall-adjacent cells.183 - . [B-58] The production of kinetic energy. but instead is computed using Eq. The boundary condition for κ imposed at the wall is ∂κ =0 ∂n where n is the local coordinate normal to the wall. they tend to become less reliable when the flow situations depart too much from the ideal conditions that are assumed in their derivation. The standard wall functions work reasonably well for a broad range of wall-bounded flows. B-2. and when the flows are in strong non-equilibrium. κ . ε . species concentration. Thus. Accordingly. Among others. Gκ . and ε . as shown here. the production of κ and its dissipation rate are assumed to be equal in the wall-adjacent control volume. temperature. Therefore. including mean velocity. the constant-shear and local equilibrium hypotheses are the ones that most restrict the universality of the standard wall functions. Under this assumption.4. Turbulence In the κ − ε models the κ equation is solved in the whole domain including the wall-adjacent cells. are all taken care of by the wall functions. Convective heat and mass transfer modeling in the κ − ε models Turbulent heat transport is modeled using the concept of Reynolds' analogy to turbulent momentum transfer. Note that. The "modeled'' energy equation is thus given by the following: . at the wall-adjacent cells.

Additional terms may appear in the energy equation. [B-29]. 1994). [B-29] works well across a very broad range of molecular Prandtl numbers. For the RNG κ − ε model. [B-29]. the effective turbulent diffusivity for mass transfer is calculated in a manner that is analogous to the method used for the heat transport. E is the total energy. . the effective thermal conductivity is k eff = α C p µ eff where α is calculated from Eq. B-3. The default value of the turbulent Prandtl number is 0. the effective thermal conductivity is given by k eff = k + C p µt Prt [B-62] where k is the thermal conductivity. [B-29] smoothly predicts the variation of effective Prandtl number from the molecular value ( α = 1/Pr) in the viscosity-dominated region to the fully turbulent value ( α = 1. The standard κ − ω model The standard κ − ω model is an empirical model based on model transport equations for the turbulence kinetic energy ( κ ) and the specific dissipation rate ( ω ). [B-63] The fact that α varies with µ mol / µ eff . Eq.1. For the RNG model. is an advantage of the RNG κ − ε model. Turbulent mass transfer is treated similarly. but with α 0 = 1/Pr = k / C p µ . which allows heat transfer to be calculated in low-Reynolds-number regions. The value of α 0 in Eq.Appendix B ⎛ ∂ ∂T (ρE ) + ∂ [u i (ρE + p )] = ∂ ⎜ k eff + u i (τ ij )eff ⎜ ∂t ∂xi ∂x j ⎝ ∂x j ⎞ ⎟ + Sh ⎟ ⎠ [B-61] where k eff is the effective thermal conductivity.184 - . For the standard and realizable κ − ε models. [B-29] is α 0 = 1/Sc. It is consistent with experimental evidence indicating that the turbulent Prandtl number varies with the molecular Prandtl number and turbulence (Kays. where Sc is the molecular Schmidt number. [B-18] The term involving τ ij ( )eff is the ( )eff represents the viscous heating.3 for more details. Eq. from liquid metals (Pr ≈ 10-2) to paraffin oils (Pr ≈ 103).393) in the fully turbulent regions of the flow. and τ ij deviatoric stress tensor.85. 1998a.7. For the standard and realizable κ − ε models. defined by Eq. See Section 2. which can also be thought of as the ratio of κ to ε (Wilcox. 1998b). as in Eq. the default turbulent Schmidt number is 0. depending on the physical models used.

Appendix B B-3.2.1.2. ω . B-3. S κ and S ω are userdefined source terms. κ . It is given by ⎛ α * + Re t ⎜ 0 Rκ * ⎜ α * = α∞ Re ⎜ ⎜ 1+ t R κ ⎝ ⎞ ⎟ ⎟ ⎟ ⎟ ⎠ [B-69] . Γκ and Γω represent the effective diffusivity of κ and ω . Gκ represents the generation of turbulence kinetic energy due to mean velocity gradients. Yκ and Yω represent the dissipation of κ and ω due to turbulence. respectively. All of the above terms are calculated as described below. are obtained from the following transport equations: ⎛ ∂κ ∂ (ρκ ) + ∂ (ρ κ u i ) = ∂ ⎜ Γκ ∂t ∂xi ∂x j ⎜ ⎝ ∂x j ⎛ ∂ϖ ∂ (ρω ) + ∂ (ρ ω u i ) = ∂ ⎜ Γω ∂t ∂xi ∂x j ⎜ ⎝ ∂x j ⎞ ⎟ + Gκ − Yκ + S κ ⎟ ⎠ ⎞ ⎟ + Gω − Yω + S ω ⎟ ⎠ [B-64] [B-65] In these equations. Transport equations The turbulence kinetic energy. Modeling the effective diffusivity The effective diffusivities for the κ − ω model are given by Γκ = µ + (Prt )κ (Prt )ω µt µt [B-66] Γω = µ + [B-67] The turbulent viscosity is computed by combining κ and ω as follows: µt = α * ρκ ω [B-68] B-3. Low-Reynolds-number correction The coefficient α * damps the turbulent viscosity causing a low-Reynolds-number correction.1.185 - . Gϖ represents the generation of ϖ . and the specific dissipation rate.

The coefficient α is given by α α= ∞ α* ⎛ α + Re t ⎜ 0 Rω ⎜ Re ⎜ ⎜ 1+ t R ω ⎝ ⎞ ⎟ ⎟ ⎟ ⎟ ⎠ [B-72] where Rω = 2. in the high-Reynolds-number form of the κ − ω model. B-3. Note that.3.186 - . [B-70] * Note that.3. Production of κ The term Gκ represents the production of turbulence kinetic energy. * α0 = βi 3 . Modeling the turbulent production B-3.4.1. Modeling the turbulence dissipation B-3. B-3.Appendix B Re t = ρκ . α * = α ∞ = 1. in the high-Reynolds-number form of the κ − ω model. Dissipation of κ The dissipation of κ is given by Yκ = ρβ * f β * κω ⎧1 ⎪ 2 = ⎨1 + 680 X κ ⎪1 + 400 X 2 κ ⎩ Xκ ≤ 0 Xκ > 0 [B-73] fβ* [B-74] . [B-69] and [B-70] respectively.3.072. α = α ∞ = 1 .2. It is defined in the same way as for the κ − ε model (see Eq. µω Rκ = 6.4. Production of ω The production of ω is given by Gω = α ω Gκ κ [B-71] where Gκ is given by Eq. [B-48]. B-3.1.95. [B-48]). α * and Re t are given by Eqs. β i = 0.

5. Ω ij . [B-78] where Re t and F (M t ) are given by Eqs.09. F (M t ) . Rβ = 8. [B-70] and [B-83] respectively.4.3. The rotation rate tensor. respectively. [B-77] and [B-83].Appendix B Xκ = 1 ∂κ ∂ω ω 3 ∂x j ∂x j [B-75] β * = β i* [1 + ζ * F (M t )] 4 ⎛ ⎞ Re t ⎜ 4 +⎛ Rβ ⎟ 15 ⎜ ⎝ ⎠ *⎜ β i* = β ∞ 4 ⎜ ⎞ Re ⎜ 1+ ⎛ ⎜ tR ⎟ ⎜ β ⎝ ⎠ ⎝ [B-76] ⎞ ⎟ ⎟ ⎟ ⎟ ⎟ ⎠ [B-77] ζ * = 1. Dissipation of ω The dissipation of ω is given by Yω = ρ β f β ω 2 fβ = 1 + 70 X ω 1 + 80 X ω [B-79] [B-80] Xω = Ω ij Ω jk Vki (β ω ) * ∞ 3 [B-81] The strain rate tensor. is defined by Eq. is given by ⎧0 F (M t ) = ⎨ 2 2 ⎩ M t − M t0 M t ≤ M t0 M t > M t0 [B-83] . Also. is defined by Eq. B-3.4. [B-46].187 - . Compressibility correction The compressibility function. B-3.2. [B-9]. * β∞ = 0. β = β i ⎢1 − ⎣ ⎡ ⎤ β i* * ζ F (M t )⎥ βi ⎦ [B-82] β i* and F (M t ) are defined by Eqs. Vij .

σ κ = 2.25. This means that all boundary conditions for wall-function meshes will correspond to the wall function approach. Wall boundary conditions The wall boundary conditions for the κ equation in the κ − ω models are treated in the same way as the equation is treated when enhanced wall treatments are used with the κ − ε models. α0 = .Appendix B M t2 = 2κ . B-3. 1 * β∞ = 0. while for the fine meshes. Rκ = 6.0 σ ω = 2. a2 M t 0 = 0. β i* = β ∞ . Rω = 2.5. Rβ = 8.52. [B-86] ⎛ ⎜ ⎝ β i (y + ) 6 2 ⎞ ⎟ ⎟ ⎠ [B-87] ⎧⎛ 50 ⎞ 2 ⎟ ⎪⎜ ⎪⎜ + ⎟ + ωw = ⎨⎝ κ s ⎠ ⎪ 100 + ⎪ ⎩ κs κ s+ < 25 [B-88] κ ≥ 25 + s κ s+ = max⎜ ⎜1. 9 ζ * = 1.0 [B-85] B-3.0. M t 0 = 0.5. the appropriate low-Reynolds-number boundary conditions will be applied. in the high-Reynolds-number form of the κ − ω incompressible form. Model constants * α∞ = 1. β i = 0. a = γRT [B-84] * model.6. α ∞ = 0. β * = β i* . In the logarithmic (or turbulent) region.09.25.95. In the Note that. ⎝ ⎛ ρκ s u * ⎞ ⎟ µ ⎟ ⎠ [B-89] and k s is the roughness height. The value of ω at the wall is specified as ρ (u * ) + ωw = ω µ 2 + ω + = min⎜ ω w .188 - .072. the value of ω + is ω+ = 1 * β∞ + du turb dy + [B-90] .

Computer Methods in Applied Mechanics and Engineering. 26..189 - . A..E.-E. (1995). Fluids Engineering Division (Publication) FED 149. and Allmaras. 755. Technical Report AIAA-92-0439. Zhu. W. Kays... Computers and Fluids.Appendix B which leads to the value of ω in the wall cell as ω= u* * β∞ κy [B-91] References Choudhury.W. and Spalding. 24. Wilcox.M. Spalart. AIAA Journal. P. 284 – 295.. Shabbir. agard report No. S. (1994). D. Calculation of turbulent separated flows using a renormalization group based k-ε turbulence model. 193 – 321. The numerical computation of turbulent flows. 26. W.E. New k-ε eddy viscosity model for high Reynolds number turbulent flows. Lectures in mathematical models of turbulence.. C. and Spalding.. Yang... (1972). American Society of Mechanical Engineers. (1992). 1311 – 1320. (1974). Jayatilleke.. Reassessment of the scale-determining equation for advanced turbulence models. Academic Press. W. Progress in Heat and Mass Transfer. (1969).B.. B.. AIAA Journal. 1. 227 – 238. .-H. Reynolds.. Liou.B. Turbulent Prandtl number. 3. Kim. Fundamentals of turbulence for turbulence modeling and simulation.. London. 116. (1993). B.. W. J. A one-equation turbulence model for aerodynamic flows. Flannery. Lecture notes for Von Karman Institute. Where are we?. Shih.C. (1998a). Launder. 1299 – 1310. D. Multiscale model for turbulent flows. Wilcox.C. (1998b). Journal of Heat Transfer.S. D. 269 – 289. (1987).. D. T. D. Launder.C. American Institute of Aeronautics and Astronautics. 177 – 187. Z. S. The Influence of Prandtl number and surface roughness on the resistance of the laminar sublayer to momentum and heat transfer.

