Modelling and Simulation in Chemical Engineering
Modelling and Simulation in Chemical Engineering
Abstract
The Chemical Engineering Science movement has served well in solving problems from micro to macro scales. Ultimately, as Professor
R. Sargent pointed out, it would be better if translated in “Scientific Engineering”.
Examples of innovation as a combination of science (concept), technology and process/product will be presented.
The first example is perfusion chromatography based on the concept of “diffusivity augmented by convection” and on the technology
of fabrication of large-pore packings. The second example, Simulated Moving Bed (SMB), is based on a concept developed to overcome
the difficulties in implementing True Moving Bed processes. Technological contributions come from adsorbent materials and rotary valve
to simulate the solid movement. SMB is now a key technology for chiral separations. Modelling/Simulation tools provide sound basis for
design/operation by using the concept of “separation volume”.
The third example is from the area of multifunctional reactors. The SMB technology is extended to the simultaneous reaction/separation.
© 2005 Elsevier Ltd. All rights reserved.
Keywords: Chemical Engineering Science; Process innovation; Technology; Perfusion chromatography; Simulated Moving Bed; Multifunctional reactors
1. Introduction—the Chemical Engineering Science I remember the statement of Professor Le Goff (1970)
movement when I was a student in Nancy “Le Génie Chimique c’est
pas de la plomberie” and the philosophy of modelling that a
The Chemical Engineering Science movement illustrated chemical engineer uses when solving a new problem involv-
in the book of Bird, Stewart, and Lighfoot “Transport ing the writing of:
Phenomena” (2002) follows the approach initiated by
• conservation equations (mass, energy, momentum and
Kramers at Delft in his lecture notes “Physische Transportver-
electric charge);
schijnselen” (Kramers, 1958). It contains the basic material
• equilibrium laws at the interface(s);
to help in developing a mathematical model defined by Aris
• constitutive laws (e.g., ideal gas law);
(1994) as “a complete set of mathematical equations which
• kinetic laws of transport and reaction;
are supposed to correspond to some entity – its prototype –
• initial and boundary conditions;
which can be a physical, biological, social . . . entity although
• optimization criteria.
here we deal with physicochemical systems”.
A process model is a relation between “outputs” and “in- This methodology has been useful to analyze problems at
puts” (feed conditions, design parameters and process ad- various scales involved in chemical engineering:
justable parameters) in view of (i) scale-up from lab to in-
dustrial scale, (ii) prediction of process dynamics and (iii) • pore scale (catalyst and adsorbent): 1–1000 nm;
optimization of operating conditions (Shinnar, 1978). • particle scale: 10 m–1 cm;
• reactor/separator scale: 1–10 m;
∗ Corresponding author. Tel.: +351 22 5081671; fax: +351 22 5081674. Models can be guided by objectives, which can seem con-
E-mail address: [email protected] (A.E. Rodrigues). tradictory: simplification of the reality/idealization and de-
0098-1354/$ – see front matter © 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2005.02.029
1168 A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183
tailed models to “better” know the reality. On one side they 2. The “art” of modelling
aim at simplification of reality or idealization; this is con-
densed in the words of Denbigh (1951) “In science it is al- Chemical engineers use some techniques in modelling
ways necessary to abstract from the complexity of the real such as: adimensionalization and scaling, averaging, appro-
world, and in its place to substitute a more or less ideal- priate choice of independent variables. However, physical
ized situation that is more amenable to analysis” and led insight is gained as a consequence of such manipulations. A
to the creation of new, simplified models which are a “dig- further step is transforming model results into useful tools
ital impression” of our profession: boundary layer theory, for real life situations.
film model for heat/mass transfer, residence time distribu-
2.1. Scaling and dimensionless groups
tion (RTD) theory (Levenspiel, 2002). On the other hand,
detailed models are necessary when simple models fail to Chemical engineers have some habits as normalization
capture essential behaviour of real systems; this is illustrated of variables; as a consequence of that mathematical opera-
by the Maxwell–Stefan treatment of multicomponent diffu- tion dimensionless groups appear with a physical meaning.
