PSE V80i3 Seminar JAReyesLabarta CAPD CMU2012

Juan A. Reyes-Labarta (ja.reyes@ua.
es)
Some Examples of Modeling in Chemical Engineering:
Thermal treatment of polymers, Phase equilibrium
calculations and Process design
PSE Seminar
Chemical Engineering Department
Center for Advanced Process Design-making (CAPD)
Carnegie
Mellon
University
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October,
2012.
Pittsburgh.
October, 2012. Pittsburgh (USA)
Outline
Some Examples of Modeling in Chemical Engineering:

Thermal treatment of polymers, Phase equilibrium
calculations and Process design
Analysis
Analysis and
and simulation
simulation (kinetic
(kinetic modeling)
modeling) of
of thermal
thermal treatments
treatments and
and
thermal
degradations
of
polymer
mixtures
thermal degradations of polymer mixtures
Problems
Problems and
and limitations
limitations of
of the
the phase
phase equilibrium
equilibrium calculations
calculations (complex
(complex
condensed
systems:
LV,
LL,
LS,
LLS,
LLSh)
condensed systems: LV, LL, LS, LLS, LLSh)
Simulation-optimization
Simulation-optimizationapproaches
approachesfor
forprocess
processdesign
design
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Analysis
Analysis and
and simulation
simulation of
of thermal
thermal treatments
treatments and
and thermal
thermal degradations
degradations
of
polymer
mixtures
of polymer mixtures
(kinetic modeling)
9 Thermal treatment of foamed and crosslinked polymer mixtures (studied

by DSC: differential scanning calorimeter)
9 Foaming process (to produce low-density polymeric materials: such as soles of
sport shoes, toys, nautical buoys, gymnasium floors, hygienic stable floors, etc. =>
reducing the weight of the final product obtained)
9 Crosslinking process (formation of chemical bonds between adjacent molecular

chains, to form a three-dimensional network, that improve the mechanical properties of the
final product, reducing also the possible migration of some components)
9 Thermal degradation (studied by TGA: Themogravimetric analysis)

9 Pyrolysis (catalytic or non-catalytic; inert atmosphere: e.g. nitrogen)
9 Combustion (presence of oxygen)
Analysis and simulation of thermal treatments

and thermal degradations of polymer mixtures
(kinetic modeling)
what process do we want to reproduce?
[CH2 CH2 ]n
9 Thermal treatment (studied by DSC):

Evolution of the heat exchanged along the process
PES(Polyethylene)
D
C P E p u ro
7
Asymmetric
(n<1)
dQ/dT (J/gK)
6
5
Variation of heat
capacities with
temperature
4
3
dQ / dT e x p.
dQ / dT c a l .
dQ/dT
dQ
/ dT cwithout
a l . s i n Cp
ccontribution
o n tr i bu c i n de C p
2
1
0
50
100
150
T e m p e ra tu(C)
ra ( C )
Temperature
200
Marcilla et al. Polymer (2001) 42(12), 5343-5350. http://dx.doi.org/10.1016/S0032-3861(00)00925-3


(kinetic modeling: multiple peaks and processes)

EVA (ethylene vinyl acetate copolymer)
[CH 2 CH 2 ]n
CH 2
CH 3
C = O
CH m
TMAX = 49 C
2.5
TMAX = 72 C
Marcilla et al. Polymer

(2004) 45(14), 49774985.
http://dx.doi.org/10.1016
/j.polymer.2004.05.016
dQ(dT (J/gK)
1.5
TMAX = 113C
1
0.5
25
50
75
100
125
150
175
200
225
250
Temperature (C)


ADC
D S C(azodicarbonamide:
A g e n te E s p ufoaming
m a n teagent)
p u ro
20
dQ/dT (J/gK)
10
0
-1 0
125
150
175
200
225
250
-2 0
d Q /d T e x p
-3 0
d Q /d T c a l
275
-4 0
-5 0
Reyes-Labarta and Marcilla. Journal

http://hdl.handle.net/10045/24682
Temperature
(C)
T e m p e ra tu
ra ( C )
of
Applied
Polymer
Science
(2008)
107(1),
339-346.
6

(kinetic modeling: multiple peaks and industrial processing)
9 Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE

mixtures (components: ADC, CA, EVA, PE)
EVA (ethylene vinyl acetate)
TMAX = 49 C
General scheme of reactions in DSC experiments.
k T, EVA
k M,EVA
EVA
EVA (T)
EVA (M)
k M, PE
PE
PE (M)
TMAX = 72 C
1.5
TMAX = 113C
1
0.5
25
50
75
100
125
150
175
200
225
250
Temperature (C)
D S C P E p u ro
7
6
D S C A g e n t e E s p u m a n t e p u ro
dQ / dT e x p.
5
4
3
dQ / dT c a l .
20
dQ / dT c a l . s i n
c o n tr i bu c i n de C p
10
dQ/dT (J/gK)
dQ/dT (J/gK)
dQ(dT (J/gK)
2.5
2
1
0
50
100
150
T e m p e ra t u ra ( C )
200
315
330
345
360
375
390
405
dQ/dT (J/gK)
175
200
225
250
275
d Q /d T e x p
d Q /d T c a l
T e m p e ra t u ra ( C )
(r.1)
(r.2)
(r.3)
(r.4)
(r.5)
(r.6)
420
435
450
465
480
495
510
525
-2
-4
CA (TBPPB)
-6
150
-3 0
-5 0
0
300
125
-2 0
-4 0
ADC thermal decomposition:

2 H4N4C2O2 H6N4C2O2 + 2 HNCO + N2
2 H4N4C2O2 H3N3C2O2 + 2 HNCO + NH3 + N2
H4N4C2O2 + 2 HNCO H4N4C2O2(HNCO)2*
H4N4C2O2(HNCO)2* H6N4C2O2 + N2 +2 CO
H3N3C2O2 Gr.5
H6N4C2O2 Gr.6
k D ,CA
CA
s D ,CA R D ,CA + (1 s D ,CA ) G D ,CA
0
-1 0
540
Auto-accelerating
effect
-8
-10

-12
-14
Temperature (K)


mixtures (components: ADC, CA, EVA, PE)
DSC
dQ DSC
dQ DSC
dQ DSC
dQ CA
dQ DSC
EVA
ADC
m
PE
= w S C PS +
EVA , m +
PE , m +
CA , m +
ADC , m + (1 w S ) C PM
dT
dT
dT
dT
dT
C P = (a T 2 + b T + c
n-order kinetics and

Arrhenius type behaviour
H j dw j
dQ j
dw
k
Ea j 1
1
= H j j =
= H j ref , j w nj exp

dT
dT
H dt
H
R T Tref
i
DSC
dQ DSC
dQ m
m
O.F. =

m =1 i = 1
dT
dT
calc .
exp .
Reyes-Labarta and Marcilla. I&ECR (2011) 50(13), 7964-7976.

http://dx.doi.org/10.1021/ie200276v
O.F.
RSD(%) =
(N P ) 100
D exp . av .
Reyes-Labarta et al. Journal of Applied

Polymer
Science
(2006).
Reyes-Labarta et al. Polymer

(2006)
47(24)
8194-8202.
http://dx.doi.org/10.1016/j.polymer.
8
2006.09.054
Reyes-Labarta and Marcilla. Journal of Applied Polymer Science
(2008) 110(5), 3217-3224. http://hdl.handle.net/10045/13312


mixtures
DSC first run (variation of ADC content)
EVA
EP(10)C(1.5)A(1)Z(1.5)
EP(10)C(1.5)A(2)Z(1.5)
EP(10)C(1.5)A(4)Z(1.5)
PE
2
Vinyl acetate
domains
dQ/dT (J/gK)
pure PE
1.5
3
p3
2
Ethylene
domains
0.5
ADC
p1+p2
dQ/dT (J/gK) [pure PE]
2.5
0
300
325
350
375
Auto-accelerating
effect
400
425
450
Temperature (K)
475
500
525
550
DSC results (1st runs) for the mixtures studied with various ADC contents:1, 2 and 4 phr.