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APPENDIX C DIMENSIONLESS NUMBERS Physical meaning and applied formulas Harmonic works. « Dimensionless travels » .

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It is named for Leonhard Euler (1707-1783). mathematician who first explained role of pressure in fluid flow. known for his work with the early development of jet engines and for discovering ways to increase rocket efficiency. and is used to characterize dissipation. The Biot number can be expressed as: Bi = Figure C-1. Biot number The Biot number is a dimensionless number used in unsteady-state (or transient) heat transfer calculations. The Euler number can be expressed as: Figure C-3. It expresses the relationship between a flow's kinetic energy and enthalpy. G. It is named for the late professor Ernst R.Appendix C C-1. The Eckert number can be expressed as: u2 Ec = C p ∆T [C-2] Figure C-2. The Euler Number can be interpreted as a measure of the ratio of pressure forces to inertial forces. Leonhard Euler Eu = p ρ u2 [C-3] . Eckert number The Eckert number is a dimensionless number used in flow calculations.193 - . Eckert (1904 – 2004). G. Ernst R. Eckert C-3. and relates the heat transfer resistance inside and at the surface of a body. Euler number The Euler number is a dimensionless value common used for analyzing fluid flow dynamics problems where the pressure difference between two points is an important variable. Jean Baptiste Biot hw ⋅ L kr [C-1] C-2. formulated basic equations of motion and so-called Bernoulli theorem and introduced the concept of cavitation and the principles of centrifugal machinery. It is named after the French physicist Jean Baptiste Biot (17741862).

Mach number The Mach number is defined as a ratio of the speed of flow relative to the speed of sound in the flowing fluid.Appendix C C-4. It is named after the German engineer Franz Grashof (1826 – 1893). It can be shown that the Mach number is also the ratio of inertial forces (also referred to aerodynamic forces) to elastic forces. an can be expressed as: Ma = u u sound [C-7] Figure C-6. Grashof number The Grashof number is a dimensionless number in fluid dynamics which approximates the ratio of the buoyancy force to the viscous force acting on a fluid. Franz Grashof gD 3 p ∆ρ ⎛ ρ ⎞ ⎜ ⎟ GrD = ⎟ ρ ⎜ ⎝µ⎠ 2 [C-6] C-6. The Froude number can be expressed as: Fr = u g Dp [C-4] Figure C-4. hydrodynamicist and naval architect who was the first to formulate reliable laws for the resistance that water offers to ships and for predicting their stability.the inertial force divided by gravitational force. William Froude C-5. It is named for William Froude (1810 – 1879). Ernst Mach . The Grashof number can be expressed as: GrH = 3 gβ (Ts − T∞ )D p ν2 [C-5] There is an analogous form of the Grashof number used in cases of natural convection mass transfer problems: Figure C-5. The Mach number is named after Austrian physicist and philosopher Ernst Mach (1838 – 1916). engineer.194 - . Froude number The Froude number is a dimensionless parameter measuring of the ratio of the inertia force on an element of fluid to the weight of the fluid element .

The most typical are as follows: Pe = D p uC p ρ kf = Re ⋅ Pr [C-9] Figure C-8. It is equivalent to the product of the Reynolds number with the Prandtl number. Jean Claude Eugene Péclet C-9. It is named after the German engineer Wilhelm Nusselt (1882 – 1957). the Péclet number is a dimensionless number relating the forced convection of a system to its heat conduction. Nusselt number The Nusselt number is a dimensionless number which measures the enhancement of heat transfer from a surface which occurs in a 'real' situation. Typically it is used to measure the enhancement of heat transfer when convection takes place. German physicist famous for his works in aeronautics. It is named after the French Physicist Jean Claude Eugene Péclet (1793 – 1857) There are various definitions of the Péclet number. Péclet number In physics. and can be expressed as: Figure C-7. Wilhelm Nusselt Nu = hD p kf [C-8] C-8. It is named after Ludwig Prandtl (1875 – 1953).195 - . compared to the heat transfer that would be measured if only conduction could occur. The Prandtl number can be expressed as: Pr = Figure C-9. Prandtl number The Prandtl Number is a dimensionless number approximating the ratio of momentum diffusivity and thermal diffusivity. Ludwig Prandtl Cpµ kf [C-10] .Appendix C C-7. pioneer in the study of the basic laws of heat transfer.

It is named after the Irish fluid dynamics engineer Osbourne Reynolds (1842 – 1912). pioneer in the field of engineering thermodynamics. The Schmidt number is the mass-transfer equivalent of the Prandtl number. It is named after Ernst Schmidt (1892 – 1975). Lord Rayleigh C-11. Ernst Schmidt . who proposed it in 1883. When the Rayleigh number is below the critical value for that fluid. and it can be expressed as: Sc = µ ρD AB [C-13] Figure C-12. Osbourne Reynolds Re = D p uρ µ [C-12] C-12. when it exceeds the critical value. the Rayleigh number for a fluid is a dimensionless number associated with the heat transfer within the fluid. It is the most important dimensionless number in fluid dynamics and provides a criterion for determining dynamic similitude. Rayleigh number In fluid mechanics. The Rayleigh number is named after John William Strutt. Typically it is given as follows for flow through a packed bed: Figure C-11.196 - . 1842 – 1919) and is defined as the product of the Grashof number and the Prandtl number. Schmidt number The Schmidt number is a dimensionless number approximating the ratio of momentum diffusivity and mass diffusivity. Reynolds number The Reynolds number is the ratio of inertial forces to viscous forces and is used for determining whether a flow will be laminar or turbulent. German scientist. heat transfer is primarily in the form of convection.Appendix C C-10. heat transfer is primary in the form of conduction. Ra = 2 D3 p ρ gβ C p ∆T kf µ = Gr ⋅ Pr [C-11] Figure C-10. 3rd Baron of Rayleigh (aka Lord Rayleigh. and is used to characterize fluid flows in where there are simultaneous momentum and mass diffusion convection processes. especially in heat and mass transfer.

Thomas Kilgore Sherwood Sh = kc D p D AB [C-14] C-14.Appendix C C-13. Sir Thomas Eduard Stanton C-15. named after the Czech professor of experimental physics Čeněk Strouhal (1850 – 1922). The Sherwood number is the mass-transfer equivalent of the Nusselt number. It is used to characterize heat transfer in forced convection flows. American chemical engineer whose primary research area was mass transfer and its interaction with flow and with chemical reaction. Stanton number The Stanton number is a dimensionless number which measures the ratio of heat transferred into a fluid to the thermal capacity of fluid. It represents the ratio of length scale to the diffusive boundary layer thickness. and the related problem of heat transmission. Čeněk Strouhal Sr = ωD p u [C-16] . It is defined in the following form: Figure C-15. St = h Cpρ u = Nu Re ⋅ Pr [C-15] Figure C-14. It is named after Thomas Kilgore Sherwood (1903 – 1976). and it can be expressed as: Figure C-13. Stanton's main field of interest was fluid flow and friction.197 - . Sherwood number The Sherwood number is a dimensionless number used in mass-transfer operation. unsteady fluid flow dynamics problems. It represents a measure of the ratio of inertial forces due to the unsteadiness of the flow or local acceleration to the inertial forces due to changes in velocity from one point to an other in the flow field. The Strouhal number. Strouhal number The Strouhal Number is a dimensionless value useful for analyzing oscillating. The Stanton number is named after Sir Thomas Eduard Stanton (1865 – 1931). is proportional to the reciprocal of vortex spacing expressed as number of obstacle diameters and is used in momentum transfer in general and Von Karman vortex streets and unsteady state flow calculations in particular.

. Turbulent numbers In the development of the dimensionless analysis there appears variations of some of the aforementioned dimensionless numbers when turbulent flow is considered (i. and Reynolds analogy was µt (White. In these cases.Appendix C C-16. (1991). White. Prandtl and Schmidt turbulent numbers). References Kays. 482 – 542. Turbulent Prandtl number. McGraw Hill. For first analysis purposes.75 < Prt < 2 for air and water (Kays. W. applied formulas to estimate this numbers are as follows: Re t = D p uρ µt C p µt kt [C-17] Prt = [C-18] Sc t = µt ρD AB [C-19] Turbulence intensity used to estimate used to estimate k t from µt was set between 1 . 284 – 295.4 %. Viscous Fluid Flow..e. 1994).M. (1994). New York. justified in the fact that majority of experimental results shows a range of variations between 0. Prt was assumed as a constant value within the bed. 116. . Where are we? Journal of Heat Transfer. Reynolds. F. pp.. 1991).198 - .

APPENDIX D FLUID PROPERTIES ESTIMATION & CFD IMPLEMENTATION Jodie Coston. « Green background » .

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For these equations. and Peng-Robinson EOS (Peng and Robinson. a. In this case. which in general form can be expressed as: z 3 − 1 + B * − uB * z 2 + A* + wB *2 − uB * − uB *2 z − A* B * − wB *2 − wB *3 = 0 where: ( ) ( ) [D-3] A* = and aP R 2T 2 [D-4] B* = bP RT [D-5] Two cubic EOS were used to estimate the density of a fluid in supercritical conditions during the development of this thesis. u and w take the values listed in Table D-1. which is implemented by default in the FV code (Fluent Inc. 2005). In this case the density is computed as: ρ= p op M w zRT [D-2] where z is the compressibility factor obtained from solving a cubic EOS. the density depends only on the operating pressure and not on the local relative pressure field. In this form.. Redlich-Kwong EOS (Redlich and Kwong. 1976) was applied for estimating the density of a mixture. . b. D-1. Density D-1. the density is computed as: ρ= p op M w RT [D-1] where R is the universal gas constant.Appendix D D-1.201 - .2. Mw is the molecular weight of the gas and pop is the operating pressure.1. Fluid @ P ≥ Pc In the case of a supercritical fluid it was chosen to define the density using a cubic equation of state (EOS). Gas @ atmospheric pressure In the case of a gas at atmospheric pressure it was chosen to define the density using the ideal gas law for an incompressible flow. 1949) was used for estimating the density of a pure substance.