sion (Maxwell, 1952): Consider the problem of diffusion/reaction in an isothermal
n
porous catalyst with slab geometry. The mass balance in
xi Nj − x j Ni
di = ∇xi = (1) steady-state for irreversible reaction of order n is:
j=1
ct DijMS
d2 ci
De − kcin = 0 (3)
The basic laws of momentum transfer (Newton’s law: dz2
τyx = µ dνx
dy ), heat transfer by conduction (Fourier’s law: with boundary conditions (symmetry condition in the centre
qy = −k dT and surface condition)
dy ), mass transfer by diffusion (Fick’s law: jy =
−DAB dρ dci
dy at constant ρ) assume infinite velocity of propa-
A
z = 0, =0
gation of the signal; this problem is eliminated following the dz (4)
proposal of Maxwell (1952) for momentum transfer z = , ci = ciS
∂σyx ∂ux The normalization of space variable x = z/ and concentra-
σyx + τ = −µ (2) tion variable fi = ci /ciS leads to:
∂t ∂y
n−1
d2 fi 2 kciS
where τ is the time constant and the shear stress σ yx − fn = 0 (5)
in a fluid or solid body σ yx ; similarly for mass trans- dx2 De i
fer (Westerterp, Kronberg, Benneker, & Dil’man, 1996) The dimensionless group φ (Thiele modulus) governing the
and heat transfer (Liu, Chen, & Xu, 1999) one should reaction/diffusion problem is:
∂q
write: j + τ ∂j ∂c ∂T
∂t = −D ∂x and q + τ ∂t = −k ∂x (Vernott and
n−1
kciS
Cattaneo—VC equation). In homogeneous substances, the 2 = φ2 = DaII (6)
De
relaxation time is 10−8 to 10−14 s and Fourier’s law works
for normal heating processes; but in biological systems τ is The physical meaning of the dimensionless group is: φ2 =
of the order of 10–30 s and VC equation applies. DaII = reaction rate/diffusion rate = diffusion time con-
A philosophy of modelling can be based in four points: stant/reaction time constant. Two extreme cases are (Fig. 1):
• start with simple models; obtain from such models in- (a) reaction rate diffusion rate—concentration profile in-
formation which remains valid for more complex models side the catalyst is almost equal to the surface concentra-
(US$ 10 approach of Levenspiel (2002): “Always start by tion; the catalyst works on “chemical regime”;
trying the simplest model and then only add complexity to (b) reaction rate diffusion rate—the catalyst works in
the extent needed”); “diffusional regime”.
• the validity of a model is not just a result of a “good fit”;
more important is the capability to predict the system be-
haviour under operating conditions different from those
used to get model parameters;
• good results can only be obtained if the model “well” rep-
resents the system;
• use models to obtain useful design parameters and their
dependence on operating conditions; use independent ex-
periments if possible to get model parameters.
In short, model development is a task to be carefully done
to avoid waste of energy in the next simulation step. “Keep
things as simple as possible, but not simpler” (Einstein). Fig. 1. Chemical regime and diffusional regime in an isothermal catalyst.
A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183 1169
shown in Fig. 3:
Multiplying both members by R2 dR, integrating over the par-
ticle volume (between 0 and Rp ) and introducing the average
concentration qi leads to: 1− K T
ĉi = , K ≤ T ≤ 1/K (14)
∂ qi 3Dh ∂qi 3Dh qiS − qi 1−K
= =
∂t Rp ∂R Rp Rp αRp
2.4. From model results to real life
15Dh
= (qiS − qi ) = kh (qiS − qi ) (9) Back to the reaction/diffusion problem for first order re-
R2p
action in isothermal slab catalyst. The concentration profile
is fi = cosh(φx)
cosh φ and the effectiveness factor of the catalyst
φ
2.3. Choice of variables is η = tanh
φ . It is important to know the effectiveness fac-
tor to calculate the amount of catalyst in the reactor needed
Let us consider the equilibrium model of an isothermal to get a given reactant conversion. But the Thiele modu-
adsorption column with plug fluid flow of a diluted stream lus requires that the kinetic constant k must be known (and
(trace system). Model equations are the mass balance of the many times it is not). Hopefully, there are always bright peo-
solute in a bed volume element and the equilibrium law at ple around to transform theoretical results in practical tools.