(kinetic modeling: multiple peaks and industrial processing)

DSC (first run)
mixtures
Vinyl acetate domains
2.25
1.75
EP(10)C(3)A(2)Z(1.5) cal.
EP(10)C(3)A(2)Z(1.5) exp.
Contribution EVA(M)
Contribution EVA(T)
Contribution PE(M)
Contribution CpS
Contribution CpM
ADC decomposition
CA decomposition
EVA(M)
EVA(T)
Reyes-Labarta
and
Marcilla.
I&ECR (2012)
51(28), 951589530.
http://dx.doi.org
/10.1021/ie300
6935
dQ/dT (J/gK)
Ethylene domains
1.25
0.75
CpM
CpS
PE(M)
0.25
-0.25
300
325
350
375
400
425
450
ADC
475
500
525
550
CA
-0.75
Temperature (K)
Experimental and calculated DSC curves (first run)

with the different contribution of each component for the mixture the mixture EP(10)C(3)A(2)Z(1.5)
10

9 Thermal degradation (studied by TGA): Crosslinked and foamed EVA-PE
mixtures
1
PE
0.9
CA
EVA
0.8
ADC
Weight fraction
Evolution
of the
weight
lost
along the
process
0.7
0.6
Two decomposition
reactions
One reaction
0.5
0.4
0.3
0.2
Multiple decomposition
reactions
0.1
0
300
350
400
450
500
550
600
650
700
750
800
Temperature (K)
Experimental TGA curves for the pure components: CA (TBPPB), ADC (azodicarbonamide), EVA and PE
11

9 Thermal degradation (studied by TGA): Crosslinked and foamed EVAPE mixtures
k DP1
EVA
s DP1 EVA * + (1 s DP1 ) G DP1
k DP2
EVA * + PE
s DP2 R DP2 + (1 s DP2 ) G DP2
ADC thermal decomposition:
2 H4N4C2O2 H6N4C2O2 + 2 HNCO + N2
2 H4N4C2O2 H3N3C2O2 + 2 HNCO + NH3 + N2
H4N4C2O2 + 2 HNCO H4N4C2O2(HNCO)2*
H4N4C2O2(HNCO)2* H6N4C2O2 + N2 +2 CO
H3N3C2O2 Gr.5
H6N4C2O2 Gr.6
(r.1)
(r.2)
(r.3)
(r.4)
(r.5)
(r.6)
k D ,CA
CA
s D ,CA R D ,CA + (1 s D ,CA ) G D ,CA
12


TGA
TGA
TGA
dw CA
dw TGA
dw mTGA dw EVA
dw PE
=
EVA , m +
PE , m +
CA , m + ADC* ADC, m
dt
dt
dt
dt
dt
TGA
dw EVA
dw
dw
dw
dw
= EVA + EVA + EVA + R =

dt
dt DP1 dt DP1 dt DP 2 dt DP 2
*
ED
= k DP1 w nEVA (1 s DP1 ) k DP 2 w nEVA* (1 s DP 2 )

DP 1
TGA
dw PE
dw PE dw R
=
+
dt
dt
dt
DP 2
TGA
dw R
dw
dw CA
= CA +
dt
dt
dt
D , CA
n-order kinetics
dw
= (1 s DP 2 ) PE = (1 s DP 2 ) k DP 2 w nPE
dt
and Arrhenius
type behaviour
DP 2
Ea
dw
n
= (1 s D,CA ) CA = (1 s D,CA ) k ref , D ,CA w CA
exp
dt
R
D , CA
dw TGA
dw ADC dw R
ADC
=
+
dt
dt
dt
*
DP 2
D , ADC*
) dwdt
= 1 s D , ADC
*
D , CA
1 1

T Tr
= (1 s D, ADC* ) k D , ADC* w ADC*
D , ADC *
n D , ADC*
13

and degradations of polymer mixtures
(kinetic modelling)

1
0.9
EVA
0.8
EP(10)C(1.5)A(1)Z(1.5)
Weight fraction
0.7
EP(10)C(1.5)A(2)Z(1.5)
0.6
0.995
EP(10)C(1.5)A(4)Z(1.5)
0.99
0.5
0.985
0.98
0.4
0.975
0.97
0.3
0.965
0.96
0.2
0.955
0.95
300
350
400
450
500
550
600
650
0.1
0
300
350
400
450
500
550
600
650
700
750
800
Temperature (K)
Experimental TGA curves for the mixtures studied with various ADC contents: 1, 2 and 4 phr
14

(kinetic modeling: multiple processes)
9 Thermal degradation (studied by TGA):

TG PYROLYSIS
1,2
Reyes et al. JAAP (2001) 58-59, 747-763.

http://dx.doi.org/10.1016/S0165-2370(00)00123-6
Pyrolysis and Combustion

of polycoated cartons
(tetra bricks) recycling
TG Exp. 5 K/min
0,8
TG COMBUSTION
TG cal. 5K/min
1,2
w/wo
TG Exp. 10K/min
TG Cal. 10 K/min
0,6
TG Exp. 25 K/min
1
TG Cal. 25 K/min
0,4
TG Exp. 5 K/min
0,8
TG cal. 5K/min
TG Exp. 10K/min
w/wo
0,2
TG Cal. 10 K/min
0,6
TG Exp. 25 K/min
0
200
TG Cal. 25 K/min
250
300
350
400
450
500
550
600
650
0,4
Temperature (C)
Chemicals and new fuels from biomass pyrolysis!!

Conesa et al. JAAP (2004) 71, 343-352.
http://dx.doi.org/10.1016/S0165-2370(03)00093-7
0,2
0
200
250
300
350
400
450
500
550
600
650
Temperature (C)
15

9 Thermal degradation (studied by TGA): catalytic pyrolysis of EVA and

PP with MCM41, ZSM5, E-cat
k1
EVA
s EVA* + (1 s) G1
Marcilla
et
al.
JAAP
(2003)
http://dx.doi.org/10.1016/S0165-2370(03)00036-6
k2
EVA*
G2
Marcilla et al. Trends in Polymer Science (2003)

http://dx.doi.org/10.1002/chim.200601239
k4
v
EVA* + c C
(1 + c) EVA*C
G3 + c C
k
dw dEVA dEVA * dC dEVA * C

dG dG 2 dG 3
=
+
+
+
= 1
dt
dt
dt
dt
dt
dt
dt
dt
dEVA *
dEVA
n
= k 1EVA
= sk 1EVA n k 2 EVA * k v EVA * C n
dt
dt
dC
dEVA * C
*
n
* n
= ck v EVA C + ck 4 EVA C
= (1 + c )k v EVA * C n (1 + c )k 4 EVA * C n
dt
dt
initial amount
E 1 1
k 3 Co
k i = k o , i exp( E i / RT ) = k o ref , i exp i

of catalyst
k
=
R
T
T
v
ref
n3
n2
n3
n3
K F + Co
constant
16

9 Thermal degradation (studied by TGA): catalytic pyrolysis of EVA with

MCM41
Different
heating
rates
Sample 1
100
Different
amount
of catalyst
We ight loss (% )
80
40 K/min-9.33% M CM -41, exp .
40 K/min-9.33% M CM -41, cal.
60
10 K/min-9.10% M CM -41, exp .

10 K/min-9.10% M CM -41, cal.
40
40 K/min-No M CM -41 exp .

40 K/min-No M CM -41 cal.
20
10 K/min-No M CM -41 exp .

10 K/min-No M CM -41 cal.
0
500
550
600
650
700
750
800
850
Te mpe rature (K)

Marcilla
et
al.
Polymer
(2001)
http://dx.doi.org/10.1016//S0032-386(01)00277-4
Marcilla et al. Polymer Deg. and Stability (2003)

http://dx.doi.org/10.1016//S0141-3910(02)00403-2
TG curves at two heating rates and for the thermal and catalytic processes
17
Calculation
Calculationof
ofphase
phaseequilibrium
equilibrium(complex
(complexsystems:
systems:LV,
LV,LL,
LL,LS,
LS,LLS,
LLS,LLSh)
LLSh)
9 Typical problems in complex LL and LLS equilibrium calculations
9 Topology of the Gibbs energy of mixing function
9 New strategies for coherent and simultaneous correlation
9 Limitations of the actual models (e.g. NRTL)

9 GAP where solutions for homogeneous binary behavior are not found
9 LVE inconsistencies
9 Empirical equations
9 Multicomponent LLE and non-ideal LVE
9 Applications: Optimal design of separation processes: distillation column and LL
extraction sequences, calculation of distillation boundaries
18
Calculation of complex LL and LLS phase equilibrium
1) Possibility of different false solutions
E
M
C
G
Topology of the Gibbs Energy

Function (binary LLE)
(minor common tangent plane criterion )
M
A
M
GM
RT
TYPICAL
TYPICALPROBLEMS
PROBLEMSLLE!!
LLE!!
2) Uncertainty in the final solution
F
H
GM
RT
xI i
xIIi
xIi
xi
xIIi
Liquid phases in equilibrium
Global Mixture
19

Topology of the Gibbs Energy Surface (ternary LLSE)
Tie
Lines
Water (B)
Organic
Solvent
(A)
Solid
Inog.
Salt
Tangent
Planes
Solid
Solid
20

Water (B)
Organic
Solvent
(A)
Inog.
Salt
Solid
21

coherent and robust equilibrium calculations
1L
2L
1L+1S
2L+1S
2 common points
Tie line
Water (B)
Tangent planes to
the GM surface
Tie line
Organic
Solvent
(A)
Tie
Triangle
Inog.
Salt
3 common points
Only 1 tangent
point each plane
Solid
Solid
Solid
Solid
Solid
22
NEW
NEWSTRATEGIES
STRATEGIESto
toavoid
avoidtypical
typicalconvergence
convergenceproblems
problems
Limit the equilibrium composition space for the LLE root determination
a) Using the second derivative of the GM function
Restricted regions for

equilibrium compositions
searching
gM
Advantages:
9 Less time consuming
9 Trivial solution is avoided
g M
x1
g
x12
2
Marcilla et al. Fluid Phase Equilibria (2010)

http://dx.doi.org/10.1016/j.fluid.2009.12.026
II
x1
0
-
xI1
x1B
x1
Minimum common
tangent
23

NEW STRATEGIES
b) Using an unambiguous definition of the plait point (pp) of the solubility curve
in ternary systems
Determinant of the
Hessian matrix of
the GM function
(=0)
L
pp
LL
Marcilla et al. IEC&R 51(13), 50985102 (2012).