real z. user-defined functions (UDF) and user-defined equations (UDE) were used.5 ⎞⎤ 0. and included within the equation system of the CFD solver. real c. real a. real r. real pr. In order to implement the aforementioned EOS within the CFD solver. real e. real z3. real z2.08664 RTc Pc 0. real b2. real q. real a2. real z1. real b.1 K% %Pr: 7380000 Pa% %EOS: REDLICH-KWONG% #include "udf. real t=C_T(cell. thread) { real ro. real d.202 - .5 Pc T 0.54226ω − 0. An example of a UDF for estimating the density of CO2 using the Redlich-Kwong EOS would be as follows: %UDF EXAMPLE% %PROPERTY TO BE MODIFIED INTO SOLVER: DENSITY% %FLUID: CO2% %Tr: 304. This strategy allowed the CFD code to compute the density of the fluid as a function of the static pressure and the temperature in every point of the computational grid. thread).Appendix D Equation RedlichKwong u 1 w 0 b 0.26992ω 2 2 Constants for the cubic equations of state used As commercial CFD codes do not offer real-gas equations of state within their default equation system.37464 + 1.45724 R 2Tc2 ⎡ ⎢1 + fω ⎜1 − ⎜ ⎟ ⎟⎥ ⎜ ⎜ Pc T ⎟ ⎟ ⎢ ⎝ ⎝ c ⎠ ⎠⎥ ⎣ ⎦ fω = 0.h" DEFINE_PROPERTY(cell_density. real tr.5 PengRobinson Table D-1. these equations have to be created and uploaded to the CFD solver if a supercritical fluid has to be modelled. real g.42748 R 2Tc2. . For the UDF creation. an analytical solution of the EOS was compiled using a build-up C++ compiler (incorporated within the CFD software). real fi. real f. 2 -1 ⎛ ⎛ T ⎞ 0. cell.07780 RTc Pc a 0.

b=0. z=d+e+(1.).3.46.0.).))+(1/3).)/27.02968.2.5)*cos(fi/3. pr=p/7380000.)+2. thread).1. For situations where the static pressure could be considered as constant along the computed model.5)*cos((fi/3. f=((-3.).42747*pr/pow(tr.)-pow(c. z3=(2*pow((-f/3./3.2.). The obtained polynomial expression (which can be written in general form as shown in Eq.*q)-2./3.2. and a graphical representation of the previously stated polynomial fitting is shown in Figure D-1.)+pow(c.*z*t). z1=(2*pow((-f/3.))./3..(5/2)). } else { fi=a*cos(-6.). tr=t/304.). z2=(2*pow((-f/3. g=((-27. } else { if (z2>z3) z=z2. b2=0.(1./3.*p/(8314..0944))+(1.1888))+(1. a2=0.). c=pow((f/3. can then be fed into the CFD solver as an UDE.0.Appendix D real p=C_P(cell.75*pow(g. e=pow(((-g/2. q=pow(b2.5)).*r)-(9.).203 - ./3.08664*pr/tr.5)). r=a2*b2. else z=z3.))..)+b2-a2. ρ = aT 6 + bT 5 + cT 4 + dT 3 + eT 2 + fT + g [D-6] A sample of the obtained coefficients for Eq. } return ro.0. [D-6] for estimating the density of supercritical CO2 can be seen in Table D-2.0. else z=z3.0) { d=pow(((-g/2.0.5)*cos((fi/3. if (z1>z2) { if (z1>z3) z=z1.*q)-1.)/3. } } ro=44.)). In order to quantify the round-up error associated . fitting the results obtained with the EOS to a 6th degree polynomial expression. a=6456696.)+4.(1. a simplified density model could be used.)+pow((g/2.3. This simplified model consisted on expressing the density of the fluid (at constant pressure) as a function of temperature. [D-6]).).)/pow(f. if (c>0.

EOS) .04 x 10-4 1.13 x 10-9 -4.48 x 105 -4.44 x 10-9 -4.98 x 104 1.05 x 10-10 -1.14 x 10-6 -1.58 x 10-5 3.05 x 103 g 3.58 x 10-3 -7.65 x 10-6 8.78 x 104 3.89 x 10-11 b -2.99 x 105 3.34 x 10-6 1.70 x 10-2 -1.01 x 10-1 -2.72 x 105 2.98 x 10-7 -3. a simulation for a density varying flow of supercritical CO2 in a Venturi tube was set.72 x 102 -1.63 x 10-1 1.18 x 101 2.78 x 103 -6. P [MPa] 8 10 12 14 16 18 20 22 Table D-2.52 x 106 -1.17 x 104 2.23 x 104 7.04 x 10-7 c 2. and obtained numerical values were compared with the prediction of the EOS.80 x 10-4 -3.75 x 100 4.30 x 101 -4.73 x 101 f -5.22 x 10-7 -3.77 x 10-7 3.Appendix D with the numerical solver.65 x 10-4 3.43 x 10-10 8. [kg/m3] from EOS Density parity plot for supercritical CO2 (numerical results vs.12 x 103 -4.77 x 101 4. 255 Density polynomial fitting for supercritical CO2 from CFD [kg/m ] 3 250 245 240 235 230 230 235 240 245 250 255 ρ ρ Figure D-2.87 x 102 -9.61 x 10-11 1.78 x 102 2.50 x 105 Obtained coefficients for Eq.51 x 10-1 -9. [D-6] for supercritical CO2 850 700 Density [kg/m ] 3 550 400 250 100 310 330 350 8 MPa 16 MPa 370 390 Temperature [K] 10 MPa 18 MPa 12 MPa 20 MPa 410 430 14 MPa 22 MPa 450 Figure D-1.79 x 10-10 1.14 x 10-3 8.22 x 10-3 -1.84 x 106 -6.81 x 106 -6. a 1.33 x 100 3.77 x 10-1 -1. resulting in a good agreement between the numerical results and the EOS estimation (see Figure D-2).94 x 10-4 d -1.86 x 104 3.76 x 10-2 e 3.65 x 100 6.24 x 10-7 -2.78 x 10-10 6.204 - .46 x 102 -6.

8 1.Appendix D D-1. [D-8].1.2 m diameter was created. From one side of the tube CO2 in laminar flow regime was fed to the model. 298. Mixtures In order to study how the density of a mixture was estimated by the CFD software.3. 0.e. a flux of 0.08 0.75 0 0. In such way the density is computed by the CFD solver as shown in Eq.. ρ= P y R ⋅T ⋅ ∑ i Mw [D-7] It was expected that for low pressure both methods would give similar results due to the low interaction forces between the molecules.06 0. incompressible ideal gas law was used to estimate density. a 2dimensional cylinder of 5 m length and 0. The numerical results obtained were compared against the estimation through equations of state (Guardo et al. 6. Density estimation for a binary mixture [C7H8/CO2] at 298 K and 0. For each of the simulations it was recorded the C7H8 mass fraction together with the mixture density at the central axis of the tube. 310 and 320 K) and four pressures (i.85 1. 8 and 20 MPa.e.1 MPa In order to study high pressure situations.95 Mixture density [kg/m ] 3 1. 298.205 - . . 310 and 320K) are very similar to the ones shown in Figure D-3. From those results it was checked that the numerical error of the CFD solver when applying the ideal gas law was neglectable. Low pressure density was determined by ideal gas law for both of the pure components assuming the flow as incompressible. Peng-Robinson EOS was implemented via UDF in order to obtain the compressibility factors. In order to impose a density gradient along the tube.01 kg/s of toluene vapor was imposed through the pipe walls. For near-critical and supercritical conditions.e. 2005). For atmospheric pressure situations. Peng Robinson equation of state for density was implemented through a C++ subroutine inside the CFD solver. In such way the density is computed by the CFD solver as shown in Eq. estimation of the mixture density was checked at 6. Three temperatures (i.02 0. 8 and 20 MPa) were taken as study cases.1 Mass fraction C7H8 CFD Estimation Figure D-3.04 EOS Estimation 0. The results obtained at the different temperatures tested (i. 1. [D-7].9 1.

2005).206 - . such a simple mixing rule is not able to predict the mixture critical point or phase changes.009 0. In this case. which is implemented by default in the FV code (Fluent Inc. the viscosity is computed as: ⎛T µ = µ0 ⎜ ⎜T ⎝ 0 ⎞ ⎟ ⎟ ⎠ n [D-9] where T0 and µ0 are reference values for temperature and viscosity. Viscosity D-2. Table D-3 shows the values of the coefficients involved in Eq.. According to this. respectively. it was noticed that despite the fact that the estimation done by the CFD solver is close to the EOS prediction for low solute mass fractions due to the good pure component density estimation. which is an acceptable value. .Appendix D ρ= P y z ⋅ R ⋅T ⋅ ∑ i Mw [D-8] An example of the results obtained for high pressure situations can be seen in Figure D-4. the greatest numerical errors obtained for the CFD simulations were located at the saturation point (equilibrium conditions at the specified pressure and temperature).003 0.006 Mass fraction C7H8 0.1. Density estimation for a binary mixture [C7H8/CO2] at 320 K and 8 MPa D-2. for all situations simulated. Gas @ atmospheric pressure In the case of a gas at atmospheric pressure it was chosen to define the density using a viscosity power law. 300 Mixture density [kg/m3] 275 250 225 200 0 0.012 EOS estimation CFD Estimation Figure D-4.24%. [D-9] for CO2 and air at moderated pressures and temperatures. Maximum error measured when estimating density was of 6. In general. For all cases analyzed the divergence between CFD estimated results and the EOS prediction increases as the mass fraction of solute increases.

716 x 10-5 T0 [K] 273.7 ) 0.79 0. which first calculates the parameters Z1 and Z2 for the reduced temperature of interest: 0 Z 1 = 0.666 Viscosity power law coefficients for CO2 and air D-2.2.807Tr0. Fluid @ P ≥ Pc In the case of a supercritical fluid it was chosen to define the viscosity following the procedure recommended by Lucas (1980).058Tr + 0.52 for D2. Lucas defines this quantity as σ r = 1.72 1.618 − 0.55(0.357e −0.96 + 0.292 − z c ) 0 F = 1 + 30. a reduced dipole moment is required.1(Tr − 0. 0 FQ = 1.340e −4. FP values are found as: FP0 = 1 + 30.15 ⎧ ⎨1 + 0.449Tr + 0.72 0. 0. To obtain the first of the aforementioned correction factors.76 for H2 and 0.55(0.207 - . FQ = 1.022 1. then ⎡ ⎤ aPre Z 2 = µ ξ ⎢1 + ⎥ −1 ⎢ bPr f + (1 + cPrd ) ⎦ ⎥ ⎣ 0 [D-14] .37 x 10-5 1.22Q 0.Appendix D Fluid CO2 Air Table D-3.75216 × 10 − 29 0 σ 2 Pc Tc2 [D-11] Then. µ0 [Pa· s] 1. H2 and D2.075 ≤ σ r [D-12] The factor FQ is used only for the quantum gases He.11 n 0. For non-quantum gases.292 − z c ) 0 P FP0 = 1 0 ≤ σ r < 0.022 ≤ σ r < 0.38 for He.11 273. If (1 < Tr < 40) and (0 < PR ≤ 100). [D-12] and [D-13] respectively.00385 (Tr − 12 ) ⎩ [ 2 ] 1 Mw Tr − 12 ⎫ ⎬ ⎭ 0 [D-13] Where Q = 1.018 FP0 FQ = µ 0ξ 0 0 ( ) [D-10] where FP and FQ are low pressure polarity and quantum correction factors determined as shown in Eqs.075 0.

