Hydrodynamic Modeling of Adsorption - Application To The Separation of Xylenes

Master in Chemical Engineering
Hydrodynamic modeling of adsorption -

Application to the separation of xylenes
Master Thesis
of
Miguel Domingos da Silva
Thesis performed in the framework of Dissertation at
Supervisor from IFP: Dr. Frédéric Augier
Supervisor from FEUP: Prof. José Carlos Lopes
Department of Chemical Engineering

July of 2014
Hydrodynamic modeling of adsorption – Application to the separation of xylenes
Acknowledgments
First, I want to thank my supervisor from IFPEN, Dr. Fréderic Augier, for every time spent
helping me and advising me during the internship, also for putting me back on track when
things seemed confusing and dispersed.
I thank Professor José Carlos Lopes for accepting to be my supervisor from FEUP.
I thank Dr. Aude Royon-Lebeaud for her help in every detail, every problem, for the interest
demonstrated about my work and for the help with some issues that I had with Linux and
Fluent.
I thank PhD Student Leonel Gomes for the help with every call and every question that I had
even before the first day I arrived at IFPEN.
To all my friends, I thank you all for the positive thoughts that you sent me, they helped me a
lot to surpass the “being far away from home” feeling and gave me more confidence conclude
the project.
Finally, to my family, I thank you for being so supportive and believe that at the end of this
little amount of time that was the course I had all the capacity and knowledge to finish it.
Thank you all!

Abstract
Xylenes production has been increasing over time and with this there has been a major
research in developing and upgrading the separation processes. The main separation process
is the Simulated Moving Bed which consists in a chromatographic separation performed in
multi fixed-bed adsorption columns.
Within these columns there are several dispersive phenomena that can be related to
hydrodynamics or the non-linearity of the adsorption equilibrium, that deviate the flow
regime from the desired plug flow. Therefore, it is needed to study the coupling between
these dispersive phenomena and adsorption, so that the separation can be accurately
modelled. Recently, these interactions were studied by Augier et al (2008).
The main objectives of this project are to study and model hydrodynamics of an adsorption
bed of the SMB, couple it with the adsorption equilibrium and study the impact of obstacles
(such as pipes and beams) placed inside the porous media, and empty chambers before and
after the fixed bed, in the process of separation.
Results from CFD simulations show that hydrodynamics have a huge role in the separation and
cannot be separated from the adsorption equilibrium, in the absence of mass transfer
limitations. When mass transfer limitations are considered results show that 1D ideal model
approximations can be made to predict the separation, in the presence or absence of
obstacles in the porous media.
Keywords: Hydrodynamics, Adsorption, Simulated Moving Bed,

Computational Fluid Dynamics, Chromatography.
Resumo
Ao longo dos ultimos anos a produção de xilenos tem vindo a aumentar, e com isto o aumento
do interesse na investigação para melhorar os processos de separação dos mesmos. O processo
de separação que mais tem vindo a ser utilizado é o Leito Móvel Simulado, que consiste numa
separação cromatográfica feita em colunas de adsorção constituídas de leitos fixos
sobrepostos.
No interior destas colunas vários fenómenos dispersivos estão presentes, estes podem estar
relacionados com a hidrodinâmica ou devido à não linearidade do fenómeno de adsorção,
estes efeitos causam um desvio no regime de escoamento que o faz sair do pretendido fluxo
pistão. Assim sendo, é necessário estudar esses efeitos para que a separação possa ser
modelisada com precisão. Este caso foi recentemente estudado por Augier et al (2008)
Este trabalho tem como objectivos principais o estudo e modelisação da hidrodinâmica de um

leito de adsorção do Leito Móvel Simulado, acoplar a esse estudo o fenómeno de adsorção e
estudar o impacto de obstáculos (como tubos e barras) colocados no meio poroso e de zonas
livres antes e depois do meio poroso, na separação.
Os resultados das simulações CFD demonstram que a hidrodinâmica tem um papel principal na
separação e a mesma não pode ser dissociada da adsorção, aquando da absência de
limitações à transferencia de massa. Quando essas limitações são tomadas em conta, os
resultados obtidos demonstram que apoximações feitas por modelos ideais podem ser feitas
para prever a separação, quer na ausência ou presença de obstaculos dentro do meio poroso.
Palavras Chave: Hidrodinâmica, Adsorção, Leito Móvel Simulado, Dinâmica

de Fluídos Computacional, Cromatografia.
Declaration
I declare, under honor commitment, that this work is original and every non-original
contribution was referenced with the source identification.
Index
1 Introduction ........................................................................................... 1
2 Bibliographic study .................................................................................. 2
2.1 Xylenes ........................................................................................... 2
2.2 Theoretical description and background .................................................. 7
2.3 Flow characterization methods ........................................................... 12
3 Technical Description ............................................................................. 19
3.1 Experimental Setup.......................................................................... 19
3.2 CFD approach ................................................................................. 20
3.3 Ideal model approximations ............................................................... 21
4 Results and discussion ............................................................................ 23
4.1 Hydrodynamics ............................................................................... 23
4.2 Adsorption ..................................................................................... 31
4.3 Ideal model approximations ............................................................... 34
5 Conclusions ......................................................................................... 39
References ................................................................................................ 40
Appendix 1 Tables and figures ..................................................................... 43
Appendix 2 User defined functions ................................................................ 45
i
List of Figures
Figure 1 – Molecular structure of the mixed xylenes. ..............................................................2
Figure 2 – Main utilizations of the mixed xylenes [Fabri et al., 2000]. .........................................3
Figure 3 – Simplified scheme of a chromatography. ................................................................5
Figure 4 – Simplified scheme of the TMB with its concentration profiles [Ruthven and Ching, 1989]. ...6
Figure 5 – Simplified scheme of the Simulated Moving Bed [Ruthven and Ching, 1989]. ....................7
Figure 6 - Example of RTD. ............................................................................................ 13
Figure 7 – Example of three RTD with the same mean times but with distinct variances. ................ 14
Figure 8 - Completely segregated system and perfectly mixed system both with the same RTD. ....... 15
Figure 9 – Schematic view of the experimental installation, respective dimensions and sensor
positions. .................................................................................................................. 19
Figure 10 – 2D geometry representative of the experimental installation. .................................. 20
Figure 11 – Inlet profile injections for experimental and simulated RTD’s .................................. 25
Figure 12 – Velocity field obtained and zoom of the inlet and outlet. ........................................ 25
Figure 13 – User defined scalar contours for the RTD simulation after injecting the profile displayed in
Figure 11. ................................................................................................................. 26
Figure 14– RTD obtained for a 2D simulation using an inlet UDF injection (solid lines) and comparison
with the experimental result (points). .............................................................................. 27
Figure 15 – Local mean age and variance obtained through Liu and Tilton’s methodology (2010) ....... 29
Figure 16 – Mean age for the three geometries for a flow rate of 6 m 3.h-1. ................................. 31
Figure 17 - Separation of the xylene mixture performed with the 2D geometry without obstacles .... 32
Figure 18 – Separation of the xylene mixture performed with the 2D geometry with the cylinder as
obstacle ................................................................................................................... 33
Figure 19 - Separation of the xylene mixture performed with the 2D geometry with the quadrangular
prism as obstacle ........................................................................................................ 33
Figure 20 – RTD comparison between the three geometries .................................................... 36
Figure 21– Adsorption separation, without mass transfer limitations, results comparison for the 2D
geometry in the absence of obstacle ................................................................................ 36
Figure 22 – Adsorption separation, without mass transfer limitations, results comparison for the 2D
geometry with a cylinder as obstacle................................................................................ 37
ii
Figure 23 – Adsorption separation, with mass transfer limitations, results comparison for the 2D
geometry with a cylinder as obstacle................................................................................ 38
Figure 24 - Schematic view of the experimental installation with the obstacles (cylinder at left and
prism at right), with the respective dimensions. ................................................................. 43
Figure 25 - Adsorption separation, with no mass transfer limitations, results comparison for the 2D
geometry with a quadrangular prism as an obstacle ............................................................. 44
iii
List of Tables
Table 1 – Physical properties of mixed xylenes [Fabri et al., 2000]. ............................................4
Table 2 – Hydrodynamic simulation parameters ................................................................... 23
Table 3 – First two RTD moments obtained with different turbulence models at the outlet of the
vessel. ..................................................................................................................... 24
Table 4 – Mean of the age distribution of the probes for the two turbulence models ..................... 24
Table 5 –Comparison of the mean ages between a CFD simulation made at a flow rate of 6.63 m 3.h-1
and the experimental results at a flow rate of 6 m3/h .......................................................... 28
Table 6 – Comparison of internal age distribution and variance for the geometry/installation with a
cylinder as obstacle. .................................................................................................... 30
Table 7 - Comparison of internal age distribution and variance for the geometry/installation with a
quadrangular prism as obstacle ....................................................................................... 30
Table 8 – Table of moments of age comparison between hydrodynamics and adsorption in the three
cases of study ............................................................................................................ 34
Table 9 – Simulated results, with Liu and Tilton’s methodology (2010), for the top and bottom free
flow zones for the first and second moments, variance and equivalent number of CSTR’s ............... 35
Table 10 – Moments distribution for the same residence time and different Schmidt number .......... 43
Table 11 – Table of moments of age comparison between the already presented cases and their
equivalent beds coupled with two CSTR’s (one on top and other on the bottom free flow zone). ...... 44
iv
Notation and Glossary

