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Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
A. E. Rodrigues
ESCAPE-14May 16-19, 2004
Fundação Calouste GulbenkianLisbon, Portugal
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
OUTLINEINTRODUCTIONTHE “ART” OF MODELLINGMODELS OF 10$, 100$ and 1000$PROCESS SIMULATIONPERFUSION CHROMATOGRAPHYSIMULATED MOVING BED (SMB)HYBRID PROCESS-SMB REACTOR
CONCLUSIONS
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
BSL
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Ingredients for Process Innovation
Science Technology
Process
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Increaseddiffusivity byconvection
Adsorbents (Materials)
Perfusion chromatography
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB conceptModellingSimulation
Adsorbent(Materials)
Technology(rotary valve)
Sorbex processes (UOP)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
ChE MethodologyLe 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 reactionInitial and boundary conditionsOptimisation criterion
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Surface diffusion
Pore diffusion External film diffusion
Axial dispersion (bulk)
Surface diffusion
Pore diffusion External film diffusion
Axial dispersion (bulk)
THE “ART” OF MODELLING
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Scaling and dimensionless groups
constant time reactionconstant time diffusion
rate diffusionrate reactionDa
Dkc
IIe
niS ====
−2
12 φl
02
2=− n
ii
e kcdz
cdD
iSi
i
cczdzdcz
==
==
,
0,0
l
01
22
2=−
−n
ie
niSi f
Dkc
dx
fdl
lzx =
iS
ii c
cf =
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Averaging
LDF
cicis
qis qis
<qi><qi>
qi(R)
⎟⎠⎞
⎜⎝⎛=
Rq
RRR
Dt
q ih
i∂∂
∂∂
∂∂ 2
21
)(,
0,0
iiSp
i
cfqRRRq
R
==
==∂∂
) )(( ⟩⟨−=⟩⟨−=⟩⟨−
==⟩⟨
iiShiiSh
p
iiS
p
h
R
i
p
hi qqkqqR
DR
qqRD
Rq
RD
tq
pp2
1533α∂
∂∂
∂
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Choice of variables
00ˆ,ˆ
i
ii
i
ii q
cc
c ==
i
ii cK
cKq
ˆ)1(1ˆ
ˆ−+
=
0ˆ1ˆˆ
=−
++t
qcq
tc
zc
u i
io
ioiii ∂
∂ε
ε∂
∂∂∂
KTKKTK
ci 1,1
1ˆ ≤≤
−
−=
⎟⎠⎞
⎜⎝⎛ −= 11
ztuT i
mξ
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
From model results to real life
eiS
obsDc
r 22 l
=ηφφφη tanh
=
0.1
1
0.1 1 10φi
η
η≈1
η≈1/φ
0
1
0.01 0.1 1 10 100
η φ2
η
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Obtaining useful relations between dependent variables
)()(
iiSe
es cc
HDTT −
∆−=−
λ
0)(2
2=− i
ie cTk
dzcd
D
0)()(2
2=∆−+ ie cTkH
dzTdλ
0,0 ===dzdT
dzdc
z i
siSi TTccz === ;,l
cis
ci(R)
cis
Ts
T(R)Ts
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
⎟⎟⎠
⎞⎜⎜⎝
⎛+=++
Ω−=⎟⎟⎠
⎞⎜⎜⎝
⎛+
−==
⎟⎟⎠
⎞⎜⎜⎝
⎛ Ω+
Ω=
Ω+
Ω
2
2
2
2
2
2
2
2
2
2
2
2
)()(
;
)()(
yC
xCD
yuC
xuC
tC
yx
xv
yu
yxyv
xu
∂∂
∂∂
∂∂
∂∂
∂∂
∂ψ∂
∂ψ∂
∂∂ψ
∂∂ψ
∂∂
∂∂ν
∂∂
∂∂
MODELS OF 10$, 100$ AND 1000$
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
10$ models:Equilibrium theory for adsorption columns
0)1(0 =⟩⟨
−++tq
tc
zc
u iii∂
∂ε
∂∂
ε∂∂
)(*iii cfqq ==⟩⟨
i
i
ish
cq
uu
∆∆−
+=
εε11)(11 '
i
i
cc
cf
utzu
ii
εε∂
∂−
+=⎟
⎠⎞
⎜⎝⎛=
dispersive front compressive front
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
100$ models:Diffusion, convection and reaction in isothermal catalysts
reaction A → B in slab catalysts
042 22
2=−− f
dxdf
dx
fdSm φλ
eS D
kl=φ
em D
v l0=λ
Thiele modulus
intraparticlePeclet number
)( 12
)12(1
)12(2 21
αααα αα
−−
=−−
shesheshf
xx
24 22
2,1Smm φλλ
α+±
=
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
21
21cothcoth
/1/1αα
ααη
−−
=dc
S
Sd φ
φη
tanh=
0=mλ
when convection is not important
eS D
kl=φ
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
1000$ models:Computational Fluid Dynamics (CFD)
L
H
ux (y) 0.2 H
0.7 H
0.1 H
y
x
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
PROCESS SIMULATION
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Increased diffusivity by convection
Adsorbents (Materials)
Perfusion chromatography
Increased diffusivity by convection
Adsorbents (Materials)
Perfusion chromatography
Perfusion Chromatography
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Perfusion Chromatography
“Old” resin producer: Rohm & Haas2003 -criou Advanced Biosciences
Amberchrom chromatographic media, Amberlite XAD (biopharmaceuticals), Ambersynth CTC resin
“New” : PerSeptive Biosystems(1990)
…Now Applied Biosystems
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Chromatography Pioneers
V
A
R
1
e
f
d
ba
c
M. Tswett D. T. Day
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Factors governing the behaviour of an adsorptive process
IntraParticle Convection
IntraParticle Diffusion
Film Mass Transfer
Hydrodynamics (RTD)
Equilibrium Data
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Concept behind Perfusion chromatography
)(1~λf
DD ee =
1
10
100
1 10 100
De
De~
λ
1/f( )λ
Enhancement factor for diffusivity due to convection, 1/f(λ)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
HETP= A + B/u + Cu
uCfuBAHETP )(λ++=
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
How to decrease intraparticle mass transfer resistance?