7332 e Tr 1.6553Tr − 1.208 - . we define Y= Z2 Z1 [D-16] and the correction factors FP and FQ.3286 e Tr [D-15] e = 1.4489 1.4489 3.2310Tr− 7. An example of a UDF for estimating the viscosity of CO2 using the Lucas method would be as follows: . [D-14] are defined as a= b = a (1.1853Tr After computing Z1 and Z2. the dense gas viscosity is calculated as µ= Z 2 FP FQ ξ [D-19] where ⎛ Tc ξ = 0.6351 e Tr 0.9425e −0.1726Tr− 0.Appendix D where µ follows: 0 ξ is found from Eq.0578Tr−37.7368 2.3088 f = 0. FP = 1 + (FP0 − 1)Y −3 FP0 0 − 1 Y −1 − 0. The values of the constants in Eq.176⎜ ⎜ M 3 P4 ⎝ w c ⎞ ⎟ ⎟ ⎠ 1 6 [D-20] The aforementioned method for viscosity estimation was implemented into the CFD solver via UDF.007(ln Y ) 1 + FQ [D-17] FQ = ( )[ 4 ] F 0 Q [D-18] Finally.245 × 10 −3 5. [D-10].2723) c= d= 0.

mu_lp=((0.-37. [D-21]).449*tr))+(0. thread). µ = aT 6 + bT 5 + cT 4 + dT 3 + eT 2 + fT + g [D-21] A sample of the obtained coefficients for Eq. a=(0. .340*exp(4. real pr.-0. and obtained numerical values were compared with the prediction of the Lucas method.0.3286)).2310*pow(tr. real c.d))).0.e))/((b*pow(pr. resulting in a good agreement between the numerical results and the theoretical estimation (see Figure D-6). mu=mu_lp*(1+((a*pow(pr.3088. e=1.1. -1)))). c=(0. tr=t/304. real e.1726*pow(tr.209 - .h" DEFINE_PROPERTY(cell_viscosity. real a. can then be fed into the CFD solver as an UDE.6553*tr)-1.6351)). In order to quantify the round-up error associated with the numerical solver. b=a*((1.9425*exp(-0. real b. a simplified viscosity model could be used. real f.058*tr))+0.7368/tr)*exp(2.1 K% %Pr: 7380000 Pa% %METHOD: LUCAS% #include "udf. real tr. [D-21] for estimating the viscosity of supercritical CO2 can be seen in Table D-4. } return mu. a simulation for a viscosity-varying flow of supercritical CO2 in a Venturi tube was set.001245/tr)*exp(5.4489)).0578*pow(tr. fitting the results obtained with the theoretical method to a 6th degree polynomial expression. pr=p/7380000. real mu_lp. For situations where the static pressure could be considered as constant along the computed model. cell.f))+pow((1+(c*pow(pr.018)/39194. f=0. thread) { real mu.807*pow(tr.4489/tr)*exp(3.Appendix D %UDF EXAMPLE% %PROPERTY TO BE MODIFIED INTO SOLVER: VISCOSITY% %FLUID: CO2% %Tr: 304. real d. d=(1.7332)). real p=C_P(cell.2723). thread).1853*pow(tr.357*exp(-0. and a graphical representation of the previously stated polynomial fitting is shown in Figure D-5.-7. This simplified model consisted on expressing the viscosity of the fluid (at constant pressure) as a function of temperature. real t=C_T(cell.618))-(0. The obtained polynomial expression (which can be written in general form as shown in Eq.92.

72 x 10-9 e 8.77 x 10-4 2. Viscosity parity plot for supercritical CO2 (numerical results vs.30 x 10-15 1.11 x 10-18 -4.E-05 310 330 350 8 MPa 16 MPa 370 390 Temperature [K] 10 MPa 18 MPa 12 MPa 20 MPa 410 430 14 MPa 22 MPa 450 Figure D-5.09 x 10-14 9.03 x 10-11 -9.60 x 10-15 5.72 x 10-12 -1.E-05 2. Viscosity polynomial fitting for supercritical CO2 2.Appendix D P [MPa] 8 10 12 14 16 18 20 22 Table D-4.41 x 10-3 -3.18 x 10-18 -3.34 x 10-7 -4.26 x 10-4 2.21 x 10-12 -1.16 x 10-4 1.74 x 10-9 7.18 x 10-5 1.84 x 10-7 -1.36 x 10-12 -3.20 x 10-6 -1.89 x 10-15 c 5.67 x 10-3 Obtained coefficients for Eq.91 x 10-4 1.47 x 10-5 g 8.18 x 10-2 -9.57 x 10-9 3.12 x 10-3 -6.52 x 10-18 -1. Lucas method) .57 x 10-15 7.16E-05 Viscosity [Pa· s] from estimation Figure D-6.57 x 10-12 d -2.28 x 10-6 -1.75 x 10-18 b -5. a 2.07 x 10-7 -1.80 x 10-10 4.52 x 10-4 -1.15E-05 2.23 x 10-3 -9.08 x 10-12 -7.17 x 10-9 4.49 x 10-4 1.01 x 10-18 -4.66 x 10-9 1.13E-05 2.32 x 10-18 -2.61 x 10-7 f -1.78 x 10-12 -8.27 x 10-15 2.45 x 10-6 -1.77 x 10-18 -4.33 x 10-2 -1.13E-05 2.19 x 10-12 -5.60 x 10-9 2.16E-05 Viscosity [Pa· s] from CFD 2.E-05 Viscosity [Pa· s] 6.210 - .07 x 10-4 6. [D-21] for supercritical CO2 9.14E-05 2.71 x 10-15 3.33 x 10-9 5.07 x 10-2 -1.22 x 10-18 -1.15E-05 2.10 x 10-15 9.01 x 10-6 -7.14E-05 2.

1 Mass fraction C7H8 CFD Estimation Lucas Estimation Figure D-8.1 MPa 1.E-05 0 0. the pure component viscosity was calculated by the aforementioned method of Lucas (1980). 1.025 0. proving as done for the density that the CFD solver fits the results expected with the selected methods for comparison. Viscosity estimation for a binary mixture [C7H8/CO2] at 298 K and 60 MPa . a mass weighted mixing rule was applied: µ = ∑ Yi ⋅ µ i i [D-22] Results obtained with the CFD solver were compared against those obtained using Lucas Method for mixtures (i.E-03 Viscosity [Pa· s] 1.075 0.1 Mass fraction C7H8 Lucas estimation CFD estimation Figure D-7.49E-05 1.05 0.57E-05 Viscosity [Pa· s] 1.Appendix D D-2.e. imposed to the CFD solver via UDF or UDE. Mixtures To estimate the viscosity of a mixture (at low or high pressure)..025 0. For estimating the viscosity of the mixture. a similar test to that described in section D-1.075 0. From Figure D-7 it can be seen that the calculations through CFD are almost exactly the same as the ones done with the contrast method.3.E-04 1. In this test. see Figure D-7).45E-05 0 0.05 0.53E-05 1. was developed.211 - .3. The results are almost identical for the three temperatures tested in atmospheric pressure situations. Viscosity estimation for a binary mixture [C7H8/CO2] at 310 K and 0.

016 ( where 3 ⎡ Tc M w N 02 ⎤ Γ=⎢ ⎥ 5 4 ⎣ R Pc ⎦ 1 6 [D-26] The aforementioned method for thermal conductivity estimation was implemented into the CFD solver via UDF. which is an acceptable range (Guardo et al.5 0. (k − k )Γz 0 5 c 5 c 5 c = 1. Fluid @ P ≥ Pc In the case of a supercritical fluid it was chosen to define the thermal conductivity using excess thermal conductivity correlations (Stiel and Thodos.. The values used for the thermal conductivities of the simulated gases were taken from experimental data and specific correlations available in the literature (Reid et al.1 K% %Pr: 7380000 Pa% %METHOD: THERMAL EXCESS% #include "udf.0 < ρ r < 2. An example of a UDF for estimating the thermal conductivity of CO2 using the thermal excess method would be as follows: %UDF EXAMPLE% %PROPERTY TO BE MODIFIED INTO SOLVER: THERMAL CONDUCTIVITY% %FLUID: CO2% %Tr: 304. 1987. Measured errors were lower than 10 %. .22 × 10 −2 e 0. for all cases analyzed the divergence between CFD estimated results and Lucas estimation increases as the mass fraction of solute increases. D-3. 1999).2.1. cell. Gas @ atmospheric pressure In the case of a gas at atmospheric pressure it was chosen to define the thermal conductivity as a constant (independent of pressure and temperature). Yaws. the greatest numerical errors obtained for the CFD simulations were located at the saturation point. thread).h" DEFINE_PROPERTY(cell_thermal_conductivity.155 ρ r + 2. D-3.069 ( (k − k )Γz 0 = 2. thread) { real ro=C_R(cell.535 ρ r − 1 ( ) ) ) ρ r < 0.5 < ρ r < 2.8 [D-23] [D-24] [D-25] (k − k )Γz 0 = 1. Thermal conductivity D-3.60 × 10 −3 e1. As happened with density. 2005)..0 2. 1964).14 × 10 −2 e 0. According to this.67 ρ r − 1.Appendix D An example of the results obtained for the estimation of viscosity in high pressure situations can be seen in Figure D-8.212 - .

ror=ro/468. } return k.0329 0.0331 0.0335 0. Yaws. In order to quantify the round-up error associated with the numerical solver.0385*(exp(0. thread). 1987.0333 0.Appendix D real real real real t=C_T(cell. 0.0082*(exp(1.016))+ko. if (ror<0.) k=(0.000000005477*pow(t.5) k=(0.).069))+ko. thermal excess method) D-4. 1999)..0337 Thermal conductivity [W/m· K] from CFD 0. else if (ror<2. and obtained numerical values were compared with the prediction of the thermal excess method.007215+(0. resulting in a good agreement between the numerical results and the theoretical estimation (see Figure D-9).036*(exp(0.535*ror)-1))+ko. ko.213 - .)(0.8) k=(0. ko=-0. else if (ror<2.2.1. Thermal conductivity parity plot for supercritical CO2 (numerical results vs.0333 0.67*ror)-1.58. Heat capacity D-4.00008015*t)+(0.0337 Thermal conductivity [W/m· K] from estimation Figure D-9.155*ror)+2. Gas @ atmospheric pressure In the case of a gas at atmospheric pressure it was chosen to define the heat capacity as a constant (independent of pressure and temperature).0329 0. ror. a simulation for a thermal conductivity-varying flow of supercritical CO2 in a Venturi tube was set. k.0335 0.00000000001053*pow(t. . The values used for the heat capacity of the simulated gases were taken from experimental data and specific correlations available in the literature (Reid et al.0331 0.3.

real e. real f. ∆C p is a residual heat capacity. cell.)) +(0.00005602*pow(t. An example of a UDF for estimating the heat capacity of CO2 using the thermal excess method would be as follows: %UDF EXAMPLE% %PROPERTY TO BE MODIFIED INTO SOLVER: HEAT CAPACITY% %FLUID: CO2% %Tr: 304.1. real t=C_T(cell.044/ro. c=0. real v.1. real c. thread).1 K% %Pr: 7380000 Pa% %METHOD: RESIDUAL HEAT CAPACITY .)). a=6. d=log((v+b)/v). f=a/(2*v*(v+b)*pow(t.3. at the same temperature and composition: 0 Cp = Cp + ∆C p [D-27] where this relation applies to either a pure gas or a mixture at constant composition.2. co=19. real co. e=8. 1983): T (∂P ∂T )V ⎛ ∂2P ⎞ ∆C p = T ∫ ⎜ ⎟dV − (∂P ∂V ) − R ⎜ ∂T 2 ⎟ ⎠ T ∞⎝ V 2 [D-28] The aforementioned method for the heat capacity estimation was implemented into the CFD solver via UDF. real b. .46. real a. Fluid @ P ≥ Pc In the case of a supercritical fluid it was chosen to define the heat capacity relating it to the value in the ideal-gas state. real h. real g.314/(v-b).)). thread). v=0. For a pressure-explicit equation of state. real dc.5)). real d.2.07344*t)-(0.214 - .h" DEFINE_PROPERTY(cell_heat_capacity.)*pow((v+b).75*a/(b*pow(t.8+(0.EOS% #include "udf.2. b=0.Appendix D D-4.2. thread) { real ro=C_R(cell.5)*pow(v.0000297.00000001715*pow(t. g=a*((2*v)+b)/(pow(t.5)). real c. ∆C p is most conveniently determined by (see Modell and Reid.0.