List of symbols
Terminology
a Spatial mean age(s) (s)
bi Langmuir coefficient of the compound i (m3/mol)
Ci Concentration of the compound i (mol/m3)
C 1 k- model parameter (-)
C 2 k- model parameter (-)
C k- model parameter (-)
CoV Coefficient of variation (-)
D Diffusivity coefficient (m2/s)
d Flow’s length scale (m)
dp Particle’s diameter (m)
DT Turbulent diffusion (m2/s)
E Exit age distribution (-)
F Liquid-solid friction force (N/m3)
I Spalding’s spatial invariant term (mol/m3)
k Turbulent kinetic energy (m2/s2)
K Bed permeability (m2)
k1 Overall mass transfer coefficient (s-1)
L Outlet’s length (m)
M Molar mass (kg/mol)
th
mn n raw moment (sn)
n Moment order (-)
N CSTR Number of CSTR (-)
p Pressure (Pa)
Pe Peclet number (-)
Pk Turbulent model equation (-)
qi Adsorbed concentration of the compound i (kg/m3)
Q Volumetric flow (m3/s)
q i* Adsorbed concentration of the compound i in equilibrium (kg/m3)
q m ,i Adsorbent mass capacity for the compound i (kg/kg)
R Molar source term (mol/m3.s)
Re Reynolds number (-)
Sc Schmidt number (-)
t Time (s)
v
t* Switching time (s)

u Fluid interstitial velocity (m/s)
u Fluid average superficial velocity (m/s)
V Vessel’s volume (m3)
v Fluid superficial velocity (m/s)
x Position (m)
Greek symbols
 Age frequency function (-)
 Molecule’s age (s)
 Molecules’ mean age (s)
p Molecule’s age in a point (s)
* Damping coefficient (-)
 Non-Darcy coefficient (m-1)
i Bed porosity (-)
T Turbulent kinetic energy dissipation rate (m2/s3)
 Volume average age frequency function (-)
 Fluid dynamic viscosity (Pa.s)
e Fluid effective dynamic viscosity (Pa.s)
n th
n central moment (sn)
 n* nth normalized central moment (-)
T Turbulent dynamic viscosity (Pa.s)
1 Mean residence time (s)
 Fluid density (kg/m3)
p Particle density (kg/m3)
2 Variance (s2)
k k- model parameter of k (-)
 k- model parameter of  (-)
 Residence time (s)
ω Specific turbulence dissipation rate (s-1)
Indexes and exponents

e Exit
in Inlet
l Longitudinal
out Outlet
t Transversal
V Volume averaged
vi
x Radial
y Axial
Abbreviations
CFD Computational fluid dynamics
CSTR Continuous stirred-tank reactor
DPFR Dispersive plug flow reactor
EB Ethylbenzene
MX m-xylene
MOX m-xylene and o-xylene mixture
OX o-xylene
PDEB p-diethylbenzene
PET Polyethylene terephthalate
PX p-xylene
RTD Residence time distribution
SMB Simulated moving bed
TMB True moving bed
UDF User defined function
vii
1 Introduction
Para-xylene (PX) is the main raw material for the manufacture of polyethylene terephthalate
(PET), a polymer used for the production of beverage bottles and polyester fibers. The
constant growth of the PET consumption has boosted the production of PX.
Since PX is always produced in a mixture with its isomers, there has been a big interest in
developing and improving the processes of separation of this mixture. The most used process
to perform this separation is the Simulated Moving Bed (SMB).
The objective of the companies that are interested in studying this process is to maximize PX
production. To do this it is necessary to evaluate the impact of the different dispersive
phenomena such as the intra-particle mass transfer and axial dispersion of the flow in the
fixed bed. It is also important to describe hydrodynamics of the system and its interactions
with adsorption, when its isotherm is not linear.
Then, for this master thesis project the main objectives proposed are to:
 Study and model hydrodynamics of an adsorption bed of a SMB through CFD

simulations and experimental tracer injections.
 Identify the effect that obstacles provoke in hydrodynamics.
 Couple the adsorption with the previous model and observe the effect of
hydrodynamics in the xylene separation.
Introduction 1
2 Bibliographic study
2.1 Xylenes
The term xylene designates the dimethylbenzene, an aromatic ring with two methyl groups.
There are three different molecular configurations in which the xylenes can appear, ortho
(1,2-dimethylbenzene, OX), meta (1,3-dimethylbenzene, MX) and para (1,4-dimethylbenzene,
PX), depending on which carbon atoms the methyl groups are attached. The term mixed
xylenes also considers the ethylbenzene (EB) which instead of two methyl groups has one
group ethyl and also shares the same molecular formula and molar mass as the xylenes, C8H10
and 106.16 g /mol. The molecular configurations of these four molecules are shown in Figure
1.
Figure 1 – Molecular structure of the mixed xylenes.
Despite the similar molecular configuration of these isomers, they do not share the same
industrial interest. The PX is by far the most important aromatic C8, followed by the OX. To
valorise the isomers of PX, they are sent to an isomerization unit so they can be converted
into PX.
2.1.1 Mixed Xylenes - production and use
There are four ways to obtain these isomers: the catalytic reforming (80%) [Chem Systems
Ltd. 1995], pyrolysis gasoline (11.1%), toluene disproportionation (7.6%) and coke-oven light
oil (1.3%). EB is not present when the xylenes are produced via toluene disproportionation
[Cannella, 2007].
During 2007-2012 the consumption of mixed xylenes increased by 15%, the capacity also
increased in a rate of 31%. So, in the next years, it is expected the operational rates to
increase. In terms of consumption and production, the Asian market is the one that has the
highest share. For the isomers of xylene, PX accounted for 79% of 2012 global mixed xylenes
Bibliographic study 2
demand, followed by the OX with 7% of the mixed xylenes consumption, after comes the MX
with 1.3% [Xylenes report, IHS Chemical, 2012].
Figure 2 shows in a schematic view the main uses for the mixed xylenes.
Figure 2 – Main utilizations of the mixed xylenes [Fabri et al., 2000].
From the mixed xylenes recovered, between 50 and 60% are destined to PX production, from
10 to 15% to OX production, 10 to 25% are sent to gasoline blending and merely 1% to MX
production [Cannella, 2007]. Around 98% of the PX is consumed in the polyester chain, mainly
to produce PET. For this, the PX must be separated from its isomers, with high level purity, so
it can be used in this valuable industrial chain.
2.1.2 Separation of Mixed Xylenes
The physical properties of the mixed xylenes are shown in Table 1.
Table 1 – Physical properties of mixed xylenes [Fabri et al., 2000].
o-xylene m-xylene p-xylene ethylbenzene
boiling point (°C) 144.4 139.1 138.4 136.2
melting point (°C) -25.2 -47.9 13.3 -95.0
density at 25°C (kg/m3) 876.0 859.9 856.7 862.4
To separate this mixture the process of distillation is not economically viable due to the close
boiling points of these isomers. If the EB and the OX were separated from the other two
isomers it would be necessary 300 theoretical trays [Cannella, 2007]. This process would have
high energy consumption and the cost of the equipment would be impracticable, also the MX
would still need to be removed from the resultant mixture.
Crystallization was the first industrial PX purification process. It consists in cooling the xylene
mixture below the PX's freezing point, so it can be extracted from the other isomers, still in
the liquid phase. Even if it is possible to achieve a purity of 99%, due to the eutectic point the
maximal recovery rate of PX is around 60-65%, resulting in a high volume of recycled xylenes
to the isomerization unit [Fabri et al., 2000].
Nowadays, around 60% [Minceva and Rodrigues, 2007] of the PX produced comes from
chromatographic processes. This kind of industrial processes consists in the exploitation of
the difference of affinities of a given adsorbent for the PX and its isomers, and can achieve a
recovery rate of around 97% per pass, much higher than the crystallization [Candella, 2007].
2.1.2.1 Chromatography
With this method, a small sample of a mixture (mobile phase) is injected in a column filled
with the adsorbent (stationary phase). To better understand this process a scheme of a
chromatographic separation is shown in Figure 3.
Figure 3 – Simplified scheme of a chromatography.
The difference of affinities of the adsorbent for the compounds within the mixture will result
in different residence times: compounds with respective higher affinity will remain longer
inside the chromatographic column, while those with lower affinity will be less affected by
the adsorbent and will have shorter residence times. These laboratory scale chromatographic
columns must have small diameters to minimize radial heterogeneities. For industrial scale
columns this problem cannot be avoided since their diameters can vary between 5 and 10
meters. To maximize the mass transfer between the mobile phase and the so called
“stationary phase”, these are put in counter current, analogously to the heat transfer in heat
exchangers.
2.1.2.2 True Moving Bed (TMB) process
The principle of the TMB consists in the motion of the solid phase (adsorbent) and the liquid
phase (xylenes) in countercurrent within a column. The PX is the more strongly adsorbed
species, and must be separated from its isomers, OX, MX and EB, that are less strongly
adsorbed. The desorbent used is the para-diethylbenzene (PDEB), for who the adsorbent has
an intermediate affinity, so the order of affinities is PX>PDEB>EB>OX/MX. The process
separates the original mixtures into two streams: the extract (PX and PDEB) and the raffinate
(OX, MX, EB and PDEB). These streams must then be purified through distillation.
A simplified diagram of the TMB is shown in Figure 4.
Figure 4 – Simplified scheme of the TMB with its concentration profiles [Ruthven and Ching,
1989].
The most used desorbent is the p-diethylbenzene (PDEB), which molecular structure is similar
to the PX, but instead of the two methyl groups (CH3), PDEB has two ethyl groups (C2H5) in
the para position. When the stationary state is achieved, two mixtures may be recovered
from the column. The role of the desorbent is to clean the solid phase from the mixed
xylenes. The boiling point of the PDEB is different from the mixed xylenes, so that a posterior
distillation can be easily performed.
The main technical difficulty of this process is the circulation of the solid. It is hard to control
its velocity, resulting in heterogeneous motion of the adsorbent and consequently a great loss
of efficiency of the mass transfer between the bulk and the solid. The movement of the solid
is expensive, and it causes its corrosion and backmixing, which highly decreases the
separation efficiency of the process [Ruthven and Ching, 1989].
2.1.2.3 Simulated Moving Bed process
In this process instead of circulating the solid, the countercurrent is simulated by periodically
switching the inlets and outlets of the column towards the fluid flow. This process is called
Simulated Moving Bed (SMB) and is schematically represented in Figure 5.
Figure 5 – Simplified scheme of the Simulated Moving Bed [Ruthven and Ching, 1989].
The adsorbent is kept in several fixed beds. TMB’s respective four sections are visible and
distinguishable. Solid arrows show the actual streams at time t and the dashed arrows show
the streams in use after the stream switch, at t+t* where t* is the switching time.
While the TMB reaches a stationary state, the SMB leans towards a cyclic steady state that is
reached after several cycles of the unit’s operation. When the cyclic steady state is achieved,
the concentration profiles change over time in each fixed bed of the adsorber, although,
these profiles are stationary in each section of the SMB.
This process is ideal for xylene separation due to its ability to work continuously and
consequently to treat industrial quantities of mixed xylenes.
2.2 Theoretical description and background
In this section the equations and models used to describe hydrodynamics in free flow and
porous media, the mass transfer and the adsorption thermodynamics equilibrium will be
presented. Since in the scope of the project is based in the separation of a mixture of
xylenes, and this separation is assumed to be isothermal, the heat transfer equations are not
presented, only the mass balance will be studied.
2.2.1 Hydrodynamics
In this work, hydrodynamics are studied while assuming the flow as steady and
incompressible. Different models were chosen for two different media: free flow and porous
media.
2.2.1.1 Free flow
For the free flow media, if the turbulence effects are non-existent, the Navier-Stokes
equations for an incompressible Newtonian fluid will be solved:
  