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. http://dx.doi.org/10.1021/ie202793r 24
Correlation of complex LL and LLS phase equilibria

NEW STRATEGIES
c1) Using a geometrical approach very good approximation to the ELL solution
(sequential series of minor cutting planes)
PREVIOUS
TIE -LINE
1. Starting with the binary LLE, two

separated
zones,
where
the
conjugated compositions must be
located, are found by intersection
between an adequate plane and the
GM surface.
MAXIMUM DISTANCE
PLANE -SURFACE
ESTIMATED
TIE -LINE
x2
x3
Plane generation points
Maximum distance points
2. The maximum distance point to

the intersection plane is located in
each one of these zones.
3. The conjugated points obtained
are used to generate a new plane
and they are also a very good
approximation to the tie-line.
25

C
NEW STRATEGIES
tie-triang le
Limited composition space for the LLLE root determination

LL
a
L
LL
LLL
c
LL
c2) Using a geometrical approach very good approximation to the LLLE solution
Marcilla et al. Fluid Phase Equilibria 281, 87-95 (2009). http://dx.doi.org/10.1016/j.fluid.2009.04.005
(sequential series of
minor cutting planes)
e.g. 1-nonanol + nitromethane + water (23 C)

1-hexanol + nitromethane + water (21 C)
26

NEW STRATEGIES
Empirical constraints for NRTL binary parameters
Border line between L and LL regions for the NRTL model
A ij = f(A ji ) = 4.4656410 8 A 3ji + 2.9574510 4 A 2ji + 1.20662 A ji + 766.908
3000
A ij < f(A ji )
Homogeneous (L)
LL
2000
A ij > f(A ji )
Heterogeneous (LL)
1000
Aij
Type island systems:
A12+ A21<0 (dissimilar binary pair)

A13+ A31>0
A23+ A32>0
-1000
MISCIBLE (1L)
PARCIALLY MISCIBLE
-2000
-2500
-1500
-500
500
1500
2500
3500
Aji
27
Correlation of complex LL and LLS phase equilibria

NEW STRATEGIES
Different objective functions

a) Minimum of the overall Gibbs Energy of mixing
Calculation of the Minimum of the overall
Gibbs Energy of mixing, along a concrete
line* for each experimental point.
M
c
S
L
G overall
G S G M liquid
i
=
+
= s
+ (1 s ) xL
i
RT
RT
RT
RT
RT
i =1
1L+1S
-0,5
0
0,05
0,1
0,15
0,2
-0,6
Goverall
-0,55
-0,65
-0,7
-0,75
-0,8
Reyes et al. IEC&R 40,902-907

http://dx.doi.org/10.1021/ie000435v
(2001).
*Line defined by a constant

ratio xOrganicSolvent/xwater
28

Olaya et al. Chem.Eng.Education 41(3), 218-224
(2007). http://hdl.handle.net/10045/14277
NEW STRATEGIES
Different objective functions
2
3
a) Isoactivity criterium O.F .(a) = (aiI aiII ) = 0
Olaya et al. Chem.Eng.Education 44(3), 236-244

i =1
b) Minimum of the overall Gibbs Energy of mixing
M
c
S
L
G overall
G S G M liquid
i
=
+
= s
+ (1 s ) xL
i
RT
RT
RT
RT
RT
i =1
-0,5
0
0,05
0,1
0,15
-0,55
-0,6
Goverall
c) Isoactivity + Minor common tangent condition
-0,65
-0,7
d) A modification of the initial vector method
-0,75
-0,8
Objective function
8.0E-05
7.0E-05
-12
O.F.(a)<10^-12
O.F. (a) < 10
O.F.=O.F.(a)+O.F.(t)
6.0E-05
Suggested method O.F.(a)
5.0E-05
a, b
liquid phases of the

binary 1-3
I, II
liquid phases of
a potential tie line
4.0E-05
3.0E-05
2.0E-05
1.0E-05
I
0.0E+00
3.13
3.14
3.15
3.16
3.17
3.18
3.19
a-angle
II
29
TL

NEW STRATEGIE RESULTS:
SIMULTANEOUS CORRELATION (including all equilibrium regions) OF LLS SYSTEMS
(NRTL and E-NRTL)
1
Experimental Data
0,9
Calculated by NRTL method
0,8
Calculated by MNRTL method
0,6
0,5
0,3
0,6
x NaCl
Calculated by NRTL method
0,7
0,4
Calculated by MNRTL method
0,7
Experimental
0,8
x NaCl
Water(1) +
Ethanol (2) +
NaCl (3) at 25C
0,9
0,2
0,1
0,5
0,4
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
x Ethanol
0,3
0,2
0,1
0
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
x Acetone
Water (1) + Acetone (2) + NaCl (3) at 25C
Water(1) +
1-Buranol (2) +
LiCl (3) at 25C
Olaya et al. IEC&R 46, 7030-7037 (2007).

http://dx.doi.org/10.1021/ie0705610
Marcilla et al. IEC&R 47, 2100-2108 (2008).
http://dx.doi.org/10.1021/ie071290w
30
0,2

CORRELATION OF (uncorrelated) COMPLEX LL SYSTEMS (NRTL)
TYPE I
Reyes-Labarta et al. Fluid Phase Equilibria 278, 9-14 (2009). http://hdl.handle.net/10045/24683

31

CORRELATION OF (uncorrelated) COMPLEX LL SYSTEMS (NRTL)
TYPE II
Dimethyl sulfoxide
2
0,0
0,0
0,1
0,1
TYPE 0
T=20C
1,0
0,9
0,2
0,2
Olaya et al. Fluid

Phase
Equilibria
265,
184-191
(2008).
http://hdl.handle.
net/10045/24681
TYPE III
0,8
0,3
0, 3
0,7
0,4
0,4
0,6
0,6
0,7
0,7
Marcilla et al. Fluid

Phase Equilibria 281,
87-95
(2009)
.
http://hdl.handle.ne
t/10045/13315
0,6
0,5
0,5
0,5
experimental (
calculated (
0,4
0,3
0,8
0,8
0,2
0,9
0,9
0,1
1,0
1,0
0,0
water
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Tetrahydrofuran
32

CORRECTION OF SOME (NRTL) INCONSISTENCIES IN LL (type I-II) SYSTEMS
using the NRTL

binary parameters
published in the
DECHEMA
Chemistry Data
Series
Inconsistent
Reyes-Labarta et al.
Fluid Phase Equilibria
278,
9-14
(2009).
http://hdl.handle.net
/10045/24683
Consistent
33
LIMITATIONS
LIMITATIONSOF
OFTHE
THEACTUAL
ACTUALMODELS
MODELS
Illustrating example of a clear limitation for NRTL (constant alpha)
gM
min = 0. 40
-0.5
0.2
0.4
-1.5
gM
0.6
0.8
gap
-2.5
-3.5
-4.5
-5.5
x2
gM
min = 0 . 45
-0.5
0.2
0.4
0.6
0.8
gM
-1.5
-2.5
-3.5
(with ij =0.2)
-4.5
-5.5
x2
If we realize a systematic study on the GM function for a totally miscible binary system,
there exist a GAP where solutions for homogeneous binary behavior are not found.
34
Phase Equilibrium calculations. Limitations of the actual models

Illustrating example of a clear limitation for NRTL (constant alpha )
A) LLE: Methanol(1) + difenilamine(2) + cyclohexane(3) at 298K
interpolated experimental data
interpolated among the calculated compositions
calculated compositions
0.050
experimental data
0.045
0.040
0.035
x2
0.030
0.025
0.020
0.015
0.010
0.005
0.000
0.0
0.2
0.4
0.6
0.8
1.0
A12=873.57
=0.2
A21=-1245.0
=4.08
x3
Data and parameters from Dechema. Sorensen and Artl, W.