)/(g-h))-8.314.41 x 106 4.70 x 10-6 -3.44 x 102 1.29 x 103 g 4.59 x 105 Obtained coefficients for Eq.00 x 10-8 -2. Heat capacity polynomial fitting for supercritical CO2 .85 x 100 -3.93 x 10-2 6.68 x 107 1.73 x 105 -4.46 x 10-10 -3.54 x 10-10 b -2.94 x 104 -1.02 x 107 2.72 x 10-3 3.80 x 10-1 -2.044.70 x 10-3 1.60 x 101 f -6.86 x 10-9 3.21 x 10-2 1. [D-29] for estimating the heat capacity of supercritical CO2 can be seen in Table D-5.37 x 104 6.50 x 100 -6. a 1.81 x 103 1.17 x 10-7 c 2.314*t/pow((v-b).Appendix D h=8.59 x 105 -3.52 x 103 2.17 x 104 -2. The obtained polynomial expression (which can be written in general form as shown in Eq. a simplified heat capacity model could be used.215 - . C p = aT 6 + bT 5 + cT 4 + dT 3 + eT 2 + fT + g [D-29] A sample of the obtained coefficients for Eq.24 x 10-7 -9.01 x 10-5 -6.67 x 10-9 2.83 x 108 -2.89 x 10-4 2.16 x 100 -1.48 x 106 2.01 x 10-1 -8.02 x 103 2. [D29]).61 x 101 -9. fitting the results obtained with the theoretical method to a 6th degree polynomial expression.69 x 103 4. } return c.90 x 105 -6.48 x 10-1 e 4.27 x 10-1 2.79 x 10-6 -9. c=(co+dc)/0. can then be fed into the CFD solver as an UDE.2).03 x 102 5.01 x 102 -5. This simplified model consisted on expressing the heat capacity of the fluid (at constant pressure) as a function of temperature.27 x 105 -1. [D-29] for supercritical CO2 10000 Cp [J/kmol· K] 7000 4000 1000 310 345 8 MPa 16 MPa 380 Temperature [K] 10 MPa 18 MPa 12 MPa 20 MPa 415 14 MPa 22 MPa 450 Figure D-10. and a graphical representation of the previously stated polynomial fitting is shown in Figure D-10.40 x 10-5 -2. For situations where the static pressure could be considered as constant along the computed model.59 x 10-7 7.15 x 107 2.2. P [MPa] 8 10 12 14 16 18 20 22 Table D-5.49 x 10-8 8.08 x 10-3 -5.05 x 107 4.08 x 10-4 7.76 x 10-9 1. dc=(c*d)-(t*pow((e+f).10 x 108 -2.32 x 106 -2.88 x 10-4 d -1.

Forth edition. Redlich. O. and Thodos. and Robinson.Y. (1980). A. Fluent Inc. L. Oliver. a simulation for a heat capacity-varying flow of supercritical CO2 in a Venturi tube was set. B. Colmar. The estimated error for the heat capacity was never superior to 15 %. Yaws. (1949). France. J. and Kwong. Larrayoz. and obtained numerical values were compared with the prediction of the residual heat capacity method method. p. Proceedings of the 10th meeting on supercritical fluids. 233 – 244.S.. McGraw-Hill.. . New York. A. G. 2100 Cp [J/kg· K] from CFD 1900 1700 1700 1900 C p [J/kg·K] from estimation 2100 Figure D-11.. 59 – 64. resulting in a reasonably good agreement between the numerical results and the theoretical estimation (see Figure D-11). Using CFD simulations to estimate properties of a supercritical binary mixture. McGraw-Hill. On the thermodynamics of solutions V: an equation of state. Chemical Reviews. C. [CD-ROM] Lucas. (2005).. Fugacities of gaseous solutions.216 - .M.. (1999). Dechema. 573.Appendix D In order to quantify the round-up error associated with the numerical solver. Poling. The thermal conductivity of nonpolar substances in the dense gaseous and liquid regions. which was considered to be within an acceptable range. (1987). Peng.B. 10. 15. (2005). Stiel. Reid. residual heat capacity method) References Fluent Inc.C. Heat capacity parity plot for supercritical CO2 (numerical results vs.P. Guardo. Chemical properties handbook.A. 26 – 30. The properties of gases and liquids. (1964). D.. R.N. Fluent 6. M.L.I.. J. AIChE Journal. Boston. Prausnitz. Phase equilibria and fluid properties in the chemical industry.. Industrial & Engineering Chemistry Fundamentals. A new two constant equation of state.... Frankfurt. K. 44. (1976).. D.2 user’s guide.

« Boundary » .APPENDIX E Description & inputs for setting up a cfd simulation BOUNDARY CONDITIONS James Stanley Daughtery.

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• • • . E-2. It is not necessary to use mass flow inlets in incompressible flows because when density is constant. They are appropriate where the exit flow is close to a fully developed condition. E-2. E-1. velocity inlet boundary conditions will fix the mass flow. the boundary conditions listed above will be described. therefore. in case of back flow). Pressure outlet boundary conditions are used to define the static pressure at flow outlets (and also other scalar variables. symmetry. solid (porous is a type of fluid zone) In this appendix. Internal cell zones: fluid. This section includes descriptions of how each type of condition selected for this work is used. They are.219 - . mass flow inlet.Appendix E Boundary conditions specify the flow. Used boundary types The boundary types used in this work are classified as follows: • • • Flow inlet and exit boundaries: velocity inlet. as the outflow boundary condition assumes a zero normal gradient for all flow variables except pressure. The use of a pressure outlet boundary condition instead of an outflow condition often results in a better rate of convergence when backflow occurs during iteration. Outflow boundary conditions are used to model flow exits where the details of the flow velocity and pressure are not known prior to solution of the flow problem. Flow inlets and exits Commercial CFD codes have a wide range of boundary conditions that permit flow to enter and exit the solution domain.1. and an explanation of how to set them and when they are most appropriately used will be provided. They are not appropriate for compressible flow calculations. and what information is needed for each one. and pole boundaries: wall. Mass flow inlet boundary conditions are used in compressible flows to prescribe a mass flow rate at an inlet. thermal and species composition variables on the boundaries of a physical model. a critical component of CFD simulations and it is important that they are specified appropriately. Recommendations for determining inlet values of the turbulence parameters are also provided. repeating. pressure outlet. Using flow boundary conditions The inlet and exit boundary condition options used in this work are as follows: • Velocity inlet boundary conditions are used to define the velocity and scalar properties of the flow at inlet boundaries. Wall.

16 Re DH u ( ) −1 8 [E-1] At a Reynolds number of 50. E-2. far-field boundaries. This section describes which quantities are needed for specific turbulence models and how they must be specified. Nevertheless. Determining turbulence parameters When the flow enters the domain at an inlet. turbulent viscosity ratio.1. . These quantities are discussed further in the following sections. Uniform specification of turbulence quantities In some situations. for example. outlet. u .Appendix E E-2. If the flow upstream is under-developed and undisturbed.2. or far-field boundary. Turbulence intensity I . making the result of the calculation relatively insensitive to the inflow boundary values. if you are simulating a wind-tunnel experiment. The turbulence intensity at the core of a fully-developed duct flow can be estimated from the following formula derived from an empirical correlation for pipe flows: I≡ u′ = 0. Ideally.2. If the flow is fully developed. caution must be used to ensure that boundary values are not so unphysical as to contaminate your solution or impede convergence. the turbulence intensity will be 4%. u ′ . you can use a low turbulence intensity. For example. For internal flows. you can specify the turbulence quantities in terms of more convenient quantities such as turbulence intensity. Alternatively.05%.000. E-2. the turbulence intensity in the free stream is usually available from the tunnel characteristics. it is appropriate to specify a uniform value of the turbulence quantity at the boundary where inflow occurs.220 - . Examples are fluid entering a duct. and turbulence length scale. you will have a good estimate of the turbulence intensity at the inlet boundary from external. to the mean flow velocity.2. as the ones presented in this work. The turbulence intensity. hydraulic diameter. measured data. higher levels of turbulence are generated within shear layers than enter the domain at flow boundaries. the CFD code requires specification of transported turbulence quantities. It also provides guidelines for the most appropriate way of determining the inflow boundary values. is defined as the ratio of the root-mean-square of the velocity fluctuations. You can use turbulence specification methods to enter uniform constant values instead of profiles. In modern low-turbulence wind tunnels. the turbulence intensity may be as high as a few percent. A turbulence intensity of 1% or less is generally considered low and turbulence intensities greater than 10% are considered high. or even fully-developed duct flows where accurate profiles of turbulence quantities are unknown. the turbulence intensity at the inlets is totally dependent on the upstream history of the flow. the free-stream turbulence intensity may be as low as 0. according to this formula. This is particularly true of external flows where unphysically large values of effective viscosity in the free stream can “swamp” the boundary layers. In most turbulent flows.2.

An approximate relationship between l and the physical size of the duct is l = 0..Appendix E E-2. the turbulence parameters are set so that 1 < µ t µ < 10 . at the free-stream boundaries of most external flows. it is a suitable approximation. from l = 0. The factor of 0. For flows downstream of turning vanes. l is restricted by the size of the duct. For wall-bounded flows in which the inlets involve a turbulent boundary layer.07 is based on the maximum value of the mixing length in fully-developed turbulent pipe flow. such as a perforated plate. it is more appropriate to base the turbulence length scale on the characteristic length of the obstacle rather than on the duct size. Turbulence length scale and hydraulic diameter The turbulence length scale. perforated plates.2. choose the Intensity and Length Scale method and use the boundary-layer thickness.2. µ t µ is fairly small. Typically. For most cases.07 L [E-2] where L is the relevant dimension of the duct. l . It should be noted that the relationship of Equation [E-2]. to compute the turbulence length scale. If the turbulence derives its characteristic length from an obstacle in the flow. you can base L on the hydraulic diameter. etc. however. In a channel of non-circular cross-section. l . • • E-2. which relates a physical dimension ( L ) to the turbulence length scale ( l ). Turbulent viscosity ratio The turbulent viscosity ratio. and fully-developed duct flows. where L is the diameter of the pipe.4δ 99 . is directly proportional to the turbulent Reynolds number layers. you can choose Turbulent Viscosity Ratio (for the Spalart-Allmaras model) or Intensity and Viscosity Ratio (for the κ − ε models and the κ − ω models). To specify quantities in terms of the turbulent viscosity ratio. choose the Intensity and Hydraulic Diameter specification method and specify the hydraulic diameter L = D H in the Hydraulic Diameter field. .221 - . Re t is large (on the order of 100 to 1000) in high-Reynolds-number boundary ) µ t µ .3. Guidelines for choosing the characteristic length L or the turbulence length scale l for selected flow types are listed below: • For fully-developed internal flows. Enter this value for l in the Turbulence Length Scale field. shear layers. In fully-developed duct flows. is not necessarily applicable to all situations. choose the Intensity and Hydraulic Diameter method and specify the characteristic length of the flow opening for L in the Hydraulic Diameter field. since the turbulent eddies cannot be larger than the duct. is a physical quantity related to the size of the large eddies that contain the energy in turbulent flows. (Re t ≡ κ 2 εν . However.4. δ 99 .