 u  u   p     2 u (2.1)
where  is the fluid density (kg/m3), u the fluid velocity (m/s), p the pressure (Pa),  the
fluid dynamic viscosity (Pa.s) and  is the Laplacian operator. Since the Reynolds number is
2
high, , the models chosen to characterize the flow are the standard k-ε
turbulence model proposed by [Launder and Spalding (1972)] and standard k-ω turbulence
model developed by [Wilcox (1998)].
For the k-ε model, the turbulent viscosity is related to the local values of turbulent kinetic
energy (m2/s2) and its dissipation rate T (m2/s3) as shown in equation (2.2).
(2.2)
is a k-ε model parameter, determined experimentally and equals to 0,09. This introduces
two new transport equations, (2.3) and (2.4).
⃗ [( ) ] (2.3)
⃗ [( ) ] (2.4)
, , , are constant parameters of the model determined experimentally and is

the production term.
The standard k-ω model is an empirical based model with transport equations for turbulent
kinetic energy and its specific dissipation rate . This model has been modified several
times to improve its accuracy and as result the turbulent viscosity is defined using a damping
coefficient , defined and characterized by [Wilcox (1998)], as shown in equation (2.5).
(2.5)
The transport equations (2.6) and (2.7) are used in this model.
( ) ( ) [( ) ] (2.6)
( ) ( ) [( ) ] (2.7)
These two turbulence models were used in a comparative study in order to perceive which
one is more suitable for this study.
2.2.1.2 Porous Media
The Brinkman-Forchheimer model, is a modification of the laminar Navier-Stokes equations

where the diffusion of momentum due to viscosity effects and the inertia due to friction
between the fluid and particles are modeled. This model has been used to simulate
hydrodynamics in porous media, [Chan et al. (2000)]. The fluids are considered to be
incompressible since they are in liquid state, and the equations to be solved are:
(2.8)
for continuity, where represents the fluid interstitial velocity (m/s).
( ) (2.9)
for momentum, is the inter-particle porosity, is the pressure (Pa), is the apparent liquid
3
viscosity (Pa.s), is the liquid density (kg/m ) and is the liquid-solid friction force (N/m3)
and is defined by,
(2.10)
v is the superficial velocity (m/s), is the permeability of the porous media (m2) and is the
non-Darcy term (m-1). In the case of fixed bed the values of and are expressed by the
Ergun’s law [Ergun (1952)] and their values can be obtained through equation (2.11) and
(2.12).
(2.11)
( )
(2.12)
These empirical expressions were originally developed for one–dimensional flows within
isotropic media, but when the first term of the equation (2.9) / viscous term, is dominant the
use of the friction term coupled in the Navier-Stokes equation is acceptable, [Zeng and Crigg
(2006)].
2.2.2 Mass Transfer
2.2.2.1 Inter-particle phase
The mass transfer equations that are presented in this section were coupled with the solution
previously obtained for hydrodynamics. In the free flow regions there is no adsorption, the
concentration of a compound is transported by diffusion and convection.
( ⃗ ) (2.13)
If the regime is turbulent, the turbulent diffusion must be added to the molecular. This
turbulent diffusion , can be obtained by assuming a turbulent Schmidt number of 0.7 and
using the turbulent viscosity obtained by turbulent model in use, either k-ε or k-ω, as shown
in equation (2.14) .
(2.14)
This turbulent diffusion, in opposite of the molecular diffusion that is assumed constant,
suffers a variation in space, this happens because it is a function of the turbulent viscosity
and consequently of the local velocity.
In the porous media the transport of species can be described by equation (2.15),
( ) ( ⃗ ) (2.15)
i is the bed porosity, is the particle density (kg/m3), the molar mass of the compound
(kg/mol) and u is the interstitial velocity (m/s). The diffusivity coefficient in the equation
(2.15) comprises the molecular diffusion and the mechanical dispersion. Contrarily to the
molecular and turbulent diffusion that are isotropic, the mechanical dispersion is described
by a diagonal tensor comprising the radial ( ) and axial dispersion ( ), relatively to the
flow direction. These two vectors are calculated through the definition of the Peclet number
that is the product of the Reynolds and Schmidt numbers and quantifies the ratio between
convective and diffusive transport.
(2.16)
The longitudinal ( ) and transversal dispersion ( ) coefficients can be calculated by using a

constant Peclet number.
(2.17)
(2.18)
Since they are dependent to the local fluid velocity, the tensor can be calculated for a two-
dimensional domain such as,
| | | | | | | |
( ) (2.19)
| | | | | | | |
( ) (2.20)
The longitudinal and transversal Peclet numbers are assumed to take the value of 2 and 11
respectively, following the results obtained by [Founemy et al (1992)].
2.2.2.2 Intra-particle phase
Two possible ways to define the adsorption term are, through direct equilibria
between both phases using partial derivative equations (PDE), equation (2.21), or through a
linear driving force (LDF), equation (2.22), to simulate the mass transfer resistance between
the bulk and the adsorbed phase.
∑ (2.21)
( ) (2.22)
is the overall mas transfer coefficient for the fluid film resistance (s-1). The equation (2.20)
can be applied when molecules migrate between the bulk and the adsorbed phases almost
instantaneously, so the mass transfer limitations are not important. When the mass transfer
limitations are substantial, the adsorbent must be discretized and the mass balance must be
solved locally taking into account a linear driving force and by adjusting the overall mass
transfer coefficient.
2.2.3 Adsorption Equilibria
The adsorbed concentration is obtained through the Langmuir multicomponent adsorption

