Modelling and Simulation in Chemical Engineering-Rodrigues - E14 PDF

Alrio E.
Rodrigues | LSRE | DEQ | FEUP
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Modelling and Simulation in Chemical Engineering:

Tools for Process Innovation
A. E. Rodrigues
ESCAPE-14
May 16-19, 2004
Fundao Calouste Gulbenkian
Lisbon, Portugal
ESCAPE-14 Lisbon, Portugal
17 | MAY | 2004
Alrio E. Rodrigues | LSRE | DEQ | FEUP
OUTLINE
INTRODUCTION
THE ART OF MODELLING
MODELS OF 10$, 100$ and 1000$
PROCESS SIMULATION
PERFUSION CHROMATOGRAPHY
SIMULATED MOVING BED (SMB)
HYBRID PROCESS-SMB REACTOR
CONCLUSIONS
17 | MAY | 2004
BSL
17 | MAY | 2004
Ingredients for Process Innovation
Science
Technology
Process
17 | MAY | 2004
Increased
diffusivity by
convection
Adsorbents
(Materials)
Perfusion
chromatography
17 | MAY | 2004
SMB concept
Modelling
Simulation
Adsorbent
(Materials)
Technology
(rotary valve)
Sorbex processes
(UOP)
17 | MAY | 2004
ChE Methodology
Le Goff (1970)
Conservation equations (mass, energy, momentum,
electric charge)
Equilibrium laws at the interface (s)
Constitutive laws (e.g., ideal gas law)
Kinetic laws of transport and reaction
Initial and boundary conditions
Optimisation criterion
17 | MAY | 2004
17 | MAY | 2004
Axial dispersion (bulk)
Pore diffusion
External film diffusion
THE ART OF MODELLING

Surface diffusion
17 | MAY | 2004
Scaling and dimensionless groups
De
d 2 ci
dz
d 2 fi
dx 2
x=
z
l
kc
i
2
l2
=0
n 1
kciS
De
fi =
dci
=0
dz
z = l, ci = ciS
z = 0,
f in = 0
ci
ciS
n 1
kciS
reaction rate diffusion time constant
l
= 2 = DaII =
=
De
diffusion rate reaction time constant
2
17 | MAY | 2004
Averaging
LDF
qis
<qi>
qis
q i
1 2 q i
= Dh
R
2
t
R
R R
<qi>
qi(R)
R = 0,
q i
=0
R
R = R p , q iS = f (c i )
ci
cis
qi 3Dh qi
=
R p R
t
=
Rp
3Dh qiS qi 15 Dh
= 2 (qiS qi
R p R p
Rp
) = kh (qiS qi )
17 | MAY | 2004
Choice of variables
ui
ci ci 1 q io q i
+
+
=0
z
t
cio t
ci =
ci
q
, q i = i
ci 0
qi 0
q i =
Kci
1 + ( K 1)ci
T=
1 ui t
1
m z
K
1
T , K T 1 K
ci =
1 K
17 | MAY | 2004
From model results to real life

=
tanh
robs l 2
=
ciS De
2
1/
0.1
0.1
10
0
0.01
0.1
10
100
17 | MAY | 2004
Obtaining useful relations between

dependent variables
De
cis
cis
ci(R)
d 2 ci
dz
d 2T
dz
z = 0,
k (T )ci = 0
+ (H )k (T )ci = 0
dci dT
=
=0
dz
dz
z = l, ci = ciS ; T = Ts
T(R)
Ts
Ts
T Ts =
De ( H )
(ciS ci )
17 | MAY | 2004
2
2
(u) (v)