222 - . a velocity inlet may be used to define the flow velocity at flow exits. E-2. so they will rise to whatever value is necessary to provide the prescribed velocity distribution. at flow inlets. Mass flow inlet boundary conditions Mass flow boundary conditions can be used to provide a prescribed mass flow rate or mass flux distribution at an inlet.) In such cases you must ensure that overall continuity is maintained in the domain. In special instances. The mass flow rate entering a fluid cell adjacent to a velocity inlet boundary is computed as: & = ∫ ρ ⋅ u ⋅ dA m [E-3] Note that only the velocity component normal to the control volume face contributes to the inlet mass flow rate. momentum fluxes. A mass flow inlet is often used when it is more important to match a prescribed mass flow rate than to match the total pressure of the inflow stream. pressure. Density at the inlet plane is either constant or calculated as a function of temperature. You will enter the following information for a velocity inlet boundary: • • • • Velocity magnitude and direction or velocity components Temperature (for energy calculations) Turbulence parameters (for turbulent calculations) Chemical species mass fractions (for species calculations) When your velocity inlet boundary condition defines flow entering the physical domain of the model.Appendix E E-2. and fluxes of energy and chemical species. . and/or species mass fractions. You should also be careful not to place a velocity inlet too close to a solid obstruction.4.3. (The scalar inputs are not used in such cases. and its use in compressible flows will lead to a non-physical result because it allows stagnation conditions to float to any level. where the mass fractions are the values you entered as an inlet condition. since this could cause the inflow stagnation properties to become highly non-uniform. specifying the mass flux permits the total pressure to vary in response to the interior solution. The total (or stagnation) properties of the flow are not fixed. Physically. while the velocity of the main flow is governed primarily by a (different) pressure inlet/outlet boundary condition pair. An example is the case of a small cooling jet that is bled into the main flow at a fixed mass flow rate. the CFD code uses both the velocity components and the scalar quantities that you defined as boundary conditions to compute the inlet mass flow rate. This boundary condition is intended for incompressible flows. Velocity inlet boundary conditions Velocity inlet boundary conditions are used to define the flow velocity. along with all relevant scalar properties of the flow.

as described earlier in this section. If the average mass flux is also specified (either explicitly by you or automatically by the CFD code). so if both the pressure inlet boundary condition and the mass flow inlet boundary condition are acceptable choices. flow direction. If a m total mass flow rate is specified. and this velocity is used to compute the fluxes of all relevant solution variables into the domain. There are two ways to specify the mass flow rate. If the inlet is subsonic. the CFD code converts it internally to a uniform mass flux by dividing the mass flow rate by the total inlet area: ρ ⋅ un = & m A [E-4] If the direct mass flux specification option is used. the static temperature and static pressure are required to compute the density: p = ρ ⋅ R ⋅T [E-5] If the inlet is supersonic. Each of these cases is examined below. . The second is to specify the mass flux.223 - . & . the static pressure used is the value that has been set as a boundary condition. for the inlet. velocity inlet boundary conditions will fix the mass flow. and total temperature are used. It is not necessary to use mass flow inlets in incompressible flows because when density is constant. the computed velocity is adjusted so that the correct mass flow value is maintained. The manner in which the density is obtained depends upon whether the fluid is modeled as an ideal gas or not. a velocity is computed for each face in that zone. the static pressure is extrapolated from the cells inside the inlet face. your inputs for mass flow rate. it is used to correct the specified mass flux profile. Once the value of ρ ⋅ u n at a given face has been determined. The first is to specify the total mass flow rate. If the fluid is an ideal gas. You will enter the following information for a mass flow inlet boundary: • Mass flow rate. ρ ⋅ u n (mass flow rate per unit area). the mass flux can be varied over the boundary by using profile files or user-defined functions. static pressure. the density at the face must be determined in order to find the normal velocity. mass flux. or (primarily for the mixing plane model) mass flux with average mass flux Total (stagnation) temperature Static pressure Flow direction Turbulence parameters (for turbulent calculations) Chemical species mass fractions (for species calculations) • • • • • When mass flow boundary conditions are used for an inlet zone. With each iteration. To compute this velocity.Appendix E The adjustment of inlet total pressure might result in a slower convergence. you should choose the former.

The total enthalpy is given by 1 h0 (T0 ) = h(T ) + u 2 2 [E-6] where the velocity is related to the mass flow rate given by Equation [E-4]. The velocity is then computed using Equation [E-4]. pressure will be extrapolated from the flow in the interior. which is determined from the total temperature that has been set as a boundary condition. When you are modeling incompressible flows. Equation [E-6] can be solved to obtain the static temperature. All other flow quantities are extrapolated from the interior. the static temperature is equal to the total temperature.5. These fluxes are used as boundary conditions for the corresponding conservation equations during the course of the solution. the flux of turbulence kinetic energy is ρ ⋅ κ ⋅ u n . The value of the specified static pressure is used only while the flow is subsonic. You will enter the following information for a pressure outlet boundary: • • Static pressure Backflow conditions o o o o • Total (stagnation) temperature (for energy calculations) Backflow direction specification method Turbulence parameters (for turbulent calculations) Chemical species mass fractions (for species calculations) Target mass flow rate (not available for multiphase flows) .Appendix E The static temperature at the inlet is computed from the total enthalpy. The density at the inlet is either constant or readily computed as a function of the temperature and (optionally) the species mass fractions. Pressure outlet boundary conditions Pressure outlet boundary conditions require the specification of a static (gauge) pressure at the outlet boundary. the specified pressure will no longer be used. To compute the fluxes of all variables at the inlet. Should the flow become locally supersonic. E-2.224 - . the flux velocity is used along with the inlet value of the variable in question. A set of "backflow'' conditions is also specified should the flow reverse direction at the pressure outlet boundary during the solution process. For example. Convergence difficulties will be minimized if you specify realistic values for the backflow quantities. Using Equation [E-5] to relate density to the (known) static pressure and (unknown) temperature.

as noted below. Outflow boundary conditions Outflow boundary conditions are used to model flow exits where the details of the flow velocity and pressure are not known prior to solution of the flow problem.6. and extrapolates all other conditions from the interior of the domain. Fully-developed flows are flows in which the flow velocity profile (and/or profiles of other properties such as temperature) is unchanging in the flow direction. when there is no area change at the outflow boundary. however. Note that outflow boundaries cannot be used in the following cases: • if a problem includes pressure inlet boundaries. even if the flow is incompressible • • The boundary conditions used at outflow boundaries are as follows: • • A zero diffusion flux for all flow variables An overall mass balance correction The zero diffusion flux condition applied at outflow cells means that the conditions of the outflow plane are extrapolated from within the domain and have no impact on the upstream flow. or model a "slip'' wall by specifying shear. Wall boundary conditions Wall boundary conditions are used to bound fluid and solid regions.Appendix E At pressure outlets. but using a symmetry boundary will apply symmetry conditions for . (You can also model a slip wall with zero shear using the symmetry boundary type. The extrapolation procedure used updates the outflow velocity and pressure in a manner that is consistent with a fully-developed flow assumption. or split mass flow): the CFD code extrapolates the required information from the interior.225 - . In viscous flows. the CFD code uses the boundary condition pressure you input as the static pressure of the fluid at the outlet plane. Only the diffusion fluxes in the direction normal to the exit plane are assumed to be zero. use pressure outlet boundary conditions instead if you are modeling compressible flow if you are modeling unsteady flows with varying density. It is important. to understand the limitations of this boundary type. You do not define any conditions at outflow boundaries (unless you are modeling radiative heat transfer. The zero diffusion flux condition applied at outflow boundaries is approached physically in fully-developed flows. a discrete phase of particles. the noslip boundary condition is enforced at walls by default. but you can specify a tangential velocity component in terms of the translational or rotational motion of the wall boundary. E-2. It is important to note that gradients in the cross-stream direction may exist at an outflow boundary. E-3.

In a laminar flow . temperature. You will enter the following information for a wall boundary: • • • • • Thermal boundary conditions (for heat transfer calculations) Wall motion conditions (for moving or rotating walls) Shear conditions (for slip walls. . Five types of thermal conditions are available: • • • • • Fixed heat flux Fixed temperature Convective heat transfer External radiation heat transfer Combined external radiation and convection heat transfer For no-slip wall conditions. The shear stress and heat transfer between the fluid and wall are computed based on the flow details in the local flow field. Wall treatments for turbulent flows are described in Appendix B. all walls use a slip condition. the CFD code uses the properties of the flow adjacent to the wall/fluid boundary to predict the shear stress on the fluid at the wall.226 - . In laminar flows this calculation simply depends on the velocity gradient at the wall. optional) Wall roughness (for turbulent flows. it will compute the tangential velocity at the boundary. For specified-shear walls. you must be sure that the grid is sufficiently fine to accurately resolve the boundary layer. If you are modeling inviscid flow. the heat flux to the wall from a fluid cell is computed as q = h f (Tw − T f ) + q rad [E-8] Note that the fluid-side heat transfer coefficient is computed based on the local flow-field conditions (e. optional) Species boundary conditions (for species calculations) When you are solving the energy equation. the wall shear stress is defined by the normal velocity gradient at the wall as τw = µ ∂u ∂n [E-7] When there is a steep velocity gradient at the wall. When a fixed temperature condition is applied at the wall. and velocity profiles).Appendix E all equations). while in turbulent flows one of the approaches described in Appendix B is used. turbulence level. you need to define thermal boundary conditions at wall boundaries. so they are frictionless and exert no shear stress on the adjacent fluid.g..