model [Ruthven (1984)].
(2.23)
∑
is the adsorbent mass capacity (kg/kg), is the adsorbent affinity (m3/mol) for each
compound on a given system, is the concentration (mol/m3) of a compound in the mobile
phase. This model is generally used for gas/solid adsorption systems. However, Daems et al.
(2006) found a good agreement between this model and experimental results for liquid/solid
adsorption for alkanes, alkenes and aromatics mixtures.
2.3 Flow characterization methods
2.3.1 Residence Time Distribution (RTD)
A classical approach to provide some basic information of the macro-mixing state and
hydrodynamics of a given system is the Residence Time Distribution (RTD) theory. To
determine the RTD of a system normally transient experiments with inert tracers are made.
These experiments consist in injecting an inert tracer at the inlet of a vessel (reactor,
column), and the measurement of its concentration at the outlet. These injections must be
close to the ideal, such as perfect step or Dirac. The RTD is represented by an external
residence time distribution or an exit age distribution, E(t). The function E(t) has the units of
time-1 and one example shown in the Figure 6.
Figure 6 - Example of RTD.
This function is defined as shown in equations (2.25) and (2.26)
∫ ( ) (2.24)
∫ ( ) ( ) (2.25)
()
̅ ∫ ∫ ( )
is the outlet tracer concentration (mol/m3), and ̅ are the fluid superficial and its
average at the outlet and is the outlet’s length. Residence time distributions can be
described by using an infinite set of parameters known as moments.
∫ ( ) (2.26)
is the nth raw moment of the distribution. For a better comprehension of these moments,
they must be centered relatively to the previous moment(s), as shown in equation (2.27).
∫ ( ) ( ) (2.27)
Where is the nth central moment. The first moment is the mean of the distribution or mean
residence time and can be obtained through equation (2.28).
̅ ∫ ( ) (2.28)
It is equal to the average residence time of a system and it is defined as the expected value
of a molecule’s age at the outlet of a system. The second central moment measures the
variance and it is the degree of dispersion around the mean, equation (2.29).
∫ ( ) ( ) ∫ ( ) (2.29)
If the value of the variance is closer to zero, it means that all the values are close to the
mean age, and the system is not very dispersive. As this value tends to grow, the dispersion
also grows and the points tend to spread out from each other and from the mean age.
One example of this variation is demonstrated in the Figure 7.
Figure 7 – Example of three RTD with the same mean times but with distinct variances.
The main limitation of the RTD calculations is that they just give information about the
system hydrodynamics at its outlet, leaving its internal information unknown. With this
limitation the RTD theory can be insufficient when non-linear phenomena is present, with this
in mind it is possible to conclude that this theory is incomplete to characterize
hydrodynamics. It is then needed to adopt a supplementary method that can enable one to
access the internal information of a vessel.
2.3.2 Degree of mixing
In the design of the continuous-flow reactors the characterization of the system made by the
RTD could be, in most of the cases, insufficient. This happens because the RTD
characterization is focused in demonstrating the macro mixing of a vessel. This problem could
be demonstrated by comparing the RTD’s of a perfectly mixed system, described by a
continuous stirred-tank reactor, and a system composed by parallel plug flow reactors. These
systems and their RTD are presented in the Figure 8, and also is their RTD.
Figure 8 - Completely segregated system and perfectly mixed system both with the same
RTD.
To better describe the internal information of these two distinct systems, Danckwerts (1958)
and Zweetering (1959) proposed a criterion that describes the quality of the mixing of a
vessel. Danckwerts uses the concept of “age of the fluid at a point”, which implies the age
averaged over a region, small compared to the whole system and even smaller compared to
the scale of segregation. If , the age of a molecule, is defined as the time passed since the
molecule entered the system, it is possible to calculate the variance of the ages of all the
molecules in the system (equation (2.30)).
̅̅̅̅̅̅̅̅̅̅̅
̅̅̅̅̅̅̅̅̅
( ̅) (2.30)
̅ is the mean age of all molecules in the system at a given time and the upper bar indicates
that the values are averaged over all the molecules. For each “point” (Danckwerts concept)
the variance of the mean age of the molecules is given by the equation (2.31).
̅̅̅̅̅̅̅̅̅̅̅̅̅
̅̅̅̅̅̅̅̅̅̅
( ̅) (2.31)
Where is the mean age of the molecules at a given point, and the upper bar indicates that
the values are averaged over all the “points” of the vessel.
For the cases described previously, in the “well-mixed” stirred tank system, the at each
point is the same and equal to the mean age of every molecule in the system, which gives a
variance for all the points the value of 0. In the other system the values for and
are the same for every molecule in the system. Danckwerts define the degree of mixing, J, as
a ratio between the two variances (equation (2.32)).
̅̅̅̅̅̅̅̅̅̅̅̅̅
(̅̅̅̅̅̅̅̅̅̅̅)
(2.32)
̅̅̅̅̅̅̅̅̅
( ̅)
This quantity lies between 0, for the systems mixed at a molecular scale, and 1, for a
completely segregated system. The degree of mixing helps to study and characterize the
internal information of a system, the impact of hydrodynamics on a system that is at a degree
of mixing between 0 and 1.
Recently, Liu (2012), developed a CFD methodology to transport the moments of internal age
distribution that allows the computation of the degree of mixing.
2.3.3 Transport of moments of internal age distribution
As shown previously, the raw moments of the RTD can be calculated through equation (2.33).
∫
∫ ( ) (2.33)
∫
The previous equation can be applied at any point in a system, as Danckwerts (1958) has
shown. The resulting equation can be solved in function of the spatial position, and can be
used to obtain local measurements of the tracer concentration in every point of the system.
∫ ( )
( ) ∫ ( ) (2.34)
∫ ( )
( ) is the nth moment frequency function.
Then when a pulse injection of tracer is performed in a steady and incompressible flow, the
transport of molecules is made by convection and diffusion, and the variation of
concentration, as function of time and position, is given by equation (2.35).
( )
( ) ( ) (2.35)
D comprises all the dispersive phenomena in the system (molecular diffusion, turbulent
mixing, mechanical dispersion, etc). If this expression is multiplied by tn and integrated over
time it results in equation (2.36).
( )
∫ ∫ ( ) ( ) (2.36)
To simplify the equation, the term on the left-hand side can be integrated by parts, resulting
in equation (2.37).
( )
∫ ( )| ∫ ( ) (2.37)
Adding to this, Spalding (1958) considered a steady and incompressible flow in a closed
system and inferred the quantity I, as shown in equation (2.38).
∫ ( ) (2.38)
I is spatially invariant. With these two equations, (2.36) and (2.37), and considering that in
the equation (2.36) the term ( )| will be zero when , because C tends to be zero
faster than t goes to infinity [Liu and Tilton (2010)]. With ( )| , replacing equation (36)
in equation (35) and dividing everything by I, results in equation (2.39)
∫ ( ) ∫ ( ) ∫ ( )
[ ( ) ( )] (2.39)
∫ ( ) ∫ ( ) ∫ ( )
Where the invariance of u and D, and spatial invariance of I have been used. The term on the
left-hand side corresponds to n times the nth-1 moment of the RTD and the transport equation
of the nth moment, for an incompressible flow, is then shown in equation (2.40).
(2.40)
With the aid of this equation it is understandable that all the RTD moments are diffused and
convected. The equation (2.39) is generally solved by CFD solvers and can be easily used to
provide the spatial distribution of ages by simply adding a source term in steady state
simulations.
2.3.4 Degree of mixing calculation using the internal age distribution
The concept of internal age distribution can be used to calculate the degree of mixing [Liu
(2012)]. By taking a case of a steady incompressible flow where the tracer concentration is
constant at the inlet, and the age of every molecule at the inlet is zero, if the age can be
identified at any point of the system, then the age at any point of the system can be sampled
with the equation (2.40).
( )
( ) (2.41)
∫ ( )
With this equation, concentration stands as a function of the molecular age. Repeating all the
steps made by Liu and Tilton (2010) and doing the integrations in molecular age, an equation
similar to the equation (2.39) can be obtained. The age frequency function of all molecules in
a system can be obtained by integrating the equation of a determined point, equation (2.41),
for all the points of the system.
By using the definition of the average age of all the molecules, ̅ it is easy to obtain a
relation that equals this average to the volume averaged distribution moments.
̅̅̅̅ ∫ ( ) ∫ ( ) ̅ (2.42)
With this equation, and knowing the concept of variance, Liu (2012) showed that Zwietering’s
(1959) degree of mixing was easily computed using the volume averaged first and second raw
moments of distribution.
̅̅̅̅ ̅̅̅̅
(2.43)
̅ ̅̅̅̅
This methodology can only be applied for steady incompressible flows. In CFD simulations this
can be a pragmatic way to obtain results about de mixing state of a given system and
compare them with others that produce the same RTD but have unrelated hydrodynamics.
3 Technical Description
3.1 Experimental Setup

In order to validate the CFD models and the chosen assumptions, concerning hydrodynamic
models, boundary conditions and the Peclet and Schmidt numbers, tracer tests were
performed using an experimental installation, represented in Figure 9.
2 34 5
7 9
6 8 10
11 12
13
Figure 9 – Schematic view of the experimental installation, respective dimensions and

sensor positions.
This installation was filled with glass spheres of a diameter of 1 mm with a resulting average
porosity of 0.357. The inlet volumetric flow varied between 2, 4, 6 and 8 m3/h. When
hydrodynamics inside the installation were stable, a saline solution was injected in a pulse
shape. The conductivity was measured throughout time with the aid of 13 conductivity
sensors with a frequency of 8 Hz. These 13 localizations of the sensors are also used for the
CFD simulations as probes in order to compare the experimental results with the numerical
results. The obtained RTD and its moments are compared with those obtained through CFD
simulations.
Technical Description 19
3.2 CFD approach

CFD simulations were performed to characterize hydrodynamics of the SMB adsorbent beds.
With such simulations it was possible to obtain the local moments of the internal age
distribution and the RTD resulting from the injection of inert tracer or obtain the outlet curve
concentrations of mixed xylenes in the presence of adsorption. In view of this knowledge, a
criterion is defined to develop new simple models that remain coherent in the presence of
non-linear phenomena, such as adsorption. This need to simplification also surges because the
real time of CFD simulations for these non-linear phenomena can take up to 72 hours, which
is a huge amount of time regarding to what is normal in simpler RTD simulations (2/3 hours).
When one needs to optimize or to perform a parameter fitting of this process, simulations of
72 hours renders such task are infeasible. It is then interesting to study the simplification of
the processes, such as 1D models which can take to converge.
3.2.1 2D CFD
In order to compare the hydrodynamic results for the experimental setup, a two-dimensional
geometry was drawn as shown in Figure 10.
Figure 10 – 2D geometry representative of the experimental installation.
To this geometry some modifications were made, such as the addition of macro scale
obstacles within the porous media, or the displacement of the inlet and outlet of the vessel.
To perform all the simulations the software ANSYS Fluent 15.0 was used. The mesh for this
geometry was optimized and adapted to all the changes made in the geometry.
Hydrodynamics of this volume were characterized through the mapping of the local moments
of internal age distribution obtained with Liu’s methodology (2012) and through RTD resulting
from pulse injections of inert tracer. These dynamic simulations performed in order to obtain
the RTD of the 2D domain can take up to 3 hours. Thus, it is interesting to study the accuracy
of traditional and simple reactor models that will be introduced in the next section.
3.3 Ideal model approximations