+
= 2 +
2
x
y
y
x
u=
;v =
MODELS
y OF 10$,
x 100$ AND 1000$
2 2
2 +
2
x
2C 2C
C (uC ) (uC )
+
+
= D 2 +
2
t
x
y
y
x
17 | MAY | 2004
10$ models:
Equilibrium theory for adsorption columns

c
c
qi
u 0 i + i + (1 )
=0
q i = q i* = f (c i )
z
t
t
ui
z
uci = =
t ci 1 + 1 f ' (c )
i
dispersive front
u sh
ui
=
1 qi
1+
ci
compressive front
17 | MAY | 2004
100$ models:
Diffusion, convection and reaction in isothermal catalysts

reaction A B in slab catalysts
d2 f
dx 2
2 m
S = l
m =
df
4 S2 f = 0
dx
k
De
Thiele modulus
intraparticle
Peclet number
v0l
De
sh 2e1 ( 2 x 1) sh1e 2 ( 2 x 1)
f =
sh( 2 1)
1,2 =
m 2m + 4 S2
2
17 | MAY | 2004
1 / 1 1 / 2
dc =
coth 1 coth 2
when convection is not important
m = 0
d =
tanh S
S = l
k
De
17 | MAY | 2004
1000$ models:
Computational Fluid Dynamics (CFD)
0.7 H
H
y
ux (y)
0.2 H
0.1 H
17 | MAY | 2004
PROCESS SIMULATION
17 | MAY | 2004
Increased
diffusivity by
convection
Adsorbents
(Materials)
Perfusion Chromatography
Perfusion
chromatography
17 | MAY | 2004
17 | MAY | 2004
Perfusion Chromatography
Old resin producer: Rohm & Haas
2003 -criou Advanced Biosciences
Amberchrom chromatographic media, Amberlite XAD
(biopharmaceuticals), Ambersynth CTC resin
New : PerSeptive Biosystems
(1990)
Now Applied Biosystems
17 | MAY | 2004
Chromatography Pioneers
1
b
M. Tswett
D. T. Day
17 | MAY | 2004
Factors governing the behaviour of

an adsorptive process
IntraParticle Convection
IntraParticle Diffusion
Film Mass Transfer
Hydrodynamics (RTD)
Equilibrium Data
17 | MAY | 2004
Concept behind Perfusion chromatography

~
De = De
1
f ( )
100
~
De
De
1/f( )
10
1
1
10
100
Enhancement factor for diffusivity

due to convection, 1/f()
17 | MAY | 2004
HETP= A + B/u + Cu
HETP = A +
B
+ Cf ( )u
u
17 | MAY | 2004
How to decrease intraparticle mass transfer

resistance?
17 | MAY | 2004
Porous materials
POROS packing
Silica Monolith
POROSHELL (Agilent Technologies)
17 | MAY | 2004
SMB concept
Modelling
Simulation
Adsorbent
(Materials)
Technology
(rotary valve)
Simulated Moving Bed

Sorbex processes
(UOP)
17 | MAY | 2004
Simulated Moving Bed - (SMB)
17 | MAY | 2004
SMB Technology
Old : UOP(1961)
Sorbex Processes: PAREX, SAREX, MOLEX
New : Novasep
First SMB in pharmaceutical industry
(UCB Pharma, 1999)
17 | MAY | 2004
Old and New

Parex
Productivity
Adsorbent capacity
120 Kg/m3 h
200 Kg/m3
Chiral separations
Productivity
Adsorbent capacity
1-10 Kg/m3 h
10 Kg/m3
17 | MAY | 2004
UOP Parex
AC=adsorbent chamber; RV=rotary valve; EC=extract column; RC=raffinate column.

Lines: 2-desorbent; 5-extract; 9-feed; 12-raffinate.
17 | MAY | 2004
NOVASEP-chiral separation
The largest unit in operation for chiral separations has only 6

columns (Blehault et al., AIChE Meeting, Chicago, March 2001).
17 | MAY | 2004
SMB unit at
Licosep 12-26 (Novasep)

17 | MAY | 2004
TMB concept
liquid circulation
Desorbent
(D)
Feed
(A+B)
Extract
(A+D)
Raffinate
(B +D)
Zone 1
Zone 2
A
Zone 3
Zone 4
solid circulation
regeneration of
the adsorbent
desorption of B
adsorption of A
regeneration of
the desorbent
17 | MAY | 2004
SMB concept
Desorbent
Desorbent
(D) (D)
Desorbent (D) (D)

Desorbent
Extract (A+D)
Extract
(A+D)
Zone 1
A more strong adsorbed
B more strong adsorbed
Zone 2
Zone 4
Extract (A+D) (A+D)