In laminar flows. They can also be used to model zero-shear slip walls in viscous flows.227 - . the fluid side heat transfer at walls is computed using Fourier's law applied at the walls in its discrete form: ⎛ ∂T ⎞ q = kf ⎜ ⎟ ⎝ ∂n ⎠ w where n is the local coordinate normal to the wall. the CFD code uses the law-of-the-wall for temperature derived using the analogy between heat and momentum transfer. Figures E-1 and E-2 illustrate two examples of symmetry boundary conditions used in this way. as noted above. The CFD code uses Equation [E-8] and your input of heat flux to determine the wall surface temperature adjacent to a fluid cell as Tw = q − q rad + Tf hf [E-9] where. and the expected pattern of the flow/thermal solution. Use of symmetry to model one quarter of a 3D duct .Appendix E When you define a heat flux boundary condition at a wall. You do not define any boundary conditions at symmetry boundaries. Symmetry boundary conditions Symmetry boundary conditions are used when the physical geometry of interest. you specify the heat flux at the wall surface. the fluid-side heat transfer coefficient is computed based on the local flow-field conditions. This section describes the treatment of the flow at symmetry planes and provides examples of the use of symmetry. have mirror symmetry. but you must take care to correctly define your symmetry boundary locations. E-4. Symmetry boundaries are used to reduce the extent of your computational model to a symmetric subsection of the overall physical system. [E-10] For turbulent flows. Figure E-1. See Appendix B for details.

or the Spalart-Allmaras model. the κ − ω model. you can choose to define the fluid zone as a laminar flow region. these conditions determine a zero flux across the symmetry plane. The only required input for a fluid zone is the type of fluid material. you will need to specify the rotation axis. Since the shear stress is zero at a symmetry boundary. Optional inputs allow you to set sources or fixed values of mass. There is no diffusion flux across a symmetry plane: the normal gradients of all flow variables are thus zero at the symmetry plane. momentum.228 - . Use of symmetry to model one quarter of a circular cross-section The CFD code assumes a zero flux of all quantities across a symmetry boundary. . Fluid conditions A fluid zone is a group of cells for which all active equations are solved. it can also be interpreted as a "slip'' wall when used in viscous flow calculations. You must indicate which material the fluid zone contains so that the appropriate material properties will be used. There is no convective flux across a symmetry plane: the normal velocity component at the symmetry plane is thus zero. The symmetry boundary condition can therefore be summarized as follows: • • Zero normal velocity at a symmetry plane Zero normal gradients of all variables at a symmetry plane As stated above. You can also define motion for the fluid zone. E-5. which is required by the definition of symmetry. species. heat (temperature). If there are rotationally periodic boundaries adjacent to the fluid zone. and other scalar quantities. turbulence.Appendix E Figure E-2. If you are modeling turbulence using one of the κ − ε models.

« List » .APPENDIX F LIST OF PUBLICATIONS in journals & congresses ´ Acclaimed Images.

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CFD allows us to obtain a more accurate view of the fluid flow and heat transfer mechanisms present in fixed bed equipment. Recasens. . and wall heat transfer parameters were chosen as validation parameters. and kr/kf are given for different values of Re (transition and turbulent flow). E.231 - . Guardo. Forty-four spheres stacked in a nonregular maximum-space-occupying arrangement in a cylindrical container were used as the geometrical model. this tool permits obtaining of mean and fluctuating flow and temperature values in any point of the bed. In this way. Air is chosen as flowing fluid. An important problem when modeling a turbulent flow fixed-bed reactor is to decide which turbulence model is the most accurate for this situation. 1733 – 1742 Influence of the turbulence model in CFD modeling of wall-to-fluid heat transfer in packed beds A. 43. 60. Egusquiza. Egusquiza. heat transfer parameters (Nuw. Estimates of the pressure drop along the bed. Abstract Computational fluid dynamics as a simulation tool allows obtaining a more detailed view of the fluid flow and heat transfer mechanisms in fixed-bed reactors. Abstract This work aims to test the application of computational fluid dynamics (CFD) modeling to fixed bed equipment design. Chemical Engineering Science. M. Fluent 6. velocity and thermal fields within the bed are obtained. M. F. together with a turbulence model when needed.A. Recasens. 2005. However.A. Larrayoz. assuming nonregular packing is a more realistic way to simulate the behavior of a fixed bed and therefore to estimate important design parameters. Coussirat. To gain insight into this subject. ¢P. M. Studies of CFD with a fixed bed design commonly use a regular packing approach to define bed geometry.Appendix F F-1. To account for the fluid flow and thermally fluctuating components in the turbulent cases. As a fluid flow simulation tool.and twoequation turbulence models were used for simulation. 2004. one. Articles in journals Industrial & Engineering Chemistry Research. In order to judge the capabilities of these turbulence models. E. Guardo. Cases of laminar and turbulent flows are presented. Numerical pressure drop. this study presents a comparison between the performance in flow and heat transfer estimation of five different RANS turbulence models in a fixed bed composed of 44 homogeneous stacked spheres in a maximum space-occupying arrangement in a cylindrical container by solving the 3D Navier–Stokes and energy equations by means of a commercial finite volume code. and they are compared to commonly used correlations. through the resolution of 3D Reynolds averaged transport equations. Larrayoz. Air was chosen as the flowing fluid. F. 7049 – 7056 CFD flow and heat transfer in nonregular packings for fixed bed equipment design A.0 ®. and their results are compared. M. kr/kf) are estimated from numerical data and together with the pressure drop are compared to commonly used correlations for parameter estimations in fixed-bed reactors. Nuw. Coussirat.

F. To gain insight in this subject. caused by temperature or composition variations. Larrayoz. M. making the buoyancy terms of the Navier-Stokes equations an important term to model when doing a Computational Fluid Dynamics (CFD) simulation under the described conditions. Escaler. In order to impose supercritical fluid properties to the model. Carbon dioxide in the supercritical conditions was selected as a flowing fluid. (2006) can be used to describe heat transfer phenomena in a packed bed under mixed convection regime at high pressures. 4341 – 4353 CFD study on particle-to-fluid heat transfer in fixed bed reactors: Convective heat transfer at low and high pressure A. M. Chemical Engineering Science. Guardo. Density gradients. Guardo. tend to control the overall flow pattern of the fluid. Recently. (2006) have presented a correlation for particle-to-fluid heat transfer in supercritical conditions. X.A. X. Solution of these equations allows to obtain velocity and temperature profiles within the reactor.e. 2006 (Submitted – under review) CFD studies on particle-to-fluid mass and heat transfer in packed beds: free convection effects in supercritical fluids A. Larrayoz. 2006. Its transport properties at high pressure were incorporated within a CFD commercial code in order to estimate them online within the simulation process. Abstract Computational fluid dynamics (CFD) has proven to be a reliable tool for fixed bed reactor design. Particle-to-fluid mass transfer in supercritical conditions was analyzed. Recasens. based on an analogy with the correlation proposed by Stüber et al. Escaler. numerical results using a modified commercial CFD solver are presented and particle-to-fluid heat transfer in fixed beds is analyzed. forced and mixed convection at high pressure) is presented. (1996) for mass transfer.. momentum and energy balances. through the resolution of 3D transport equations for mass. The obtained numerical results presented in this work validates the idea that the modified correlation presented by Guardo et al. Two different configurations are studied: forced convection at low pressure (with air as circulating fluid) and mixed (i. M. M. Guardo et al. Recasens.A. . free + forced) convection at high pressure (with supercritical CO2 as circulating fluid). Particle-to-fluid heat transfer coefficient is of primal importance when analyzing the performance of a fixed bed reactor. Abstract Free convection effects of heat and mass transfer are of prime importance when modeling the behavior of supercritical fluids in packed bed reaction equipment and in solid extractors. Computations were made using a 3-dimensional CFD modeling strategy. because the experimental option is very expensive and time demanding. The purpose of this work was to visualize by means of CFD techniques the influence of the buoyancy forces over flow patterns and the convective flow in a packed bed filled with a supercritical fluid. and transport coefficients were obtained and validated. Coussirat. F. The numerical results obtained allow estimating useful parameters applicable to equipment design. 61.Appendix F Chemical Engineering Science.232 - . Coussirat. The obtained numerical data is compared to previously published data and a novel CFD-based correlation (for free. modifications into the CFD code were introduced by means of user defined functions (UDF) and user defined equations (UDE).

D. 1966). Intra-particle concentration profiles for all species present in the mixture (oil triglycerides and hydrogen) are obtained and compared against experimental results.A. F. Different particle sizes are studied and external mass transfer and intra-particle diffusional effects are analyzed.233 - . November 2002 Abstract In a bed of solid particles. Verified kinetic constants and intra-particle diffusion coefficients are fed into a 3D packed bed reactor model. 1999). Martínez. Ramírez. while at high flow rates it varies approximately with the square of the fluid velocity. and conversion profiles are obtained F-2. Recasens.. F. heat and mass transfer parameters in packed beds do not show sharp changes of the type noted at the transition to turbulence in pipes.Appendix F Chemical Engineering Science.. This is analogous to the law governing pressure drop in a pipe and has been corroborated with experimental data in some studies (Jolls et al. Larrayoz. Recasens Barcelona. There has been a fast growing in the study of applications in fluid flow and heat transfer. In this work. 2006 (Submitted – under review) CFD modeling on external mass transfer and intra-particle diffusional effects on the supercritical hydrogenation of sunflower oil A. Fitting of the intraparticle concentration profiles allowed to verify the kinetic reaction model. Computational Fluid Dynamics (CFD) has proven to be a powerful tool to numerically solve Navier-Stokes equations. the Navier-Stokes equations for steady-state fluid flow through a fixed bed are solved using a commercially available finite element code. Guardo. and several authors have used it to analyse flow patterns in fixed-bed equipment and to predict heat transfer parameters in studied cases (Dixon et al. A 2D CFD model of a single Pd-based catalyst pellet is presented. Guardo. like fixed bed reactors or extraction equipment. External mass transfer coefficients are obtained and presented. M.A. Larrayoz. laminar-to-turbulent flow transition has not been extensively reviewed with CFD numerical simulation. Abstract Computational Fluid Dynamics (CFD) is applied to the study of the catalytic hydrogenation of sunflower oil in the presence of a supercritical solvent. 2001. Logtenberg et al. because there is no reliable guideline to predict the flow transition in complex geometries. However. Participation in congresses 9 Congreso Mediterráneo de Ingeniería Química CFD Approach to laminar-to-turbulent flow transition in fixed-bed equipment A. However. E. Spain. Velo. and there is still doubts about when the turbulent model should be activated.. Magaña. M. M. Casanovas. GiD® (Rienzi and . the existing relationship between fluid velocity and pressure drop. I. E. at low flow rates the pressure drop has a linear dependency with the fluid velocity.