Generally, to ease the modelling of industrial processes, these are assumed to behave as ideal
vessels. The two main simple models are the Continuous Stirred-tank Reactor and the Plug
Flow Reactor. The first assumes that the vessel is perfectly mixed and that the concentration
is the same in every point of the vessel at any given time.
3.3.1 Continuous Stirred Tank Reactor
In ideal Continuous stirred tank reactors, the assumption that the concentration is uniform
throughout the vessel is made. Thus, the outlet concentration is equal to the concentration
inside the reactor, and its temporal variation can be calculated by:
Ci Q
 Ci ,in  Ci   Ri  Ci ,in  Ci   Ri
1
(3.1)
t V 
Q is the volumetric flow (m3/s) fed to the vessel, Ci,in the inlet concentration (mol/m3), τ is
the vessel's residence time (s) and Ri the molar source term (mol/m3.s). It must be assumed
that the fluid's density is constant, which is a decent assumption since xylenes are in liquid
state when separated.
As said before, the degree of mixing of a CSTR is equal to zero. The central moments of the
RTD of a CSTR were deduced with the help of an equation similar to (2.39) knowing that the
inlet moment mn,in is null equation (3.2),
1
m  mn ,in   mn 1  n  mn    mn 1  n (3.2)

n
The resulting equation for the distribution central moments is equation (3.3),
n  n  1! n (3.3)
where (n-1)! is the factorial of the order of the moment minus 1. When the process deviates
from perfect mixing, a cascade of CSTR is generally used for the modelling. It consists in
several consecutive CSTR linked between themselves. The equations of the distribution
moments of an enchainment of CSTR can be deduced with the help of the equation (3.2) but
where mn,in is not null, (except for the first reactor of the enchainment) since the moments of
a given reactor i depend on the moments of the previous reactor (equation (3.4)).
1
m  mn ,in   mn 1  n  mn    mn 1  n  mn ,in (3.4)

n
where mn is the distribution raw moment of order n of the reactor i, mn-1 is the moment of
order n-1 of the reactor i and mn,in is the moment of order n of the reactor i-1.
Using this equation, the distribution central moments of a cascade of NCSTR reactors can be
deduced, if they share their residence times, and is equal to equation (3.3) multiplied by
NCSTR:
1  N CSTR  (3.5)
 2  N CSTR  2 (3.6)
  2  NCSTR  3 (3.7)
The fourth distribution moment does not follow the logic order of the previous ones, and is
equal to 3(2+NCSTR)τ4. The degree of mixing for a homogeneous (constant τ) cascade of CSTR
was deduced. It only depends on the number of consecutive reactors:
N CSTR  1
J (3.8)
N CSTR  5
By changing the two variables of a cascade of CSTR, NCSTR and τ, it is possible to fit two from
four parameters (three distribution moments and J) to a more complex case.
4 Results and discussion
4.1 Hydrodynamics
With the geometry shown in the previous chapter it is possible to study hydrodynamics of the
system by CFD simulations. The set of parameters used for these simulations are shown in
Table 2.
Table 2 – Hydrodynamic simulation parameters
Value Units
μ 1E-3 Pa.s
ρ 998.2 kg/m3
dp 1E-3 m
Pel 2
Pet 11
The bed porosity εi was calculated experimentally and the average value for this parameter
was 0.357. The diffusivity of the species is given by an user defined function (Appendix 2) and
has two different calculations, one for the porous media and the other for the free flow zones.
The inlet flow rate of the simulations was defined as being 6 m3/h since it gives a superficial
velocity of the fixed bed close to the one passing through the SMB beds.
4.1.1 Comparison with experimental results
The goal of such simulations is to obtain the spatial distribution of ages at every point and the
RTD of the experimental installation, and validate de CFD results with the aid of
experimental ones.
4.1.1.1 Turbulent models comparison
With the geometry drawn, it was necessary to study which hydrodynamic turbulent model was
best suited for this study, and their results must be compared to experimental data. These
comparisons were made by converging hydrodynamics of the system in steady state and then
use the equation (2.39), to calculate the internal age distribution for the probes shown in
Figure 9. The moments of the resulting simulations are displayed in Table 3.
Results and discussion 23

Table 3 – First two RTD moments obtained with different turbulence models at the outlet of
the vessel.
Turbulent Model μ1 (s) σ2 (s2)
Standard k-ε model 29.06 3.23
Standard k-ω model 29.04 3.10
This table only includes the first two moments in the outlet. The moments of the age
distribution at the internal probes are displayed in the Table 4.
Table 4 – Mean of the age distribution of the probes for the two turbulence models
Top probes Middle probes Bottom probes Outlet
(s)
4.85 1.44 0.99 16.33 14.68 13.98 13.80 13.94 27.00 27.70 29.06
(s)
4.63 1.56 1.04 16.25 14.78 14.09 13.78 14.03 27.07 27.80 29.04
Since the experimental residence time obtained was 27.2 seconds and the variance at the outlet was
equal to 2.5 s2 the best method to do the simulations and represent hydrodynamics is the Standard k-
ω model since the residence time and the variance at the outlet are almost the same, the
criteria to choose was based in the first layer of probes and taking it into account the k-ω
model was chosen to be the model used in all the simulations of this project.
4.1.1.2 RTD and Internal age distribution
After choosing the best turbulence model for the system it was possible to do RTD
simulations. The simulations were made in transient state and the input was an injection
profile developed to represent the experimental injections of tracer, the profile was then
compiled to the solver as an UDF (Appendix 2). The profile result and comparison with the
experimental injection is presented in the Figure 11. This injection profile has this shape
because it is difficult to represent experimentally the perfect Dirac injection, since it is
manually controlled. Thus, for better accuracy of the results comparison, an approximated
profile was developed.

1.4
1.2
0.8
E(t) (1/s)
Experimental
0.6
Simulated
0.4
0.2
0
0 1 2 3 4
t(s)
Figure 11 – Inlet profile injections for experimental and simulated RTD’s
The experimental values (red squares) are mean values calculated with the information of all
the injections made experimentally. With this profile and the velocity field obtained for a
steady state simulation of hydrodynamics, (Figure 12), RTD simulations were made.
Figure 12 – Velocity field obtained and zoom of the inlet and outlet.
Snapshots at different times, of a RTD simulation, were taken and are shown in Figure 13.
Figure 13 – User defined scalar contours for the RTD simulation after injecting the profile
displayed in Figure 11.
Figure 13 shows the behavior of the tracer injected along the column. It is possible to see
that exist dispersion inside the bed since the area covered by the tracer increases. To study
the behavior of the tracer inside the geometry and also to compare it with the experimental
ones, the concentration curves were obtained for each probe of the experimental
installation, and compared to the curves obtained experimentally. This data is divided in 3
sections depending on the zone of the bed where the probes are, Figure 14.

(a) top (c) bottom

and outlet
(b) middle
Figure 14– RTD obtained for a 2D simulation using an inlet UDF injection (solid lines) and
comparison with the experimental result (points).
For better comprehension of the figure, the graphic (a) (top) presents the results of the
probes 2 (blue), 3 (green) and 5 (red) of the Figure 9, the graphic (b) (middle) the probes 6
(dark blue), 7 (red), 8 (green), 9 (violet) and 10 (light blue) and the graphic (c) (bottom and
outlet) the probes 11 (green), 12 (red) and 13 (blue).
As it has been demonstrated before the probes inside the column are distributed by three
zones. The results of the first zone, in the beginning of the porous media, are represented in
the graphic (a) of the Figure 14, the second zone, in the middle of the porous media and the
representation of results appears in the graphic (b) and the third zone is at the end of the
experimental set-up, graphic (c).After analyzing these graphics some conclusions could be
made. In the graphic (a) it is shown that the numeric tracer takes more time since it enters
the column in the opposite side, this would be a problem because it could cause the
concentration profile shown in the snapshot of the Figure 13, to solve this problem other
simulations were made doing some changes in the diffusive term for the free zones, by
decreasing the Schmidt number which increases the degree of mixing. This turned out to be
discarded after showing that even for a very small Schmidt number the solution would be
better for the point that is far from the inlet, but for the other two it would be worse (Table
10 in Appendix 1). In the middle zone (graphic (b)) results show that the first half of the
installation in the experiments was more dispersive that in the simulations, one option of
solution was to decrease the axial Peclet ( ). After one simulation this option was dropped
because it influenced the dispersion at all zones and the variance at the outlet would
increase, turning it far away from the experimental value.
Observing the graphic (c) it was easy to conclude that the variance at the outlet was almost
the same but the mean residence time had a delay of 1.5 seconds. to solve this delay without
changing the dispersion of the result, the solution proposed was to make simulations
considering a bigger flow rate to equalize the mean residence time of the experiments. The
best result for this solution was at a flow rate of 6.63 m3/h and it is shown in the next table.
This delay could be related to the flow meter error of 5% to highest flow rate
(5%*12m3/h=0.6m3/h).
This representation of the results was made graphically in order to avoid the integration
errors provoked by the noise read by the experimental sensors, which can result in an
overestimation of the moments.
Table 5 –Comparison of the mean ages between a CFD simulation made at a flow rate of 6.63
m3.h-1 and the experimental results at a flow rate of 6 m3/h
Top probes Middle probes Bottom probes +Outlet
(s)
4.58 2.30 1.96 15.38 14.23 13.64 13.31 13.75 25.53 26.03 27.00
(6.63 m3/h)
(s)
4.17 2.73 1.87 18.90 16.31 15.72 15.52 15.10 25.83 27.19 27.26
(6 m3/h)
The result brought another point of study, since the mean age is almost equal at the outlet.
The increase of flow rate just shows that the porosity inside the experimental installation is
not constant. This conclusion could also be validated based in the difference of residence
times between the top half of the installation and the bottom half. For the first half this
difference is around 12 seconds but for the experiments it is about 13~14 seconds, this result
shows that the top half of the installation could have a higher value of porosity than the
medium value of 0.357. In the bottom half the opposite situation is verified, 11 seconds for
the simulations and 9~11 seconds for the experiments. After some calculations it was possible
to have some approximation for the porosity of these two situations, those values were 0.37
in the top part and 0.32 in the bottom. This conclusion can also explain the difference