Chemistry Data Series; Vol. V/2, DECHEMA, 1980. Page 129.
A13=578.07
A31=578.07
opposite slopes!
A23=-987.32
A32=-856.11
35
Phase Equilibrium calculations. Limitations of the actual models

exp
T(x,y)

B) LVE: water + 1,2-propanediol at 25 mmHg
(DECHEMA,Vol 1,Part 1a,p.256)
Selected VLE
data point
Calculated
VLE data point
120
100
80
All data (DECHEMA)
A12 = -53.57 K
A12 = -136.05
=3.0
=2.8
A21 = 293.90 K
1 data
60
Vcal
Lexp
Vexp
40
A21 = 402.92
20
0
0
GM,V
=
RT
y ln p (T) + y ln y
0.2
d(GM,L / RT )
dx1
GM,L / RT
o
i
0.6
0.8
Lexp
= 2.47
x exp
x exp
0.4
x,y
= 0.65
it is impossible to obtain a good

correlation and also to correlate
only one LVE point
GM liq
GM
gap
There is no
solution
(NRTL)
Vcal
Vexp
GMliq
DECHEMA
GM vapor
36
Phase Equilibrium calculations. More limitations of the actual models

Just one set of these data pass the
C) LVE: water + 1-propanol at 760 mmHg
thermodynamic test of consistency,
(DECHEMA,Vol 1,Part 1a,p.286292)
however, the corresponding NRTL
parameters predict an incoherent
7dataseriesat 760mmHg,with different
behavior
NRTLconstant:
A12
(cal/mol)
A21
(cal/mol)
-13,0045
1872,0758
0,2803
619,3422
2708,5773
0,6185
294,7832
1893,5152
0,4276
152,5084
1866,3369
0,3747
412,0253
1735,4304
0,4465
444,3339
1997,5504
0,4850
152,5084
1866,3369
0,3747
Type
3+type5
37
PITFALLS OF THE TERMODINAMIC CONSYSTENCY TESTS

D) LVE: SOME CONSISTENCY TEST USE THERMODYNAMIC MODELS AS NRTL TO
VALIDATE THE VLE EXPERIMENTAL DATA, e.g. Frenkel-NIST point-to-point
test (van Ness)
BUT. WHAT HAPPENDS IF WE CANNOT FIND A GOOD CORRELATION?

Metilvinilcetone (1) + water (2) at 743 mmHg
(DECHEMA Vol . I-1, p. 355).
Acetone (1) + water (2) at 2570 mmHg

(DECHEMA, Vol. I-1a Sup. 1, p. 197)
ARE THE DATA INCONSISTENT OR IS THE MODEL

UNCAPABLE OF REPRESENTING THE
EXPERMIENTAL BEHAVIOUR?
38
Phase Equilibrium calculations

New factors
Effective molecular weights
But
ButWhat
Whatcan
canwe
wedo
doininthe
themeanwhile?
meanwhile?
A) Possible modification for NRTL model:
GE
= Fi x i
RT
i
ji
ji
xj
G x
li
-3.000
-0.5
-3.200
0
0.2
0.4
0.6
0.8
-3.5
-4
-1
The
Theinitial
initialGAP
GAPisiscompleted!
completed!
-2.98
-0.25
-1.5
-0.22
-2
gM
-0.35
-2.5
-0.38
Experimental
Experimentaldata
data
correlation
is
correlation is
considerably
considerablyimproved
improved
for
several
systems,
for several systems,even
even
island
islandtypes!
types!
-0.4
-3
-0.500
-3.5
-1
-1.5
-4
-2
-4.5
x1
-2.5
-2.8
Marcilla et al. The Open Thermodynamics

Journal - Special Issue. 5, 48-62 (2011).
Marcilla et al. I&ECR 49(20), 10100-10110 (2010).

39

B.1) EMPIRICAL EQUATIONS (Logarithmic eq.)
LLE FOR QUATERNARY SYSTEMS (TYPE 1)
Organic phase
(y)
Aqueous phase
(x)
LVE FOR TERNARY SYSTEMS (including composition and enthalpy data)
and are the composition (components i,j,k) and transformed enthalpy (l) of vapor and liquid phase,
respectively, and C=cte.
40

EMPIRICAL CORRELATIONS
Marcilla et al. IEC&R 38(8), 3083-3095 (1999).
2
2
y 'k

x '4
x '4
x '4
x '4
= ak , p + bk , p + ck , p + d k , p + ek , p + f k , p log x'2 +
log
x'
x'
x'
x'
x'
y'
1
2
2
2
2
p
2
2
x '4
x'4 x'2
+ g k , p + hk , p + ik , p log
x '2
x'2 x'1
y ' (3)
= k1
log
y ' (2)
y ' ( 4)
= k3
log
y ' (3)
y ' (2)
= k 2
log
y ' (1)
y ' (1) + y ' (2) + y ' (3) + y ' (4) = 1 + 4 C
y ' (i ) = y (i ) + C
Four equations with four variables !!

41

B.2) EMPIRICAL EQUATIONS (Polynomial eq.)
LVE FOR NON-IDEAL AND AZEOTROPIC TERNARY SYSTEMS (y vs x)
xi
xi
c
yi =
a i ,j x j
j =1
xq
q =1
a q ,j x j
j =1
yi =
c 1
j i
j i
j i
x i + a i , j x j + a i ,c 1+ j x i x j + a i , 2 c 2 + j x j x j+1
c
xq
q =1
x q + a q , j x j + a q ,c 1+ j x q x j + a q , 2 c 2 + j x j x j+1
c 1
j i
j q
j q
where xi and yi are the composition of the conjugated liquid and vapour
phases in equilibrium, and the subscripts i,j and q refer to the different
component of the mixture. ai,j represent the correlation parameters of the
equation, which are independent of the composition. Such parameters must
be obtained by correlation of the experimental data.
Marcilla et al. VIII Iberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design
42

LVE FOR NON-IDEAL AND AZEOTROPIC TERNARY SYSTEMS (T vs x)

3
T = T0 + Ti
3
i =1
xi
ai , j x j
T = T0 + Ti
i =1
j =1
xi
c
c 1
j i
j i
j i
xi + ai , j x j + ai ,c 1+ j xi x j + ai ,2c 2 + j x j x j +1
T = Tb ,1 (Tb , 2 Tb ,1 )x1 ( A + B( x1 x2 ) )( x1n1 )( x2n 2 ) + C x1 ln( x1 ) + D x2 ln( x2 )

It is necessary to introduce the mathematical constraints corresponding to
the azeotropic points!!!
2
2T
T
x 2 (x 1,az , x 2 ,az ) x x (x 1,az , x 2 ,az )

1
2
H(x 1,az , x 2 ,az ) = 2 1
T
T
(x1,az , x 2 ,az )
(
)
x
,
x
1, az
2 , az
x 22
x 2 x 1
43
Phase Equilibrium calculations

LVE FOR NON-IDEAL TERNARY SYSTEMS (T vs x)

In this case, it is important to remark that it is necessary to introduce the mathematical
restrictions corresponding to the azeotropic points:
dT
(x az ) = 0
dx 1
Binary azeotropes:
yi,az = xi,az and
Ternary azeotrope (AT):
yi,az = xi,az and depending on the type of ternary azeotrope:
AT with minimum boiling temperature: H(x1,az, x2,az) > 0 and
2T
(x1,az , x 2 ,az ) > 0
x 12
AT with maximum boiling temperature: H(x1,az, x2,az) > 0 and
2T
(x1,az , x 2 ,az ) < 0
x 12
AT with intermediate boiling temperature: H(x1,az, x2,az) <0

where H(x1,az, x2,az) is the determinant of the Hessian matrix of the temperature function:
2
2T
T
(
)
(x1,az , x 2 ,az )
x
,
x
x 2 1,az 2 ,az
x 1x 2
H(x 1,az , x 2 ,az ) = 2 1
2
T (x 1,az , x 2 ,az ) T (x 1,az , x 2 ,az )
x 2 x 1
x 22
44
Optimal design of separation process

EMPIRICAL EQUATIONS APPLICATIONS
1. EXTENTION OF CLASICAL TRAY BY TRAY METHOD FOR THE DESIGN OF

DESTILLATION COLUMNS from binary to multicomponent systems
Marcilla et al. Latin American Applied Research International Journal 27(1-2), 51-60
GOAL: to
avoid the
optimal
design of
distillation
columns by
repeated
simulations
45

1. EXTENTION OF THE GRAPHICAL METHODS

McCABE-THIELE AND HENGSTEBECK METHOD
MULTICOMPONENT DESTILLATION COLUMNS
FOR
THE
DESIGN
OF
EQUILIBRIUM (y vs x) AND McCABE DIAGRAM (MOLAR)

1
0.9
yeq
diagonal
Eq.pisos
BM-Roperat.
XD,XB
R.Op.1
R.Op.2
R.Op.3
0.8
0.7
1
0.9
0.8
0.7
0.6
0.6
0.5
0.4
0.5
0.3
0.2
0.1
0.4
0
0
0.3
0.2
0.1
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Marcilla et al. Review and

extension of the McCabeThiele
method
covering
multiple feeds, products and
heat transfer stages (2012).
3195
46

2. GRAPHICAL CONCEPTS TO ORIENTATE THE MINIMUM REFLUX RATIO

CALCULATION
Reyes-Labarta et al. IEC&R 39(10),3912-3919 (2000).