310 K). solution of equations and graphical post-processing of numerical results. 18th International Symposium on Chemical Reaction Engineering. with a uniform velocity at the bed inlet and a fixed velocity condition around the spheres and at the wall.Appendix F Font. E. geometry-based models and computational algorithms have permitted to develop flow profile predictions in packed columns [5]. M. June 2003 Abstract Fixed-bed structure study and its effects in heat and mass transfer have been widely reviewed by several authors. 60. Larrayoz. Coussirat. Regular packing types for CFD simulation of SCF extraction and reaction equipment A. M. Results are presented based on numerical convergency of the method. Several numerical simulations are developed at different values of Re.234 - . No thermal boundary conditions are applied to the model. 310 K) and in steady state flow regime. Recasens Versailles. Guardo. 6th International Symposium on Supercritical Fluids. Recasens. Fluid analyzed is taken to be CO2 in supercritical conditions (165 bar. Larrayoz. Fluid analyzed is taken to be CO2 in supercritial conditions (165 bar. Egusquiza. Regular packing of spheres has also been studied. mesh generation. Determination of geometrical properties of randomly packed beds with computational simulation has conduced to the development of algorithms for simulating the construction of random packings in cylindrical containers [1]. June 2004 . Guardo. USA. and several authors have used it to analyse flow patterns in fixed-bed equipment and to predict heat transfer parameters in studied cases [6-7] In this work we review prior approaches to geometrical sphere-based models for packed beds and propose three different geometrical arranges for packed bed equipment computer simulation. developing uniform geometries [2-4]. Influence of the Turbulence Model in CFD Modeling of Wall-to-Fluid Heat Transfer in Packed Beds A. France. F. This software includes modules for geometrical model generation. These models are used in CFD simulation of supercritical extraction and reaction equipment. M. 1733 – 1742 Abstract in prior section. F. Chicago. Computational Fluid Dynamics (CFD) has proven to be a powerful tool to numerically solve Navier-Stokes equations. Chemical Engineering Science. There has been a fast growing in the study of applications in fluid flow and heat transfer.A. No thermal boundary conditions are applied to the model. with an uniform velocity at the bed inlet and a fixed velocity condition around the spheres and at the wall. 2001). 2005.A.

6 solver). M.e.A. and several authors have used it to analyze flow patterns in fixed-bed equipment and to predict heat transfer parameters in studied cases [1-2]. a physical properties database (i. C-written programme modules based on the SRK equation of state[4]. momentum and energy calculations. Guardo. and therefore are used during simulations. the available correlations have been implemented in the modules. Energy balances permit to calculate heat transfer parameters (i. Nup. enthalpy. Larrayoz. hp. M. So this gives a wider application to SCF cases. density. In this work. June 2004 Abstract Computational Fluid Dynamics (CFD) has proven to be a powerful tool to numerically solve the fluid-flow equations so it gives a further insight into the flow pattern of contacting equipment. jh) at different operating conditions.. Newtonian and in laminar or transitional flow regime (10 < Re < 300). Fluid is taken to be compressible. and estimated values via CFD are compared with previously published heat transfer correlations estimated under similar conditions applied to simulations [5-6] . Fernández Trieste. Buoyancy terms were found to be relevant in calculations through a dimensionless analysis done to Navier-Stokes equations. For transport properties. There has been a fast growing in the study of applications in fluid flow and heat transfer. have been implemented for use with CFD commercial codes. F. entropy. Properties database was fed to CFD simulator in order to do properties estimation simultaneously with the mass.Appendix F 7th Italian Conference on Supercritical Fluids and their applications / 9th European Meeting on Supercritical Fluids CFD simulation of particle-to-fluid heat transfer under supercritical conditions: preliminary results A. thermal conductivity and sound speed) was created using accepted correlations for high pressure properties estimation [3-4]. Supercritical CO2 was chosen as circulating fluid. particle-to-fluid heat transfer is studied in a maximum-occupying-space arrangement of solid spheres in a cylindrical container. Cp.e.235 - . Cv. Boundary conditions applied to the model are as follows: • • • • • Constant velocity and temperature of the fluid at the inlet Constant temperature of the particles surface Constant pressure defined within a point of the fluid Adiabatic reactor’s wall Non-slip condition applied to wall and particle surfaces Velocity and temperature fields are obtained within the bed. together with physical properties profiles at any point of the fluid domain. Italy. Navier-Stokes equations together with energy balance are solved using a commercially available finite volume-element code (Ansys CFX 5.. viscosity. Recasens. in order to simulate via CFD the heat transfer behavior in a supercritical catalytic reactor under steady state conditions.

F. caused by temperature or composition variations. Buoyancy and sinking forces interact with forced flow in extraction with SC fluids. Flow and temperature fields are presented. Ramírez. Recasens. October 2005 . Carbon dioxide in the supercritical conditions has been selected as a flowing fluid. and heat transfer coefficients are determined and compared against empirical correlations available in the literature.Appendix F 7th International Symposium on Supercritical Fluids. A.A. Larrayoz. E. A. Santana No abstract available Valladolid. F. for both heat and mass transport. tend to control the volume forces and the overall flow pattern of the fluid. Flow and Heat Transfer simulation in a packed bed with supercritical solvent: CFD modeling of free convection effects. and flow pattern is analysed according to density profiles obtained. Guardo. The ranges of heat and mass transfer are defined where those free convective effects show themselves. Guardo. Rayleigh number is large in SCF because of liquid-like densities and gas-like viscosities.A. Particle-to-fluid heat transfer is analysed. Upflow and downflow operation regimes are modelled in order to study the influence of gravity on the free convection effects and on the heat transfer rate in the reactor. Recasens Orlando. Spain. 2ª Reunión de expertos en fluidos comprimidos Hidrogenación catalítica de aceite de girasol en fluido supercrítico y su interés en la industria alimentaria A. making the buoyancy terms of the Navier-Stokes equations an important term to model when doing a CFD simulation of a fixed bed under the described conditions. USA. M. May 2005 Abstract The CFD simulation methodology is applied to the study of the natural convection flow in equipment used in SCF technology that involves a packed bed of particles. Free convection effects of heat and mass transfer are of prime importance when modelling the behavior of supercritical fluids in empty tube and fixed bed reaction equipment and in solid extractors. Their transport and thermal properties at high pressure are incorporated within the CFD code in order to estimate them online within the simulation process. The purpose of this work was to visualize the influence of the buoyancy forces over flow patterns and the convective flow in a fixed bed reactor using a 3-dimensional CFD modelling strategy. Density gradients.236 - . M. This happens at low particle Reynolds number and large Rayleigh (either Gr·Pr or Gr·Sc) numbers. Different inflow velocities have been selected (5 < Re < 100) and contribution of free and forced convection effects is analyzed in each case. Larrayoz. making them sensitive to the gravity field.

Appendix F 10th European Meeting on Supercritical Fluids Using CFD simulations to estimate properties of a supercritical binary mixture. A. December 2005. There has been a fast growing in the study of applications in fluid flow and heat and mass transfer. making them sensitive to the gravity field [1-3] . A. The ranges of heat and mass transfer are defined where those free convective effects show themselves. Guardo. Oliver. France. for both heat and mass transport. Guardo. Fluid is taken to be compressible. December 2005. In order to impose near-critical or supercritical conditions to the fluid. Density gradients. This happens at low particle Reynolds number and large Rayleigh (either GrPr or GrSc) numbers. M. Newtonian and in laminar flow regime. Buoyancy and sinking forces interact with forced flow in extraction with SC fluids. F. tend to control the volume forces and the overall flow pattern of the fluid. M. Free convection effects of heat and mass transfer are of prime importance when modelling the behaviour of supercritical fluids in fixed bed reaction equipment and in solid extractors.A. Peng Robinson equation of state was imposed to the CFD model through a C++ subroutine compiled within the solver CFD code. In this work. a mass flux of toluene was imposed through the pipe walls. Near-critical or supercritical CO2 was chosen as circulating fluid. Abstract The CFD simulation methodology is applied to the study of the natural convection flow in equipment used in SCF technology that involves a packed bed of particles. caused by temperature or composition variations. Rayleigh number is large in SCF because of liquid-like densities and gas-like viscosities.237 - .2 solver). in order to obtain a composition profile. Abstract Computational Fluid Dynamics (CFD) has proven to be a powerful tool to numerically solve the fluid-flow equations so it gives a further insight into the flow pattern of contacting equipment. Larrayoz. France. [1-2].A. Recasens Colmar. Navier-Stokes equations together with Peng Robinson EOS and species transport and diffusion model are solved using a commercially available finite volume-element code (Fluent 6. making the buoyancy terms of the Navier – Stokes equations an important term to model when doing a CFD simulation of a fixed bed under the described conditions. Larrayoz Colmar. 10th European Meeting on Supercritical Fluids CFD flow and mass transfer simulation in a packed bed with supercritical solvent: preliminary results A. M. a prediction of the physical properties of a near-critical or supercritical binary mixture is obtained via CFD simulations in a 2D pipe flow model. Coussirat.

Mesh sensitivity analysis is done and results of a preliminary simulation are shown. Particle-to-fluid mass transfer is analysed [4]. X. Casanovas. Germany. Chemical Engineering Science. Potsdam. Ramírez. E. Downflow operation regime is modelled. Germany. but also offers a clean. June 2007 (Submitted) Abstract Hydrogenation of vegetable oil is an important process in the food industry because of its widespread application to produce margarines. Larrayoz. Recasens. Guardo. M. Escaler. M. M. a Toluene – CO2 system is analysed. CFD studies on particle-to-fluid mass and heat transfer in packed beds: free convection effects in supercritical fluids A. CFD is applied to the study of the catalytic hydrogenation of sunflower oil in the presence of a supercritical solvent. CFD modeling on external mass transfer and intra-particle diffusional effects on the supercritical hydrogenation of sunflower oil A. Computational Fluid Dynamics (CFD) modeling applied to the supercritical hydrogenation reaction can be useful in visualizing and understanding the mass transfer phenomena involved. Larrayoz. Martínez. Chemical Engineering Science. 19th International Symposium on Chemical Reaction Engineering. and flow pattern is analysed according to density profiles obtained.A. Ramírez.238 - . Recasens. Their transport properties at high pressure are incorporated within a CFD commercial code in order to estimate them online within the simulation process. M. Larrayoz. Guardo. Intra-particle concentration profiles are obtained . and other food components. 2006 (Submitted – under review) Abstract in prior section. Carbon dioxide in the supercritical conditions has been selected as a flowing fluid. E. Segovia. Spain. F. I.A. M.A. shortenings. September 2006 19th International Symposium on Chemical Reaction Engineering. September 2006 5th International Symposium on High Pressure Processes Technology and Chemical Engineering Using CFD to estimate external mass transfer coefficients and intra-particle diffusional effects on the supercritical hydrogenation of sunflower oil A. M. Supercritical technology has proven to be a reliable alternative to conventional hydrogenation process because not only the trans isomer levels can be reduced. 2006 (Submitted – under review) Abstract in prior section. Recasens. D. Guardo. and flow and composition contour fields are presented. Casanovas. Coussirat.Appendix F In order to simulate a supercritical extraction. F. Magaña. Potsdam. F. economic and environmental friendly process.

Appendix F and compared against experimental data.239 - . . The purpose of this work was to visualize the mass transfer phenomena over a single catalyst pellet and the intra-particle diffusional effects associated with particle size for the supercritical hydrogenation of sunflower oil using a 2D CFD modeling strategy. hydrogen and supercritical propane (used as a solvent) is the flowing fluid. flow velocities and particle sizes are studied and external and internal mass transfer phenomena is analyzed. Their transport properties at high pressure are incorporated within a CFD commercial code in order to estimate them online within the simulation process. A 2D CFD model of a single Pd-based catalyst pellet is presented. Intra-particle and surface concentration profiles and surface mass fluxes for all species present in the mixture (oil triglycerides and hydrogen) are obtained and compared against experimental results. flow velocities and particle sizes are studied and external and internal mass transfer phenomena is analyzed. Different temperatures. External mass transfer coefficients for hydrogen and oil triglycerides are obtained and a correlation for estimating them is presented. A mix of sunflower oil. Different temperatures.