between the mean residence time obtained experimentally and through CFD simulations for
equal flow rate, and showed that if the porosity in the bed would be described by a constant
value, there would be no possibilities to approximate the simulated values to the
experimental ones. The transport of the moments of the internal age distribution was also
simulated. The local mean age and variance are shown in Figure 15, for the case where no
obstacle is placed inside the porous media.
Figure 15 – Local mean age and variance obtained through Liu and Tilton’s methodology
(2010)
Figure 15 demonstrates the result of a simulation through Liu’s methodology (2012). The
result for the mean age shows that the flow at the left side of the column is higher, as
expected, also there are highly delayed regions in the bottom corners and finally the mean
residence time is near the one obtained by a RTD simulation, 26.80 seconds. In the case of
the variance, the left side of the column has higher values derived from the delay observed in
the mean age distribution. . The result at the outlet for the variance is also near the values
obtained before, 2.04 s2.
The next step was to simulate the flow perturbations provoked by the presence of obstacles
inside the porous media and evaluate the resulting dispersion. The obstacles chosen and
added to the experimental setup were a cylinder and a quadrangular prism with the same
volume, the representation of these geometries is displayed in Figure 24 of Appendix 1, with

their respective dimensions. The results of those simulations and the comparison with the
experimental ones are displayed in the next tables.
Table 6 – Comparison of internal age distribution and variance for the geometry/installation
with a cylinder as obstacle.
Bottom probes +
Cylinder Top probes Middle probes
Outlet
(s) 4.65 2.49 1.66 12.79 12.08 20.17 11.16 10.51 25.56 23.77 27.03
(s2) 3.59 0.31 0.58 2.31 0.58 6.13 0.60 0.99 1.08 1.52 5.69
(s) 3.73 2.96 1.64 14.08 13.84 22.12 12.85 12.07 23.87 23.34 24.99
(s2) 0.27 0.25 0.07 1.78 1.78 6.78 1.72 1.46 2.85 1.51 3.84
Table 7 - Comparison of internal age distribution and variance for the geometry/installation
with a quadrangular prism as obstacle
Bottom probes
Prism Top probes Middle probes
+ Outlet
(s)
4.23 2.56 1.70 12.06 11.66 27.69 10.60 10.37 24.95 23.39 26.88
(s2)
1.98 0.27 0.65 0.64 0.43 18.25 0.40 1.11 0.68 1.73 9.26
(s)
3.74 3.21 2.05 13.77 13.65 26.25 12.38 11.84 23.18 23.11 24.71
(s2)
0.34 0.32 0.14 1.78 1.67 10.43 1.62 1.62 1.51 3.21 4.79
After analyzing the results for the two tables it is possible to take some conclusions about the
influence of the obstacles in hydrodynamics of the system in the experiments and in the
simulations.
For the first topic, the presence of obstacles shows that the residence time inside the column
decreases, as expected, because the obstacles occupy a portion of the bed’s total volume. Its

presence increases the variance at the outlet which was also expected because with the
inclusion of obstacles causes some perturbations in the system (deviations of the
streamlines), the changes on the results are well represented by the middle probe of the
middle probes line, where, comparing to the case without obstacles, the difference of the
mean age was about 1.74 seconds between the probe 8 and the other four and in the
presence of the cylinder this difference raises to 9.66 seconds and it is even higher in the
presence of the prism, 17.32 seconds.
The transport of moments of the age distribution was simulated, and the mean age, for the
three geometries, is shown in the Figure 16.
Figure 16 – Mean age for the three geometries for a flow rate of 6 m3.h-1.
The effect of the obstacles in the internal age distribution is well verified by this figure where
it is demonstrated that the geometry with no obstacles tend to have high delay regions in the
bottom corners of the geometry and the below the obstacle which can influence the
adsorption separation that will be discussed in the next chapter.
4.2 Adsorption
After studying hydrodynamics with the aid of an inert tracer injection, the adsorption was
studied. The parameters used to describe the adsorption equilibria were inserted in a UDF
presented in the Appendix 2.

The procedure of simulating this equilibrium was the same as the one of a RTD simulation.
The compounds for these simulations were the desorbent (PDEB), the PX and the mixture of
MX and OX, or MOX (the abbreviation used in the simulations).
For these simulations the mass transfer limitations were considered negligible, so the values
given to the mass transfer coefficients were much higher than the real ones, with this it will
be possible to compare the simplified models with the CFD for the most unfavorable case. For
this case, the geometries simulated were the ones presented and studied in the previous
chapter, but some changes were made, the inlet was changed to the same abscissa point as
the outlet.
The simulations were performed with the k- turbulence model and a flow rate of 6 m3/h.
The outlet concentration profiles of PX and MOX for the three geometries are in the Figures
17, 18 and 19.
0.25
0.2
0.15
E (-)
0.1 PX
MOX
0.05
0
30 35 40 45 50 55 60 65 70
Time (s)
Figure 17 - Separation of the xylene mixture performed with the 2D geometry without
obstacles

0.25
0.2
0.15
E (-)
0.1 PX
MOX
0.05
0
30 35 40 45 50 55 60 65 70
Time (s)
Figure 18 – Separation of the xylene mixture performed with the 2D geometry with the
cylinder as obstacle
0.25
0.2
0.15
E (-)
PX
0.1
MOX
0.05
0
30 35 40 45 50 55 60 65 70
Time (s)
Figure 19 - Separation of the xylene mixture performed with the 2D geometry with the
quadrangular prism as obstacle
For the three cases the chromatographic separation is evident, although it is possible to see
the long tails of both curves (PX and MOX) leaning to the right, when the obstacles are placed
inside the porous media. The adsorbent has the highest affinity for the PX which is retained
longer and has higher values of residence time than the MOX mixture. Residence times
increase comparing to the result of hydrodynamics, this happens because there are mass
transfer interactions between liquid and solid phases. The differences between the
hydrodynamic and adsorption results in terms of moments are in the Table 8.

Table 8 – Table of moments of age comparison between hydrodynamics and adsorption in the
three cases of study
Adsorption
Hydrodynamics
PX MOX
2

Case 1 (s) 2 (s2) CoV 1 (s) CoV 1 (s) 2 (s2) CoV
(s2)
2D 28.44 2.16 0.052 51.64 6.03 0.048 45.60 5.25 0.050
2D + Cylinder 27.04 5.69 0.088 47.06 14.02 0.080 41.54 10.43 0.078
2D + Prism 26.89 9.25 0.113 46.75 29.34 0.110 41.44 26.35 0.124
The previous table demonstrates what has been said previously, when comparing the
moments of age distribution with the moments of the concentration curves in the presence of
adsorption, for the same case both increase. The rise is more pronounced for the PX since is
the component with more affinity.
To better compare the results it was used another term, the coefficient of variation that is
defined to be the square root of the normalized variance [Liu and Tilton, (2010)]. With this
coefficient it is possible to compare the normalized dispersion of the RTD and the
concentration curves, as presented in the Table 9.
The results show values of CoV are not affected when adsorption is taken into account in the
absence of obstacles, but when an obstacle is added to the porous media there are some
changes. When the cylinder is placed, it increases the normalized dispersion (CoV) but in the
presence of adsorption the peaks are compressed and the CoV decreases (from 0.88 to ~ 0.8).
When the prism is placed inside the porous media the CoV gets even more increased, and in
the presence of adsorption the curve of MOX gets even more dispersed (higher CoV value).
This conclusion shows that it is important and necessary to study the coupling between
hydrodynamics and adsorption, because there is no linearity in the results.
This is an important result because it validates that hydrodynamics and adsorption are not
independent and also that hydrodynamics could strongly impact the efficiency of the
adsorption, it increases the variance of the system turning it more dispersive.
4.3 Ideal model approximations

As it was said previously, to ease the modelling of processes ideal approximations must be
made. In this project it was made the assumption that the free flow zones of the bed could
be modeled as CSTR’s. This simplification, if successful, can simplify the modeling of the bed
and decrease the simulation times.