GOAL:
to
simplify
the
rigorous
calculation
of
the
minimum
reflux ratio
47

3. OPTIMAL DESIGN OF MULTICOMPONENT LL EXTRACTION COLUMNS

(using tray by tray methods)
Marcilla
et
al.
IEC&R,
38(8),
3083-3095
(1999).
48

4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS using

MINLP Techniques or Generalized Disjunctive Programming (GDP)
Side Solvent Feeds
R0
EL2
EL1
Final Extract
Product
E1
ELn-1
Initial Solvent Feed
ELn=E0
E2
1
R0,ext
n-1
2
R1
Initial
Raffinate
Feed
RLk,byp
Rdef
Final
Raffinate
Product
Bypass
R0,byp
Side
Reyes-Labarta & Grossmann,
Side
Product
AIChE 47(10), 2243-2252 (2001).
Feed
http://dx.doi.org/10.1002/aic.690 RLk Streams
PL Streams
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. q
471011
49

Generalized Disjuntive Programming (GDP)
Multiple Interconnected Extractors

EL11
E11
EL1n1-1
E1o
1
R1o
n1-1
n1
R1n1
Rdef
R2n2
R2o
1
E21
n2-1
n2
E2o
EL21
EL2n2-1
Reyes-Labarta & Grossmann,

Computer Aided Chem.Eng.
(2001).
http://dx.doi.org/10.1016/S157050
7946(01)80076-6

The selection of the stages in the optimal extraction cascade will be performed
using the following stage existence disjunction.
existing stage
Ej
Ej+1
equili
Rj-1
j
brium
Rj
non existing stage
Ej= Ej+1
Rj-1= Rj
For existing stages:

i) Total and individual mass transfer balances.
ii) Nonlinear equilibrium equations.
iii) Relation between total and individual flowrates (bilinear terms).
For non-existing stages the equations considered are simply input-output
relations in which no mass transfer takes place (inlet and outlet flows are
the same for each phases).
51

Z j
x j ,c = x j 1,c ; y j ,c = y j +1,c
E j = E j +1,c ; E j ,c = E j +1,c
Zj
Equilibrium : ( y j ,c , x j ,c ) = 0 R j = R j 1,c ; R j ,c = R j 1,c
Bilinear terms : F j ,c = F j u j ,c RLk , j = 0 ; RLk , j ,c = 0
PLq , j = 0 ; PLq , j ,c = 0
EL j = 0 ; EL j ,c = 0
j NT
c COMP
k K
q Q
F {R, E, PLq,
RLk, EL, Rdef}
u = {x or y}
Zj is a boolean variable which can be true or false depending if the stage j is

selected or not.
To avoid equivalent solutions that are due to the multiplicity of representation
for a given number of trays, the following logic constraints are added:
Z j Z j 1
Solution strategy: an logic-based Outer

Approximation
algorithm
(NLP
j
NINT
subproblems-MILP master problem).
52

COMPLEX EXTRACTOR DESIGN (GDP)

http://newton.cheme.cmu.edu/interfaces/extractor/main.html
53
Introduction: Topology Azeotropic Liquid-Vapour Equilibrium

LV Equilibria (P = cte). Homogeneous Ternary Azeotropic Systems
A
E
E
A
E
E B
B
A
Gmez et al. Ingeniera

Qumica,
379,
253-262
(2001)
54
Introduction: Topology Azeotropic Liquid-Vapour Equilibrium

3
Ternary system with:

1 heterogeneous binary azeotrope
1 LLV region (tie triangles)
1
Last V-Lhet
point
V-Lhet Curve
PP
. .
LLV
Heterogeneous
azeotropic
binary
LL
Solubility
surface
x,y
Heterogeneous
lquids at boiling
temperature
Gmez et al. Ingeniera Qumica, 377, 219-229 (2001)
55

5. DESTILLATION BOUNDARIES CALCULATION

S y s tem M ethanol-A c etone-H ex ane. Dis tillation c urv es
1.2
AB12min
0.8
Acetone (2)
AB23min
0.6
0.4
ATmin
0.2
AB13min
-0.2
-0.2
0.2
0.4
0.6
M ethanol (1)
0.8
1.2
*
56
Topological concept used:

x0
when there exists, the trajectory of a

distillation
boundary
continuously
contains not only the composition of the
liquid phase, but also the composition
of the vapor phase in equilibrium
y0
x1
L-V tie lines

x2
y1
distillation boundary trajectory
y2
x3
y3
x4
57
DISTILLATION BOUNDARIES CALCULATION
Mathematical algorithm:
Trajectory: origin/end, nipt and function (nincs or n )
X2,k (k=1,2,nipt)
Independent variable (e.g. x2)
Stable node
*
*
trajectory to test
x1,kcal=f(x2)
-^
ycal1,k
Singular points
Compositions: x2,k(k=1,2,,nipt)
Initial values for parameters Aj (or cs nodes, x1,k)

yeq
i,k
Unstable
node
*
X1,k(k=1,2,, nincs)
Compositions: xcal1,k(k=1,2,,nipt)
Compositions: yeq1,k(k=1,2,,nipt)
Compositions: ycal1,k(k=1,2,,nipt)
ycal1,k=yceq1,k?
y1,kcal=f(y2)
yes
End
no
New values for parameters Aj or (cs nodes: x1,k k=1,2,, nincs)
58

NUMERICAL EXAMPLES: Ternary Distillation Boundaries (LV)
Dietilether(1)-Ethanol(2)-Water(3) System at 2156.3 mmHg
1,00
0,90
0,90
0,80
0,80
0,70
0,70
0,60
0,60
x2
x2
Benzene(1)-Cyclohexane(2)-Toluene(3) System at 760 mm Hg

1,00
0,50
0,50
0,40
0,40
0,30
0,30
0,20
0,20
0,10
0,10
0,00
0,00
0,10
0,20
0,30
0,40
0,50
x1
0,60
0,70
0,80
0,90
0,00
0,00
1,00
0,10
0,20
0,40
0,50
x1
0,60
0,70
0,80
0,90
1,00
Ethanol(1)-Benzene(2)-Water(3) System at 760 mmHg
1,00
1,00
0,90
0,90
0,80
0,80
0,70
0,70
0,60
0,60
X2
x2
2-Butanol(1)-2-Butanone(2)-Water(3) System at 760 mm Hg
0,30
0,50
0,50
0,40
0,40
0,30
0,30
0,20
0,20
0,10
0,10
0,00
0,00
0,20
0,40
x1
0,60
0,80
1,00
0,00
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
X1
0,90
1,00
59

Methanol(1)-Acetone(2)-Chloroform(3) System at 760 mmHg
Water(1)-Ethanol(2)-Toluene(3) System at 760 mmHg
1,00
0,90
0,90
0,80
0,80
0,70
0,70
0,60
0,60
X2
x2
1,00
0,50
0,50
0,40
0,40
0,30
0,30
0,20
0,20
0,10
0,10
0,00
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
0,00
0,00
1,00
0,20
0,40
x1
0,90
0,90
0,80
0,80
0,70
0,70
0,60
0,60
0,50
0,40
0,30
0,30
0,20
0,20
0,10
0,10
0,20
0,30
0,40
0,50
x1
1,00
0,50
0,40
0,10
0,80
Acetone(1)-Methanol(2)-Cyclohexane(3) System at 760 mmHg
1,00
X2
x2
2-Propanol(1)-Benzene(2)-Water(3) System at 760 mmHg

1,00
0,00
0,00
0,60
X1
0,60
0,70
0,80
0,90
1,00
0,00
0,00
0,20
0,40
0,60
0,80
1,00
X1
Reyes-Labarta et al. I&ECR, 50(12), 7462-7466 (2011). http://dx.doi.org/10.1021/ie101873g

60

Heterogeneous ternary system with:
1 heterogeneous azeotropic binary composition
2 homogeneous azeotropic binary compositions
1 homogeneous azeotropic ternary composition
1
0.9
Reyes-Labarta et al. Computer Aided Chem.Eng.