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Porous materials
POROSHELL (Agilent Technologies)POROS packing Silica Monolith
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB conceptModellingSimulation
Adsorbent(Materials)
Technology(rotary valve)
Sorbex processes (UOP)
SMB conceptModellingSimulation
Adsorbent(Materials)
Technology(rotary valve)
Sorbex processes (UOP)
SimulatedSimulated MovingMoving BedBed
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Simulated Moving Bed - (SMB)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB Technology
“Old” : UOP(1961)Sorbex Processes: PAREX, SAREX, MOLEX…
“New” : NovasepFirst SMB in pharmaceutical industry
(UCB Pharma, 1999)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
“Old” and “New”
• ParexProductivity 120 Kg/m3 hAdsorbent capacity 200 Kg/m3
• Chiral separationsProductivity 1-10 Kg/m3 hAdsorbent capacity 10 Kg/m3
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 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.
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 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).
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB unit at
Licosep 12-26 (Novasep)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
TMB concept
Desorbent(D)
Feed (A+B)
Extract(A+D)
Raffinate (B +D)
A B
liquid circulation
Zone 1 Zone 2 Zone 3 Zone 4
solid circulation
A A B
B
regeneration of the adsorbent
regeneration of the desorbent
desorption of B adsorption of A
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB concept
Desorbent (D) Extract (A+D)
Feed (A+B) Raffinate (B+D)
Port switching direction
Desorbent (D)
Raffinate (B+D)
Extract (A+D)
Feed (A+B)
Zone 1
Zone 3
Zone
4 Zone 2
B more strong adsorbedA more strong adsorbed
Extract (A+D)Desorbent (D)
Feed (A+B)Raffinate(B+D)
Desorbent (D)
Extract (A+D)
Feed (A+B)
Raffinate(B+D)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB-TMB equivalence
Solid phase Liquid phase
SMB 0 ∗jv
TMB ∗=tLu c
s sjj uvv −= *
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Concentration profiles in TMB
EE XX FF RR
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMB Cyclic steady state
00.20.40.60.8
11.21.41.61.8
2
0 50 100 150 200 250
t ( min)
c (g
/l)
0
0.5
1
1.5
2
0 1 2 3 4 5 6 7 8
c, g
/l
E X F R
0%
50%
100%
B
0
0.5
1
1.5
2
0 1 2 3 4 5 6 7 8
c, g
/l
E X F R
0%
50%
100%
A
0
0.5
1
1.5
2
0 1 2 3 4 5 6 7 8
c, g
/l
E X F RE X F R
0%
50%
100%
A
0
0.2
0.4
0.6
0.8
1
1.2
0 50 100 150 200 250
t ( min)
c (g
/l)
A
B
EXTRACT
A
B
RAFFINATE
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Design of SMBSeparation constraints - equivalent TMB
1>IAS
IAIqQcQ
1>IIBS
IIBIIqQcQ
1<IIAS
IIAIIqQcQ
Zone I
Zone II
1<IIIAS
IIIAIIIqQcQ
1>IIIBS
IIIBIIIqQcQZone III
1<IVBS
IVBIVqQcQ
Zone IV
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Separation regions-Equilibrium theory
linear isotherms nonlinear isotherm
m1>KA KA< m2 m3<KB and m4<KB
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
no masstransfer
resistance
masstransfer
resistance
Influence of the mass transfer resistance
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
“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
Triangle theory vs. Separation volume methodology
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Design of SMB: ”separation volume” methodology
Influence of γ4 on the separationregion
Influence of γ1 on the separationregion
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Optimization procedure concept
constant γ4
productivity unchanged
desorbent consumption increases
productivity increases
violation of separation requirements
constant γ1
violation of separation requirements
productivity unchanged
desorbent consumption decreases
max (γ3−γ2)=max(QF)=max(productivity)
min (γ1−γ4)=min(QD)=min(desorbent consumption)
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMBREluent (E) Extract (B+E)
Feed (A) Raffinate (C+E)
Port switching direction
Eluent (E)
Raffinate (C+E)
Extract (B+E)
Feed (A)
Zone 1
Zone 3
Zone
4 Zone 2
A B + C
)
Extract (B+E)
Extract (B+E)
Eluent (E) Eluent (E)
Raffinate (C+E)
Raffinate (C+E) Feed (A) Feed (A)
A → B + C
Port switching direction
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMBR movie
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
SMBR-inversion of fructose
sucrose → fructose + glucose
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Cashew apple juice chromatograms
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
Separation regions: multicomponent mixturesin the frame of the equilibrium theory
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004
JO Process
IVQ4 QS
IIIQ3 QS
IIQ2 QS
IQ1 Q S
QR
QF
QX
QEl
IVQ4
IIIQ3
IIQ2
IQ1
QFQI
QEl1
IVQ4 QS
IIIQ3 Q S
IIQ2 Q S
IQ1 Q S
QR
QX
True Moving Bed Pseudo-SMBSTEP 1 STEP 2
QEl2
V. G. Mata, A. E. Rodrigues, J. Chromatography, 2001
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 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".
Modelling and Simulation in Chemical Engineering: Tools for Process Innovation
Alírio E. Rodrigues | LSRE | DEQ | FEUP
ESCAPE-14 Lisbon, Portugal 17 | MAY | 2004