The first thing to do was to calculate the first and second moments of the internal age
distribution at the end of each free flow zone and then calculate the number of CSTR
equivalent to that distribution, Table 9.
Table 9 – Simulated results, with Liu and Tilton’s methodology (2010), for the top and
bottom free flow zones for the first and second moments, variance and equivalent number of
CSTR’s
1,e (s) 2,e (s2) 2 (s2) NCSTR

Top 0.991 2.115 1.133 0.866
Bottom 1.633 5.477 2.810 0.949
Since the result for the number of CSTR’s is close to one, each zone was replaced by a CSTR
with the same residence time, and consequently almost the same variance.
Thus, the top free flow zone it was simulated as being on CSTR with a mean residence time of
0.993 seconds, and to do the input for each simulation it was necessary to create a UDF with
the corresponding profile of the CSTR (Appendix 2). The bottom free flow zone was simulated
by feeding the results of simulations with the previous CSTR profile plus the porous media to
a second CSTR. With the mean residence time of the bottom free flow zone and the result of
the simulations it was possible calculate the moments of the age distribution at the outlet of
the system and compare them with simulations that include the complete geometries. The
simulations were made for the cases of the 2D geometry without obstacles, with a cylinder
and with a quadrangular prism inside the geometry. The results and comparisons are
displayed in the Table 11 on Appendix 1. Notice that the comparisons were made in the
presence or absence of adsorption. This was made to get a general overview of the
differences in every case and every phenomenon.
To better understand the results of the comparisons s the results were plotted and are
presented in the Figures 20, 21, 22 and 23.

0.35
0.3
0.25
2D
0.2 1D + CSTR
E (-)
Prism
0.15
Prism + CSTR
0.1 Cylinder
Cylinder + CSTR
0.05
0
10 15 20 25 30 35 40 45
Time (s)
Figure 20 – RTD comparison between the three geometries
Figure 20 shows that the geometries with obstacles suffer the same effect when the free flow
zones are substituted, by decreasing their peaks and increasing the variation. In the other
way in the absence of obstacles, when the free media regions are replaced by the two CSTR,
and the bed simulated as a plug flow reactor the opposite happens.
0.2
0.15
2D global PX
E (-)
0.1 1D + CSTR PX
2D global MOX
1D + CSTR MOX
0.05
0
30 35 40 45 50 55 60 65 70
Time (s)
Figure 21– Adsorption separation, without mass transfer limitations, results comparison for
the 2D geometry in the absence of obstacle

The Figure 21 represents the results comparison between the 2D geometry without obstacles
and an approximate model composed by a 1D plus two CSTR’s (one for each free flow zone).
Results showed that the model represents almost identically the 2D simulation. Then, the
next step was to simulate this phenomenon with the 2D geometries that contained the
obstacles and compare them with the respective models. The plots with the results of these
simulations are in Figures 22, for the cylinder, and Figure 25 of Appendix 1, for the
quadrangular prism.
0.25
0.2
0.15 Cylinder PX
E (-)
Cylinder MOX
0.1
Cylinder + CSTR PX
0.05 Cylinder + CSTR MOX
0
30 35 40 45 50 55 60 65 70
Time (s)
Figure 22 – Adsorption separation, without mass transfer limitations, results comparison for
the 2D geometry with a cylinder as obstacle
As it is displayed in Figure 22, the fact of using the real free flow zones or model them by
CSTR changes the behavior of the outlet results for the separation. The simplified model
increases the variance, for both obstacles (prism results in Figure 25 of Appendix 1). These
differences can be explained by the already higher variances given by the simplified model
when studying the RTD (Figure 20).
The final step was to simulate the separation with the real mass transfer coefficient and
compare them with the model approximations, since the differences of the results were
higher for the cases with the obstacles, in terms of variance, it was made the comparison
with a cylinder as an obstacle, Figure 23.

0.045
0.04
0.035
0.03
0.025 Cylinder PX
E (-)
0.02 Cylinder + CSTR PX

Cylinder MOX
0.015
Cylinder + CSTR MOX
0.01
0.005
0
0 10 20 30 40 50 60 70 80 90 100
Time (s)
Figure 23 – Adsorption separation, with mass transfer limitations, results comparison for the
2D geometry with a cylinder as obstacle
This final comparison shows that with the real mass transfer limitations the use of a simple
model to substitute the free flow zones is possible, even in the presence of obstacles in the
porous media. It also shows that separation is worse than in the absence of mass transfer
limitations, which was expected.
Therefore, it is possible to conclude that the 1D model approximation is satisfactory in the

absence of obstacles, for every scenario of mass transfer limitations. For the cases where the
obstacles are placed inside the porous media, this is not possible because they disturb the
streamlines which cannot be represented directly by just one plug flow reactor, this could be
solved by substituting the porous media by several parallel dispersive plug flow reactors with
different lengths.
Another option to simplify this case is to replace the top free flow zone by a horizontal PFR
with several outlets and the bottom zone by a PFR with several inlets, in order to reproduce
the correct radial delay.
Finally, the simpler model is able to predict the chromatographic separation in the presence
of obstacles and considerable mass transfer limitations, this happens because these
limitations provoke a strong dispersion of the concentration fronts, which tend to conceal the
effect of the obstacles.

5 Conclusions
In this work, hydrodynamic modelling of an adsorption bed was studied through the use of
CFD simulations. This modelling was made by coupling the RTD theory and the methodology
developed by Liu and Tilton (2010) to transport the moments of the age distribution. The
results obtained were compared to experimental ones, and it was concluded that there was a
delay in terms of mean age that was solved by increasing the simulated flow rate to match
the same residence time as the one from the experimental results. With these results the
coupling between the turbulence model k-and the porous media Brinkman-Forchheimer
model was validated.
Two dispersive agents that influence the separation were discussed, free flow zones and
presence of obstacles. For the effect of obstacles inside the porous media of the bed results
show that this presence cause perturbations by deviating the streamlines and increase the
variance of the outlet results.
Adsorption equilibrium was also simulated throughout CFD simulations, firstly in the absence
of mass transfer limitations. These simulations demonstrated that hydrodynamics have a
major impact on the chromatographic separation, and the characterization of the adsorption
phenomena is not possible without first having hydrodynamics well defined.
The final step was to define simpler (ideal) model approximations that could reproduce the
behavior of some zones of the bed, this approximations were made by replacing the free flow
zones of the bed by CSTR’s with the same residence time. The results show that these
approximations are acceptable in absence of obstacles or when in the presence of strong mass
transfer limitations.
As a final overview, the objectives proposed were accomplished, there were some limitations
caused by the lack of time available for the study since the subject matter is complex and has
a quite big amount of its development recently done. This lack of time brought limitations to
represent one SMB bed by simpler 1D models, plug flow reactors and CTSR in the presence of
obstacles and to easily simulate the chromatographic separation in an industrial case. These
points can also be done in future studies to efficiently upgrade the xylene separation
performed by the SMB.
Conclusions 39
References
 Augier, F., Laroche, C., & Brehon, E. (2008). Application of computational fluid
dynamics to fixed bed adsorption calculations: effect of hydrodynamics at laboratory
and industrial scale. Separation and Purification Technology, 63(2), 466-474.
 Cannella, William J. "Xylenes and ethylbenzene." Kirk-Othmer Encyclopedia of

Chemical Technology (2007).
 Daems, I., Leflaive, P., Méthivier, A., Baron, G. V., & Denayer, J. F. (2006). Influence
of Si: Al-ratio of faujasites on the adsorption of alkanes, alkenes and aromatics.
Microporous and mesoporous materials, 96(1), 149-156.
 Danckwerts, P. V. (1958). The effect of incomplete mixing on homogeneous reactions.

Chemical Engineering Science, 8(1), 93-102.
 Delgado, J. M. P. Q. (2006). A critical review of dispersion in packed beds. Heat and

mass transfer, 42(4), 279-310.
 Ergun, S. (1952). Fluid flow through packed columns. Chem. Eng. Prog., 48.
 Fabri, J., Graeser, U. and Simo, T. A. 2000. Xylenes. Ullmann's Encyclopedia of

Industrial Chemistry.
 Giese, M., Rottschäfer, K., & Vortmeyer, D. (1998). Measured and modeled superficial
flow profiles in packed beds with liquid flow. AIChE Journal, 44(2), 484-490.
 Liu, M. (2012). Age distribution and the degree of mixing in continuous flow stirred
tank reactors. Chemical Engineering Science, 69(1), 382-393.
 Liu, M., & Tilton, J. N. (2010). Spatial distributions of mean age and higher moments
in steady continuous flows. AIChE Journal, 56(10), 2561-2572.
 Minceva, M. and Rodrigues, A. E., AIChE J., 53(1), 138–149 (2007). (Understanding and
Revamping of Industrial Scale SMB Units for p-Xylene Separation)
 Minceva, M., & Rodrigues, A. E. (2002). Modeling and simulation of a simulated moving
bed for the separation of p-xylene. Industrial & engineering chemistry research,
41(14), 3454-3461.
 Xylenes market report, IHS Chemical Week, November 2012
 Ruthven, D. M. (1984). Principles of adsorption and adsorption processes.
References 40
 Ruthven, D. M., & Ching, C. B. (1989). Counter-current and simulated counter-current

adsorption separation processes. Chemical Engineering Science, 44(5), 1011-1038.
 Sandberg, M. (1981). What is ventilation efficiency?, Building and Environment, 16(2),