28(C), 643-648 (2010).
http://dx.doi.org/10.1016/S1570-7946(10)28108-7
Escape20: http://hdl.handle.net/10045/14203
0.8
Isopropanol
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Benzene
61

NUMERICAL EXAMPLES: Quaternary Distillation Boundaries (LV)
Homogeneous quaternary system with:
2 homogeneous azeotropic binary compositions
Acetone (1)
Quaternary Distillation
Boundary (surface)
Quaternary Distillation
Boundary (curve)
BA1,2
Ternary Distillation
Boundary (curve)
Methanol
(2)
i-propanol (3)
BA3,4
Water
(4)
The quaternary distillation boundary curve is formed by the two different distillation
boundary surfaces, that intersect in one curve.
62
Simulation-optimization
Simulation-optimizationapproaches
approachesfor
forprocess
processdesign
design
9 Optimal design of generalized distillation columns
n=i
Reyes-Labarta et al.. Computer Aided Chemical

Engineering.
2012,
30,
1257-1261.
http://dx.doi.org/10.1016/B978-0-444-59520-1.50110-X
9 Optimal design of absorption systems including LCA

Reyes-Labarta et al. Computer Aided Chemical Engineering.
2011, 29, 301-305. http://dx.doi.org/10.1016/B978-0-44453711-9.50061-4
9 Design of Internally Heat-Integrated Distillation Columns (HIDiC)

EV
(low pressure)
Reyes-Labarta
et
al.
AIChE
Meeting
Ln,RS
2012.
https://aiche.confex.com/aiche/2012/webprogram/Paper267732.html
p-H
V1,SS
cond
Comp
QD
Ws
F
Reb
QR
-QIHT
SS
IHE
RS
Ln,RS
(high pressure)
QIHT
63
Optimal design of generalized distillation columns
Generalized
Generalizedscheme
schemeof
ofaadistillation
distillationcolumn
column
n=i
Hysys Flowsheet (tray by tray calculations)
Lk,n(=Lk,NTk)
(Lk+1,0)
Vk,n+1-(VGFk)
(LGFk)
Multiple side streams (feeds,
products or intermediate
heat exchangers)
Lk,n+1
Vk,n+2
k= k (or k+1)
64
Optimal design of generalized distillation columns

Optimal location of all the side streams:
where zopt refers to the phase

composition at the optimal change
point of sector k. L and H are the
indexes for light and heavy key
components, respectively.
(two phases) Side feed stream
Side product stream (liquid or vapor)
Intermediate Heat exchanger
Schematic representations of the internal existing

streams at the zone connecting consecutive sectors in
the case of a generalized feed side stream (GFk).
Marcilla et al. Review and extension of the McCabe-Thiele

method covering multiple feeds, products and heat transfer
stages (2012). http://hdl.handle.net/10045/23195
65
Optimal design of absorption systems including LCA

Distillation
Column
(binary variables)
Water-Ammonia
Water-AmmoniaAbsorption
AbsorptionCycle
Cycle
Novel framework for the

optimal
design
of
sustainable thermodynamic
cycles
Combined the use of A)

rigorous process simulation
tools,
B)
optimization
software and C) LCA (Life
cycle assessment)
The problem is mathematically formulated as a multi-objective mixedinteger non-linear programming (moMINLP) problem (that simultaneously
accounts the minimization of the total annualized cost and the total
environmental performance of the cycle)
min z = { f1(x, u, xD ),..., fn (x, u, xD )}
Solution strategy: an logic-based Outer

Approximation algorithm (MILP master problem
[Gams]-NLP subproblems [Matlab-Aspen])
xD
s.t.
hI (x, u, xD ) = 0
hE (x, u, xD ) = 0
gE (x, u, xD ) 0
66

Water-Ammonia Absorption Cycle: Flowchart of the proposed algorithm
Brunet, R. et al.
Computers
and
Chemical
Engineering, 2012,
46,
205-216.
http://hdl.handle.net/
10045/24678
67

Water-Ammonia Absorption Cycle: Objective Functions
TAC = C c + C op = ( C D + C HXS + C p )cr f + ( C q Q k =D + C e Wk =P )t op
Environmental damaged = df bd LCI b

b
Environmental
Impact category
Unit
Steam [kg]
Electricity [kWh]
Steel [m2]
Carcinogencis
Points/Unit
1.1810-4
4.3610-4
7.8310-1
Climate change
Points/Unit
1.6010-3
3.6110-6
1.70
Ionising radiation
Points/Unit
1.1310-3
8.2410-4
3.3010-2
Ozone depletion
Points/Unit
2.1010-6
1.2110-4
1.0010-3
Respiratory effects
Points/Unit
7.8710-7
1.3510-6
10.2
Acidification
Points/Unit
1.2110-4
2.8110-4
1.24
1.6710-4
2.40
Ecotoxicity
Points/Unit
2.8010-3
Land occupation
Points/Unit
8.5810-5
4.6810-4
3.1110-1
Fossil fuels
Points/Unit
1.2510-2
1.2010-3
8.64
10
Mineral extraction
Points/Unit
8.8210-6
5.7010-6
9.1110-1
68

Water-Ammonia Absorption Cycle: e.g. Contribution of each component
Environmental Impact category

69
Design of Internally Heat-Integrated Distillation Columns (HIDiC)

Conventional distillation column
QD
LD+D
n=1
LD
Distillate
Possible
Heat
Integration!!
...
Feed
...
n=N
Residue
(bottom)
QQR
B
70
Inter-Condenser and inter-reboiler benefits (McCabe-Thiele Method)

L 1, 0+ D
QD
L 1, 0
yQE
Q E1
s1
D,xD
s2
yF
QE
xopt,F
2
F2
s3
3
QB
B,xB
xB
xF
zF
yQE
xD
71
Inter-Condenser and inter-reboiler benefits (McCabe-Thiele Method)

L 1, 0+ D
QD
D
D,xD
L 1, 0
s1
yF
xopt,F
s2
F1
F
2
s3
QA
A2
B
QB
B,xB
xB
xQA xF
zF
xD
72
General
Generalrepresentation
representationof
ofan
aninternally
internallyheat-integrated
heat-integrateddistillation
distillationcolumn
column
QD
L 1, 0+ D
D,xD
L 1, 0
(high pressure)
Rectifying sector
(light components)
Q E1
Internal
Heat
Integration
2
F2
3
(low pressure)
Q
4
QB
A3
Stripping sector
(heavy components)
B,xB
73
General
Generalconfiguration
configurationof
ofan
aninternally
internallyheat-integrated
heat-integrateddistillation
distillationcolumn
column
EV
(low pressure)
Ln,RS
p-H
V1,SS
cond
Comp
QD
Ws
F
Reb
Stripping
SS
Sector
Q
QRB
RB
-QIHT
Rectifying
RS Sector
IHE
Ln,RS
(high pressure)
QIHT
PSO algorithm
74
Condenser and reboiler duties, and compressor shaft work vs overall

internal heat transfer (QIHT)
2500
It is possible
to optimize the TAC!!!
QD
QR
WS
2000
But
the
solution
depends strongly
on the cost of the
electricity
and
the
system studied, purity
of the final products,
etc.!!
Q (kW)
1500
1000
500
200
400
600
800
1000 1200
QIHT (kW)
1400
1600
1800
2000
75
Design of sustainable processes
General
Generalconfiguration
configurationof
ofaavapour
vapourrecompression
recompressiondistillation
distillationcolumn
column(VRC)
(VRC)
p-cond
EV
R=L1,0
Qp-cond
D
Qp-H
cond
p-H
F1
Ws
(high pressure)
Comp
QIHT
F2
(low pressure)
Reb
Mainly for systems with small

temperature difference between the top
and bottom products
76
Biography (I. Kinetic modelling)