the interface fluid/solid: Weisz and Prater (1954) changed η = f(φ) in a more useful plot
∂ci ∂ci ∂q∗ η = g(ηφ2 ), where ηφ2 does not require the knowledge of k;
u0 +ε + (1 − ε) i = 0 (10) but only measurable quantities since ηφ2 = rcobs 2
∂z ∂t ∂t iS De
(Fig. 4).
qi∗ = f (ci ) (11)
2.5. Obtaining useful relations between dependent
For an adsorption isotherm of “constant separation factor” variables
type and normalizing the dependent variables, ĉi = cci0i , q̂i =
qi
qi0 we get: Consider the diffusion/reaction/conduction problem in a
non-isothermal slab catalyst. For slab geometry and first order
∂ĉi ∂ĉi 1 − ε qi0 ∂q̂i irreversible reaction conservation equations of mass/energy
ui + + =0 (12)
∂z ∂t ε ci0 ∂t are:
1170 A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183
d2 f df
2
− 2λm − 4φS2 f = 0 (24)
dx dx
This result is valid for first order reactions. For other reaction
kinetics, it gives the limit when the flow is completely segre-
gated; in the limit of maximum micromixing the Zwietering
equation (1959) holds. Fig. 7. Asymmetric concentration profiles in large-pore catalysts.
1172 A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183
4. Process simulation
Fig. 15. HETP vs. u (Van Deemter equation and Rodrigues equation).
Fig. 17. Porous materials: (a) POROS packing, (b) Silica Monolith (Merck) and (c) POROSHELL (Agilent Technologies).
1176 A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183
Fig. 18. Parex process with rotary valve (AC: adsorbent chamber; RV: rotary valve; EC: extract column; RC: raffinate column; lines: 2—desorbent; 5—extract;
9—feed; 12—raffinate).
isomers column diameter is D = 10 m (maximum) and bed sorbed and carried with the solid phase. Section 2 is the zone
height H = 1 m and particles are of 600 m diameter; in chi- of desorption of the less retained species B, while section
ral separations (Fig. 19), D = 1 m (maximum) and H = 0.1 m 3 is the zone of adsorption of the more retained component
(similar D/H ratio) with particles of 20 m diameter. The A. The role of section 4 is to clean the eluent, which is then
adsorbent capacity is 200 kg/m3 in the Parex process com- recycled to the section 1 where the adsorbent is regenerated.
pared with 10 kg/m3 in chiral separations; the productivity is The operation of this ideal TMB has several drawbacks as-
120 kg/m3 h in the Parex and 1–10 kg/m3 h in chiral separa- sociated with the movement of the solid phase. A Simulated
tions. Moving Bed technique was developed in order to retain the
The principle of SMB operation can be best understood advantages of continuous and countercurrent flow without
by analogy with the equivalent True Moving Bed (TMB) pro- introducing the problems associated with the actual move-
cess. The TMB unit (Fig. 20) is divided into four sections: ment of the solid phase. In the SMB system, the adsorbent is
section 1, between the eluent and extract ports; section 2, fixed and the positions of the inlet and outlet streams move
between the extract and feed ports; section 3, between feed periodically.