Extract
Port switching direction

Raffinate (B+D)
Raffinate(B+D)
Zone 3
Raffinate (B+D)
Raffinate(B+D)
(A+B)
FeedFeed
(A+B)
Feed (A+B)
Feed
(A+B)
17 | MAY | 2004
SMB-TMB equivalence
Solid phase
Liquid phase
SMB
v j
TMB
us =
Lc
t
v j = v *j u s
17 | MAY | 2004
Concentration profiles in TMB
E
R
17 | MAY | 2004
SMB Cyclic steady state

2
A
1.5
0%
50%
c, g/l
c, g/l
1.5
50%
0%
100%
100%
0.5
0.5
0
1.2
EXTRACT
1
0.8
c (g/l)
c (g/l)
0.6
0.4
0.2
0
0
50
100
150
t ( min)
200
250
2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
RAFFINATE
A
0
50
100
150
200
250
t ( min)
17 | MAY | 2004
Design of SMB
Separation constraints - equivalent TMB
Zone I
Zone II
QI c AI
QS q AI
>1
QII c AII
QS q AII
Zone III
<1
QIII c AIII
QS q AIII
Zone IV
QIV cBIV
QS qBIV
<1
QII cBII
QS qBII
>1
QIII cBIII
QS qBIII
>1
<1
17 | MAY | 2004
Separation regions-Equilibrium theory

linear isotherms
m1>KA
nonlinear isotherm
KA< m2 m3<KB and m4<KB
17 | MAY | 2004
Influence of the mass transfer resistance
no mass
transfer
resistance
mass
transfer
resistance
17 | MAY | 2004
Triangle theory vs. Separation volume methodology
Triangle theory
Separation volume
Design
100% product purities
any product purities
Design
parameters
flow rates-zone 2 and 3
flow rates-zone 2, 3 and 1 (or 4)
Mathematical
model
equilibrium model
general rate model
Design result
two dimensional
three dimensional
Optimal point
vertex
vertexes
17 | MAY | 2004
Design of SMB: separation volume methodology
Influence of 1 on the separation

region
Influence of 4 on the separation

region
17 | MAY | 2004
Optimization procedure concept

constant
violation of separation
requirements
productivity unchanged
desorbent consumption
increases
productivity increases
constant
productivity unchanged
desorbent consumption
decreases
violation of separation
requirements
max (32)=max(QF)=max(productivity)
min (14)=min(QD)=min(desorbent consumption)

17 | MAY | 2004
SMBR
Eluent
Eluent
(E)
Eluent
Eluent
(E)
(E)
(E)
Extract (B+E)
Extract
(B+E)
Zone 1
Raffinate(C+E)
(C+E)
Raffinate
Zone 2
Zone 4
Extract (B+E)
Extract
(B+E)
Portswitching
switching direction
Port
direction
A B
+CC
A
B+
Zone 3
Raffinate(C+E)
(C+E)
Raffinate
Feed
(A)
Feed
(A)
Feed
(A)
Feed
(A)
17 | MAY | 2004
SMBR movie
17 | MAY | 2004
SMBR-inversion of fructose
sucrose fructose + glucose
17 | MAY | 2004
Cashew apple juice chromatograms
17 | MAY | 2004
Separation regions: multicomponent mixtures

in the frame of the equilibrium theory
17 | MAY | 2004
JO Process
Pseudo-SMB
True Moving Bed
STEP 2
STEP 1
IV
Q4
IV
QS
IV
Q4
Q4
QR
QS
QR
III
QF
QI
II
II
II
QS
QS
Q3
Q3
QF
Q2
III
III
QS
Q3
Q2
Q2
QX
QS
QX
I
Q1
QEl
QS
Q1
Q1
QEl1
QS
QEl2
V. G. Mata, A. E. Rodrigues, J. Chromatography, 2001

17 | MAY | 2004
CONCLUSIONS
Modelling/Simulation - second paradigm of ChE
Molecular transformation? third paradigm of ChE
Astarita: the amount of information available
grows continuously but the amount of information
that any one of us can usefully digest does not
grow".
17 | MAY | 2004
17 | MAY | 2004

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Alrio E.

Rodrigues | LSRE | DEQ | FEUP

Modelling and Simulation in Chemical Engineering: Tools for Process Innovation