Reyes-Labarta, J.A.*; Marcilla, A. Thermal Treatment and Degradation of Crosslinked Ethylene Vinyl
Acetate-Polyethylene-Azodicarbonamide-ZnO Foams. Complete Kinetic Modelling and Analysis. Industrial
& Engineering Chemistry Research. 2012, 51(28), 9515-9530 (http://dx.doi.org/10.1021/ie3006935).
Reyes-Labarta, J.A.*; Marcilla, A.; Sempere, J. Kinetic Study of the Thermal Processing and Pyrolysis of
Crosslinked Ethylene Vinyl Acetate-Polyethylene Mixtures. Industrial & Engineering Chemistry Research,
2011, 50(13), 79647976 (http://dx.doi.org/10.1021/ie200276v)
Reyes-Labarta*, J.A.; Marcilla, A. Differential Scanning Calorimetry Analysis of the Thermal Treatment
of Ternary Mixtures of Ethylene Vinyl Acetate, Polyethylene and Azodicarbonamide. Journal of Applied
Polymer Science, 2008, 110(5), 3217-3224 (http://dx.doi.org/10.1002/app.28802). Repositorio
Institucional RUA: http://hdl.handle.net/10045/13312.
Reyes-Labarta, J.A.; Marcilla, A. Kinetic Study of the Decompositions Involved in the Thermal
Degradation
of
Commercial
Azodicarbonamide.
Journal
of
Applied
Polymer
Science
(http://dx.doi.org/10.1002/app.26922).
Repositorio
Institucional
RUA:
http://hdl.handle.net/10045/24682.
Reyes-Labarta, J.A. ; Olaya, M.M.; Marcilla, A. DSC Study of the Transitions Involved in the Thermal
Treatment of Foamable Mixtures of PE and EVA Copolymer with Azodicarbonamide. Journal of Applied
Polymer Science, 2006, 102(3), 2015-2025 (http://dx.doi.org/10.1002/app.23969). Repositorio
Institucional RUA: http://hdl.handle.net/10045/24680.
Reyes-Labarta, J.A. ;Olaya, M.M.;Marcilla, A. DSC and TGA Study of the Transitions Involved in the
Thermal Treatment of Binary Mixtures of PE and EVA Copolymer with a Crosslinking Agent. Polymer,
2006, 47(24), 8194-8202 (http://dx.doi.org/10.1016/j.polymer.2006.09.054)
77

Marcilla, F.J. Sempere y J.A. Reyes-Labarta. Differential Scanning Calorimetry of Mixtures of EVA and
PE.
Kinetic
Modeling.
Polymer,
2004,
45(14),
4977-4985
(http://dx.doi.org/10.1016/j.polymer.2004.05.016)
Conesa, J.A.; Caballero, J.A.; Reyes-Labarta, J.A. Artificial Neural Network for Modelling Thermal
Decompositions.
Journal
of
Analytical
and
Applied
Pyrolysis,
2004,
71,
343-352
(http://dx.doi.org/10.1016/S0165-2370(03)00093-7)
Reyes-Labarta, J. A.; Herrero, M.; Mijangos, C.; Reinecke. H. Wetchemical Surface Modification of
Plasticized PVC. Polymer, 2003, 44, 2263-2269 (http://dx.doi.org/10.1016/S0032-3861(03)00140-X)
Marcilla, A.; Gmez, A.; Reyes-Labarta, J.A.; Giner, A.; Hernndez, F. Kinetic study of polypropylene
pyrolysis using ZSM-5 and an equilibrium fluid catalytic cracking catalyst. Journal of Analytical and
Applied Pyrolysis, 2003, 68-69, 467-480 (http://dx.doi.org/10.1016/S0165-237(03)00036-6)
Marcilla, A., Gmez, A., Garca, A.N., Beltrn, M., Reyes-Labarta, J.A., Menargues, S., Olaya, M.M.,
Hernndez, F., Giner, A., Valds, F. The use of zeolites and other acid solids as catalysts in the pyrolysis
of
polymers
in
N2
and
air.
Trends
in
Polymer
Science,
2003,
8,
1-25
(http://dx.doi.org/10.1002/chin.200601239)
(http://www3.interscience.wiley.com/cgi-bin/fulltext/112194285/HTMLSTART)
Marcilla, A.; Gmez, A.; Reyes-Labarta, J.A.; Giner, A. Catalytic pyrolysis of polypropylene using MCM41.
Kinetic
model.
Polymer
Degradation
and
Stability,
2003,
80,
233-240
(http://dx.doi.org/10.1016/S0141-3910(02)00403-2).
78
Marcilla, A.; Reyes, J. A.; Sempere, F. J. DSC Kinetic Study of the Transitions Involved in the Thermal
Treatment of Polymers. Methodological Considerations. Polymer, 2001, 42(12), 5343-5350
(http://dx.doi.org/10.1016/S0032-3861(00)00925-3)
Marcilla, A.; Gmez, A.; Reyes, J. A. MCM-41 Catalytic Pyrolysis of Ethylene-Vinyl Acetate Copolymers.
Kinetic Model. Polymer, 2001, 49(19), 8103-8111(http://dx.doi.org/10.1016/S0032-3861(01)00277-4)
Reyes, J. A.; Conesa, J. A.; Marcilla, A. Pyrolysis and combustion of polycoated cartons recycling. kinetic
model and ms analysis. Journal of Analytical and Applied Pyrolysis, 2001, 58-59, 747-763
(http://dx.doi.org/10.1016/S0165-2370(00)00123-6)
Sempere, J. Estudio de los Procesos de Reticulado, Espumado y Descomposicin Trmica de
Formulaciones Industriales de Copolmeros de EVA y PE. Anlisis Cintico . Biblioteca Virtual Miguel de
Cervantes (Universidad de Alicante), 2003.
http://www.cervantesvirtual.com/FichaObra.html?Ref=9612
79
Biography (II. Phase equilibria)

-Marcilla, A.; Reyes-Labarta, J.A.; Olaya, M.M.; Serrano M.D. Simultaneous Correlation of LL, LS and
LLS Equilibrium Data for Water + Organic Solvent + Salt Ternary Systems. Hydrated Solid Phase
Formation.
Industrial
&
Engineering
Chemistry
Research,
47,
2100-2108
(2008).
http://dx.doi.org/10.1021/ie071290w
-Olaya, M.M.; Marcilla, A.; Serrano,M.D.; Botella A.; Reyes-Labarta, J.A. Simultaneous Correlation of LL,
LS and LLS Equilibrium Data for Water + Organic Solvent + Salt Ternary Systems. Anhydrous Solid
Phase.
Industrial
&
Engineering
Chemistry
Research,
46,
70307037
(2007).
-Reyes, J.A.; Conesa, J.A.; Marcilla, A.; Olaya, M.M. Solid-Liquid Equilibrium Thermodynamics: checking
stability in multiphase systems using Gibbs Energy Function. Industrial & Engineering Chemistry
Research, 40, 902-907 (2001). http://dx.doi.org/10.1021/ie000435v
-Reyes-Labarta, J.A.; Olaya, M.; Velasco, R.; Serrano M.D.; Marcilla, A. Correlation of the Liquid-Liquid
Equilibrium Data for Specific Ternary Systems with One or Two Partially Miscible Binary Subsystems.
Fluid Phase Equilibria 278, 9-14 (2009). http://hdl.handle.net/10045/24683
-Marcilla, A; Olaya, M.; Serrano M.D.; Velasco, R.; Reyes-Labarta, J.A. Gibbs Energy Based Procedure
for the Correlation of Type 3 Ternary Systems Including a Three-Liquid Phase Region. Fluid Phase
Equilibria 281, 87-95 (2009). http://hdl.handle.net/10045/13315
-Olaya, M.M.; Reyes-Labarta, J.A.; Velasco, R.; Ibarra, I.; Marcilla A. Modelling Liquid-Liquid Equilibria
for
Island
Type
Ternary
Systems.
Fluid
Phase
Equilibria
265,
184-191
(2008).
-Marcilla, A; Olaya, M.; Serrano M.D.; Reyes-Labarta, J.A. Methods for Improving Models for Condensed
Phase
Equilibrium
Calculations.
Fluid
Phase
Equilibria
296(1),
15-24
(2010).
80
Biography (II. Phase Equilibria)
-Reyes, J.A.; Olaya, M.M.; Gmez, A.; Marcilla, A. Calculation of liquid-vapor and liquid-liquid equilibrium
in multicomponent systems using correlations of equilibrium data. V Iberoamerican Conference on Phase
Equilibria and Fluid Properties for Process Design. EQUIFASE 99 Book of Abstracts.
-Olaya, M.M.; Reyes-Labarta, J.A.; Serrano, M.D.; Marcilla, A. Vapor-Liquid Equilibria using the Gibbs
Energy and the Common Tangent Plane Criterion. Chemical Engineering Education 44(3), 236-244 (2010).
-Olaya, M.M.; Ibarra, I.; Reyes-Labarta, J.A.; Serrano, M.D.; Marcilla, A. Computing Liquid-Liquid Phase
Equilibria: An exercise to understand the nature of false solutions and how to avoid them. Chemical
Engineering Education 41 (3), 218-224 (2007). http://hdl.handle.net/10045/14277
-Gmez, A.; Ruiz, F.; Marcilla, A.;Reyes, J.; Menargues, S. Diseo de la separacin de mezclas ternarias
(I). Conceptos grficos del equilibrio entre fases . Ingeniera Qumica, 377, 219-229 (2001).
-Gmez, A.; Ruiz, F.; Marcilla, A.;Reyes, J.; Menargues, S. Diseo de la separacin de mezclas ternarias
(II). Aplicacin de conceptos grficos a la separacin de mezclas azeotrpicas. Ingeniera Qumica, 379,
253-262 (2001).
-Marcilla, A.; Olaya, M.M.; Reyes, J.; Gmez, A. Graphical analysis of the phase equilibria diagram. V
Iberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design. EQUIFASE 99
Book of Proceedings, pag. : 3 10. Vigo (Espaa), 1999 (http://hdl.handle.net/10045/2482).
81
Biography (II. Phase Equilibria)