and raffinate points; section 4, between the raffinate and the This shift, carried out in the same direction of the liquid
eluent inlet. In the ideal TMB operation, liquid and solid flow phase, simulates the movement of the solid phase in the op-
in opposite directions, and are continuously recycled: the liq- posite direction. The four liquid access lines between each
uid flowing out of section 4 is recycled to section 1, while column can be used to perform a discrete movement of the
the solid coming out of section 1 is recycled to section 4. In inlet and outlet streams in the same direction of the liquid
the TMB operation, the solid flow rate is constant all over phase.
the unit; however, the liquid flow rates differ from section In the Sorbex SMB technology developed by UOP
to section. Let us consider a feed mixture containing species (Fig. 18), a rotary valve is used to periodically change
A, the more retained component and recovered in the extract the position of the eluent, extract, feed and raffinate lines
(Fig. 19a) and species B, the less adsorbed species and pref- along the adsorbent bed. At any particular moment, only
erentially recovered in the raffinate. In sections 2 and 3, the four lines between the rotary valve and the adsorbent bed
two components must move in opposite directions. The less are active. However, there are alternative techniques to per-
retained component B must be desorbed and carried with the form the port switching, like the one developed by NovaSep
liquid phase, while the more retained species A must be ad- (France), which uses a set of individual on-off valves connect-
A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183 1177
Fig. 19. (a) SMB technology for chiral separations and (b) SMB unit Licosep 12-26 (Novasep) at the LSRE.
ing the inlet and outlet streams to each node between columns other hand, the SMB approach examines each column indi-
(Fig. 19). vidually. Due to the switching of inlet and outlet ports, each
column plays a different role during whole cycle, depending
on its location. The model of the SMB unit is constituted of k
4.2.2. Modelling of SMB (k = number of the columns) identical models of the column,
The SMB can be modelled as an equivalent TMB where
the solid movement is taken into account and equivalence re-
lations are used to relate the results with a real SMB (Table 1) Table 1
Equivalence relations between a SMB and a TMB
or as a real SMB; each bed is analyzed individually and the
periodic change in boundary conditions is taken into account. SMB TMB
With reference to Fig. 20, the TMB unit is divided by inlet Solid phase velocity 0 us = Lc /t*
and outlet ports into four zones. The TMB steady-state in- Liquid phase velocity vSMB vTMB = vSMB − us
ternal concentration profiles are presented in Fig. 21. On the t* is the switching time and Lc is the column length.
1178 A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183
Fig. 22. Cyclic steady-state concentration profiles at the beginning, half and end of the switching time period: (a) species A, (b) species B, (c) extract
concentration history and (d) raffinate concentration history.
the equilibrium theory is a triangle shown in Fig. 23a. The model and explore the influence of the flow rates in zones 1
section constraints are explicit inequality relations between and 4 (desorbent flow rate). The “separation volume” method-
solid and liquid flow rates in the four TMB sections (Ruthven ology offers two possibilities: if the flow rate in zone 1 (m1 )
& Ching, 1989; Storti, Mazzotti, Morbidelli, & Carrà, 1993): is fixed, the design leads to a (m2 × m3 × m4 ) volume for a
given separation requirement; if the flow rate in zone 4 (m4 )
m1 > KA KB < m2 , m3 < KA m 4 < KB (38) is fixed, the design will result in a (m2 × m3 × m1 ) volume
For non-linear isotherms the “triangle” is distorted as shown for a given separation requirement (see Fig. 25). In previous
in Fig. 23b. works (Azevedo & Rodrigues, 1999; Minceva & Rodrigues,
Higher mass transfer resistances lead to a decrease of the 2002; Rodrigues & Pais, 2004) it was found that the flow rate
separation region as shown in Fig. 24 (Pais, 1999). in zone 4 has less influence on the separation performance.