123-135.
 Spalding, D. B. (1958). A note on mean residence-times in steady flows of arbitrary

complexity. Chemical Engineering Science, 9(1), 74-77.
 Zeng, Z., & Grigg, R. (2006). A criterion for non-Darcy flow in porous media. Transport
in Porous Media, 63(1), 57-69.
 Zwietering, T. N. (1959). The degree of mixing in continuous flow systems. Chemical

Engineering Science, 11(1), 1-15.
References 41
Appendix 1 Tables and figures

Table 10 – Moments distribution for the same residence time and different Schmidt number
Schmidt
0.7 0.5 0.4 0.3 0.01
number
μ(s) σ²(s2) μ(s) σ²(s2) μ(s) σ²(s2) μ(s) σ²(s2) μ(s) σ²(s2)
3.91 2.59 3.94 2.54 3.95 2.43 3.96 2.28 3.00 1.32
Top probes 1.54 0.07 1.55 0.07 1.55 0.07 1.55 0.07 1.71 0.52
1.21 0.85 1.22 0.80 1.22 0.75 1.20 0.66 1.05 0.15
14.91 0.60 14.93 0.72 14.94 0.80 14.95 0.88 14.55 1.46
13.74 0.33 13.74 0.33 13.74 0.34 13.74 0.34 13.82 1.02
Middle probes 13.14 0.35 13.14 0.35 13.14 0.35 13.14 0.35 13.34 0.72
12.81 0.37 12.82 0.36 12.82 0.36 12.82 0.36 13.12 0.61
13.28 1.52 13.26 1.38 13.23 1.29 13.21 1.17 12.88 0.45
Bottom 25.30 1.07 25.30 0.98 25.29 0.91 25.27 0.82 25.06 0.24
probes 25.78 0.09 25.78 0.09 25.78 0.09 25.78 0.10 25.89 0.69
Outlet 26.80 2.04 26.80 1.99 26.80 1.96 26.80 1.92 26.80 1.45
Figure 24 - Schematic view of the experimental installation with the obstacles (cylinder at
left and prism at right), with the respective dimensions.
43
Table 11 – Table of moments of age comparison between the already presented cases and
their equivalent beds coupled with two CSTR’s (one on top and other on the bottom free
flow zone).
Adsorption
Hydrodynamics
PX MOX
Case 1 (s) 2 (s2) CoV 1 (s) 2 (s2) CoV 1 (s) 2 (s2) CoV
2D global 28.44 2.16 0.051 51.64 6.03 0.048 45.60 5.25 0.050
1D + CSTR 28.24 1.87 0.048 52.44 6.04 0.047 45.91 5.56 0.051
2D + Cylinder 27.04 5.69 0.088 47.06 14.02 0.080 41.54 10.43 0.078
2D + Cylinder
27.16 7.93 0.104 47.15 20.59 0.096 41.52 17.67 0.101
+ CSTR
2D + Prism 26.89 9.25 0.113 46.75 29.34 0.116 41.44 26.35 0.124
2D + Prism +
26.85 9.02 0.112 46.84 29.08 0.115 41.49 29.57 0.131
CSTR
Note: Adsorption cases have no mass transfer limitations.
0.25
0.2
0.15
Prism PX
E (-)
Prism MOX
0.1
Prism + CSTR PX
Prism + CSTR MOX
0.05
0
30 35 40 45 50 55 60 65 70
Time (s)
Figure 25 - Adsorption separation, with no mass transfer limitations, results comparison for
the 2D geometry with a quadrangular prism as an obstacle
44
Appendix 2 User defined functions

/******************************** **
UDF to define the anisotropic diffusivity
*******************************************/
#include "udf.h"
/**********************************
************************************/
#define sct 0.7

#define dp 0.001
#define eps 0.357
#define Peax 2
#define Pera 11
DEFINE_ANISOTROPIC_DIFFUSIVITY(udf_anis,c,t,i,dmatrix)
{
if(THREAD_VAR(t).fluid.porous)
{
dmatrix[0][0]=C_R(c,t)*eps*(1e-
8+dp*(fabs(C_V(c,t)/Pera)+fabs(C_U(c,t)/Peax)));
dmatrix[0][1]=0;
dmatrix[1][0]=0;
dmatrix[1][1]=C_R(c,t)*eps*(1e-
8+dp*(fabs(C_V(c,t)/Peax)+fabs(C_U(c,t)/Pera)));
}
else
{
dmatrix[0][0]=1e-8*C_R(c,t)+C_MU_T(c,t)/sct;
dmatrix[0][1]=0;
dmatrix[1][0]=0;
dmatrix[1][1]=1e-8*C_R(c,t)+C_MU_T(c,t)/sct;
}
}
45
/*********************************************************************
**
UDF to specify steady-state parabolic pressure profile boundary
**********************************************************************
**/
#include "udf.h"
DEFINE_PROFILE(uds1_profile,t,i)
{
real x[ND_ND]; /* this will hold the position vector
*/
real y;
face_t f;
real flow_time=RP_Get_Real("flow-time");
real tempszero;
real buf;
tempszero = 0;
begin_f_loop(f,t)
{
F_CENTROID(x,f,t);
y = x[1];
buf=1.05*(0.91-exp(-(flow_time-0.2-tempszero)/0.2))*exp(-
(flow_time-0.72-tempszero)/0.43);
if (buf>=0.00001)
{
F_PROFILE(f,t,i) = buf;
}
else
{
F_PROFILE(f,t,i) = 0;
}
}
end_f_loop(f,t)
46

Hydrodynamic Modeling of Adsorption - Application To The Separation of Xylenes

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Hydrodynamic Modeling of Adsorption - Application To The Separation of Xylenes

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Master in Chemical Engineering

Hydrodynamic modeling of adsorption -

Miguel Domingos da Silva

Thesis performed in the framework of Dissertation at

Supervisor from IFP: Dr. Frédéric Augier

Supervisor from FEUP: Prof. José Carlos Lopes

Department of Chemical Engineering

Thank you all!

Keywords: Hydrodynamics, Adsorption, Simulated Moving Bed,

Este trabalho tem como objectivos principais o estudo e modelisação da hidrodinâmica de um

Palavras Chave: Hidrodinâmica, Adsorção, Leito Móvel Simulado, Dinâmica

2 Bibliographic study .................................................................................. 2

2.1 Xylenes ........................................................................................... 2

2.2 Theoretical description and background .................................................. 7

2.3 Flow characterization methods ........................................................... 12

3 Technical Description ............................................................................. 19

3.1 Experimental Setup.......................................................................... 19

3.2 CFD approach ................................................................................. 20

3.3 Ideal model approximations ............................................................... 21

4 Results and discussion ............................................................................ 23

4.1 Hydrodynamics ............................................................................... 23

4.2 Adsorption ..................................................................................... 31

4.3 Ideal model approximations ............................................................... 34

Appendix 1 Tables and figures ..................................................................... 43

Appendix 2 User defined functions ................................................................ 45

Figure 3 – Simplified scheme of a chromatography. ................................................................5

Figure 6 - Example of RTD. ............................................................................................ 13

Figure 10 – 2D geometry representative of the experimental installation. .................................. 20

Figure 20 – RTD comparison between the three geometries .................................................... 36

Table 2 – Hydrodynamic simulation parameters ................................................................... 23

Notation and Glossary

t* Switching time (s)

Indexes and exponents

 Study and model hydrodynamics of an adsorption bed of a SMB through CFD

 Identify the effect that obstacles provoke in hydrodynamics.

Figure 1 – Molecular structure of the mixed xylenes.

2.1.1 Mixed Xylenes - production and use

Figure 2 – Main utilizations of the mixed xylenes [Fabri et al., 2000].

2.1.2 Separation of Mixed Xylenes

The physical properties of the mixed xylenes are shown in Table 1.

Table 1 – Physical properties of mixed xylenes [Fabri et al., 2000].

o-xylene m-xylene p-xylene ethylbenzene

boiling point (°C) 144.4 139.1 138.4 136.2

melting point (°C) -25.2 -47.9 13.3 -95.0

density at 25°C (kg/m3) 876.0 859.9 856.7 862.4

Figure 3 – Simplified scheme of a chromatography.

2.1.2.2 True Moving Bed (TMB) process

A simplified diagram of the TMB is shown in Figure 4.

2.1.2.3 Simulated Moving Bed process

2.2 Theoretical description and background

2.2.1.1 Free flow

, , , are constant parameters of the model determined experimentally and is

2.2.1.2 Porous Media

The Brinkman-Forchheimer model, is a modification of the laminar Navier-Stokes equations

for continuity, where represents the fluid interstitial velocity (m/s).

2.2.2 Mass Transfer

2.2.2.1 Inter-particle phase

The longitudinal ( ) and transversal dispersion ( ) coefficients can be calculated by using a

2.2.2.2 Intra-particle phase

2.2.3 Adsorption Equilibria

The adsorbed concentration is obtained through the Langmuir multicomponent adsorption

2.3 Flow characterization methods

2.3.1 Residence Time Distribution (RTD)