-Reyes-Labarta, J.A.; Caballero, J.A.; Marcilla, A. Numerical Determination of Distillation Boundaries for
Multicomponent Homogeneous and Heterogeneous Azeotropic Systems. Computer Aided Chem.Eng.
28(C), 643-648 (2010). http://dx.doi.org/10.1016/S1570-7946(10)28108-7
Escape20: http://hdl.handle.net/10045/14203
-Reyes-Labarta, J.A.; Serrano, M.D.; Velasco, R.; Olaya, M.M.; Marcilla, A. Approximate Calculation of
Distillation Boundaries for Ternary Azeotropic Systems. Industrial & Engineering Chemistry Research,
50(12), 7462-7466 (2011). http://dx.doi.org/10.1021/ie101873g
-Marcilla, A.; Serrano, M.D.; J.A. Reyes-Labarta. J.A.; Olaya, M.M. Checking Liquid-Liquid Critical Point
Conditions and their Application in Ternary Systems. Industrial & Engineering Chemistry Research
51(13), 5098-5102 (2012). http://dx.doi.org/10.1021/ie202793r
- Marcilla, A.; Reyes-Labarta, J.A.; Serrano M.D.; Olaya, M.M. GE Models and Algorithms for Condensed
Phase Equilibrium Data Regression in Ternary Systems: Limitations and Proposals. The Open
Thermodynamics Journal - Special Issue. 5, 48-62 (2011). http://hdl.handle.net/10045/19865
-Marcilla, A; Olaya, M.M.; Serrano M.D.; Reyes-Labarta, J.A. Aspects to be considered for the
development of a correlation algorithm for condensed phase equilibrium data for ternary systems.
I&ECR 49(20), 10100-10110 (2010). http://dx.doi.org/10.1021/ie1010383
-Marcilla, A.; Reyes-Labarta J.A.; Velasco, R.; Serrano, M.D.; Olaya, M.M. Explicit Equation to Calculate
the Liquid-Vapour Equilibrium for Ternary Azeotropic and Non Azetropic Systems. VIII Iberoamerican
Conference
on
Phase
Equilibria
and
Fluid
Properties
for
Process
Design
(2009).
82
Biography (III. Unit operations)

-Reyes-Labarta, J.A. Diseo de Columnas de Rectificacin Y Extraccin Multicomponentes. Biblioteca
Virtual Miguel de Cervantes (Universidad de Alicante), 1998.
http://www.cervantesvirtual.com/FichaObra.html?Ref=4845&ext=pdf
-A. Marcilla, A. Gmez, J.A. Reyes, M.M. Olaya.; New Method for Quaternary Systems Liquid-liquid
Extraction Tray to Tray Design. Industrial & Engineering Chemistry Research, 38, 3083-3095 (1999).
-A. Marcilla, A. Gmez, J.A. Reyes; New Methods for Designing Distillation Columns of Multicomponent
Mixtures. Latin American Applied Research and International Journal of Chemical Engineering, 27, 5160 (1997). http://hdl.handle.net/10045/24679
-Reyes, J.A.; Gomez, A.; Marcilla, A. Graphical concepts to orient the minimum reflux ratio calculation on
ternary mixtures distillation. Industrial & Engineering Chemistry Research 39(10),3912-3919 (2000).
-J.A. Reyes-Labarta, I.E. Grossmann; Disjunctive Programming Models for the Optimal Design Of Liquidliquid Multistage Extractors and Separation Sequences. AIChE Journal. 2001, 47 (10), 2243-2252.
http://dx.doi.org/10.1002/aic.690471011
- J.A. Reyes-Labarta y I.E. Grossmann. Optimal Synthesis of Liquid-liquid Multistage Extractors.

Escape-11 (European Symposium of Computer Aided Process Engineering), Capec (Computer Aided
Process Engineering Center). ISBN: 0-444-50709-4 (Dinamarca, 2001). http://dx.doi.org/10.1016/S1570-
7946(01)80076-6
83
Biography (III. Unit operations)

-Reyes-Labarta, J.A.; Caballero, J.A.; Marcilla, A. A Novel Hybrid Simulation-Optimization Approach for
the Optimal Design of Multicomponent Distillation Columns. Computer Aided Chemical Engineering. 2012,
30, 1257-1261. http://dx.doi.org/10.1016/B978-0-444-59520-1.50110-X
-Reyes-Labarta, J.A.; Brunet, R.; Caballero, J.A.; Boer, D.; Jimnez, L. Integrating process simulation
and MINLP methods for the optimal design of absorption cooling systems. Computer Aided Chemical
Engineering. 2011, 29, 301-305. http://dx.doi.org/10.1016/B978-0-444-53711-9.50061-4
-Brunet, R.; Reyes-Labarta, J.A.; Guilln-Goslbez, G.; Jimnez, L.; Boer, D. Combined SimulationOptimization Methodology for the Design of Environmental Conscious Absorption Systems. Computers
and Chemical Engineering, 2012, 46, 205-216 http://hdl.handle.net/10045/24678
-Marcilla et al. Review and extension of the McCabe-Thiele method covering multiple feeds, products
and heat transfer stages (2012). http://hdl.handle.net/10045/23195
-Reyes-Labarta, J.A.; Navarro M.A.; Caballero, J.A. A Hybrid Simulation-Optimization Approach for the
Design of Internally Heat-Integrated Distillation Columns. AIChE 2012 Annual Meeting (Energy
Efficiency by Process Intensification).
https://aiche.confex.com/aiche/2012/webprogram/Paper267732.html
84
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh

web: http://iq.ua.es/~jareyes/
Thanks very much for your attention
Any question?
85

PSE V80i3 Seminar JAReyesLabarta CAPD CMU2012

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Juan A. Reyes-Labarta (ja.reyes@ua.

Some Examples of Modeling in Chemical Engineering:

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

9 Thermal treatment of foamed and crosslinked polymer mixtures (studied

9 Crosslinking process (formation of chemical bonds between adjacent molecular

9 Thermal degradation (studied by TGA: Themogravimetric analysis)

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC):

Marcilla et al. Polymer (2001) 42(12), 5343-5350. http://dx.doi.org/10.1016/S0032-3861(00)00925-3

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC):

Marcilla et al. Polymer

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC):

Reyes-Labarta and Marcilla. Journal

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE

General scheme of reactions in DSC experiments.

ADC thermal decomposition:

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE

n-order kinetics and

Reyes-Labarta and Marcilla. I&ECR (2011) 50(13), 7964-7976.

Reyes-Labarta et al. Journal of Applied

Reyes-Labarta et al. Polymer

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE

dQ/dT (J/gK) [pure PE]

Analysis and simulation of thermal treatments

9 Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE

Experimental and calculated DSC curves (first run)

Analysis and simulation of thermal treatments

Analysis and simulation of thermal treatments

9 Thermal degradation (studied by TGA): Crosslinked and foamed EVAPE mixtures

Analysis and simulation of thermal treatments

9 Thermal degradation (studied by TGA): Crosslinked and foamed EVAPE mixtures

= EVA + EVA + EVA + R =

= k DP1 w nEVA (1 s DP1 ) k DP 2 w nEVA* (1 s DP 2 )

= (1 s D, ADC* ) k D , ADC* w ADC*

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

Analysis and simulation of thermal treatments

9 Thermal degradation (studied by TGA): Crosslinked and foamed EVAPE mixtures

Analysis and simulation of thermal treatments

9 Thermal degradation (studied by TGA):

Reyes et al. JAAP (2001) 58-59, 747-763.

Pyrolysis and Combustion

Chemicals and new fuels from biomass pyrolysis!!

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

Analysis and simulation of thermal treatments

9 Thermal degradation (studied by TGA): catalytic pyrolysis of EVA and

Marcilla et al. Trends in Polymer Science (2003)

dw dEVA dEVA * dC dEVA * C

k i = k o , i exp( E i / RT ) = k o ref , i exp i

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

Analysis and simulation of thermal treatments

9 Thermal degradation (studied by TGA): catalytic pyrolysis of EVA with

10 K/min-9.10% M CM -41, exp .

40 K/min-No M CM -41 exp .

10 K/min-No M CM -41 exp .

Te mpe rature (K)

Marcilla et al. Polymer Deg. and Stability (2003)