For the systems where mass transfer resistance inside par-
ticles is important, the “triangle theory” can only give initial 4.2.4. Optimization of SMB
guesses for a feasible operating point of the process, since it is The optimization of SMB unit considers selection of the
based on the assumption of the equilibrium model. Very often, operating conditions and/or geometric parameters that min-
100% purity in both extract and raffinate is either unnecessary imize/maximize a given objective function(s), in the frame
or would require an extremely large adsorbent inventory to be of previously defined constraints. Most commonly the ob-
accomplished. Furthermore, the approach based on equilib- jective is to maximize the SMB productivity and mini-
rium model does not allow explicit prediction of the product mize the eluent (desorbent) consumption, for a given con-
purities that are generally the main constraints for a feasible straints defined in terms of minimum required product purity
operating point. and/or recovery. Maximum productivity implies maximum
These are the reasons why the concept of separation vol- feed flow rate, max(QF ) = max(γ 3 − γ 2 ) and minimum elu-
ume was introduced (Azevedo & Rodrigues, 1999). The “sep- ent (desorbent) consumption implies minimum eluent flow
aration volume” methodology uses realistic mathematical rate min(QE ) = min(γ 1 − γ 4 ), where γj = (1−ε)
ε mj , j = 1, 2,
1180 A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183
Table 2
Transient SMB and TMB model equations
Simulated Moving Bed model equations
Mass balance over a volume element of the bed k
∂Cik 1 ∂2 Cik ∂Cik (1 − ε)
= γk∗ − = ∗
αk (qik − qik )
∂θ Pek ∂x 2 ∂x ε
Initial conditions
θ = 0 : Cik = qik = 0
Global balances
Eluent node : ν1∗ = ν4∗ + νE ; extract node : ν2∗ = ν1∗ − νX
Feed node : ν3∗ = ν2∗ + νF ; raffinate node : ν4∗ = ν3∗ − νR
Initial conditions
θ = 0 : Cij = qij = 0 Fig. 23. Separation region for: (a) linear isotherms and (b) non-linear
isotherm.
Boundary conditions for section j
1 dCij
x = 0 : Cij − = Cij,0
Pej dx
where Cij,0 is the inlet concentration of species i in section j 3, 4. The influence of γ 1 and γ 4 on the SMB productivity and
x = 1: eluent consumption is presented in Fig. 26. The separation
ν1
For the eluent node: Ci4 = Ci1,0 ; for the extract node: region increases by increasing γ 1 up to some value and the
ν4
Ci1 = Ci2,0
ν3 νF
vertex moves from lower to higher values of (γ 2 , γ 3 ), higher
For the feed node: Ci2 = Ci3,0 − CiF ; for the raffinate productivity could be reached. When the separation region
ν2 ν2
node: Ci3 = Ci4,0 size does not increase more, further increment in γ 1 will lead
and qi4 = qi1,0 , qi1 = qi2,0 , qi2 = qi3,0 , qi3 = qi4,0 just to increase of the eluent consumption, since (γ 1 − γ 4 )
increases. When the value of γ 1 is fixed (Fig. 26b) the sep-
Global balances
Eluent node: ν1 = ν4 + νE ; extract node: ν2 = ν1 −νX aration regions are similar until some value of γ 4 and then
Feed node: ν3 = ν2 + νF ; raffinate node: ν4 = ν3 −νR they start to decrease if the value of γ 4 further increases. The
value of the flow rate in zone 4 (γ 4 ) does not influence the
Multicomponent adsorption equilibrium isotherm feed flow rate and SMB unit productivity, but it affects the
∗ = f (C , C )
qAj A Aj Bj
∗ = f (C , C ) desorbent consumption. We proposed a two-level optimiza-
qBj B Aj Bj
tion procedure based on the concept of “separation volume”
and equivalent TMB design (Minceva, 2004).
A.E. Rodrigues, M. Minceva / Computers and Chemical Engineering 29 (2005) 1167–1183 1181
Fig. 24. Influence of mass transfer resistance on the separation region for
non-linear isotherms.
Fig. 27. Comparison between the two different techniques: (a) TMB and (b) pseudo-SMB JO process.
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