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

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


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

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)

9 Thermal treatment (studied by DSC):


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

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)

9 Thermal treatment (studied by DSC):


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

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

(2008)

107(1),

339-346.
6

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(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

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


-12

-14

Temperature (K)

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)

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


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).
http://hdl.handle.net/10045/24680

Reyes-Labarta et al. Polymer


(2006)
47(24)
8194-8202.
http://dx.doi.org/10.1016/j.polymer.
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
8
2006.09.054
Reyes-Labarta and Marcilla. Journal of Applied Polymer Science
(2008) 110(5), 3217-3224. http://hdl.handle.net/10045/13312

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)

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


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

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and industrial processing)

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


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

10

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)
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
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

11

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)

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

12

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple peaks and processes)

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


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*

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

13

Analysis and simulation of thermal treatments


and degradations of polymer mixtures
(kinetic modelling)

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


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

14

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(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)

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

15

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple processes)

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

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

n2

n3

n3

K F + Co

constant

16

Analysis and simulation of thermal treatments


and thermal degradations of polymer mixtures
(kinetic modeling: multiple processes)

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

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

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

19

Calculation of complex LL and LLS phase equilibrium


Topology of the Gibbs Energy Surface (ternary LLSE)
(minor common tangent plane criterion )
Tie
Lines

Water (B)
Organic
Solvent
(A)

Solid

Inog.
Salt

Tangent
Planes

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

Solid
20

Calculation of complex LL and LLS phase equilibrium


Topology of the Gibbs Energy Surface (ternary LLSE)
(minor common tangent plane criterion )
Water (B)
Organic
Solvent
(A)

Inog.
Salt

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

21

Calculation of complex LL and LLS phase equilibrium


Topology of the Gibbs Energy Surface (ternary LLSE)
(minor common tangent plane criterion )
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
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

22

Calculation of complex LL and LLS phase equilibrium

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

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

23

Calculation of complex LL and LLS phase equilibrium


NEW STRATEGIES
Limit the equilibrium composition space for the LLE root determination
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

Limit the equilibrium composition space for the LLE root determination
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.

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

25

Calculation of complex LL and LLS phase equilibrium


C

NEW STRATEGIES

tie-triang le

Limited composition space for the LLLE root determination


(minor common tangent plane criterion )

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)

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

26

Calculation of complex LL and LLS phase equilibrium


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

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

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

28

Calculation of complex LL and LLS phase equilibrium


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


(2010). http://hdl.handle.net/10045/24677

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

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

29

TL

Calculation of complex LL and LLS phase equilibrium


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

30

0,2

Calculation of complex LL and LLS phase equilibrium


NEW STRATEGIE RESULTS:
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


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

31

Calculation of complex LL and LLS phase equilibrium


NEW STRATEGIE RESULTS:
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

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

32

Calculation of complex LL and LLS phase equilibrium


NEW STRATEGIE RESULTS:
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

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

33

Calculation of complex LL and LLS phase equilibrium

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

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

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

35

Phase Equilibrium calculations. Limitations of the actual models


exp

T(x,y)

Illustrating example of a clear limitation for NRTL (constant alpha )


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)

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

Vcal

Vexp
GMliq
DECHEMA

GM vapor
36

Phase Equilibrium calculations. More limitations of the actual models


Illustrating example of a clear limitation for NRTL (constant alpha )
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

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

37

PITFALLS OF THE TERMODINAMIC CONSYSTENCY TESTS


Illustrating example of a clear limitation for NRTL (constant alpha )
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?
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

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).
http://hdl.handle.net/10045/19865

Marcilla et al. I&ECR 49(20), 10100-10110 (2010).


http://dx.doi.org/10.1021/ie1010383

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

39

Calculation of complex LL and LLS phase equilibrium


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

40

Calculation of complex LL and LLS phase equilibrium


EMPIRICAL CORRELATIONS
Marcilla et al. IEC&R 38(8), 3083-3095 (1999).
http://dx.doi.org/10.1021/ie9900723
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 !!


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

41

Calculation of complex LL and LLS phase equilibrium


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
(2009). http://hdl.handle.net/10045/14276
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

42

Calculation of complex LL and LLS phase equilibrium


B.2) EMPIRICAL EQUATIONS (Polynomial eq.)

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

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

43

Phase Equilibrium calculations


B.2) EMPIRICAL EQUATIONS (Polynomial eq.)

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

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

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
(1997). http://hdl.handle.net/10045/24679

GOAL: to
avoid the
optimal
design of
distillation
columns by
repeated
simulations

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

45

Optimal design of separation process


EMPIRICAL EQUATIONS APPLICATIONS

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

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

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).
http://hdl.handle.net/10045/2
3195
46

Optimal design of separation process


EMPIRICAL EQUATIONS APPLICATIONS

2. GRAPHICAL CONCEPTS TO ORIENTATE THE MINIMUM REFLUX RATIO


CALCULATION

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


http://dx.doi.org/10.1021/ie9907021

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

47

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

Optimal design of separation process


EMPIRICAL EQUATIONS APPLICATIONS

3. OPTIMAL DESIGN OF MULTICOMPONENT LL EXTRACTION COLUMNS


(using tray by tray methods)

Marcilla
et
al.
IEC&R,
38(8),
http://dx.doi.org/10.1021/ie9900723
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

3083-3095

(1999).
48

Optimal design of separation process


EMPIRICAL EQUATIONS APPLICATIONS

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

4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS using


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

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

Reyes-Labarta & Grossmann,


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

4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS using


Generalized Disjuntive Programming (GDP)

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

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

4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS using


Generalized Disjuntive Programming (GDP)

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).

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

52

4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS using


Generalized Disjuntive Programming (GDP)

COMPLEX EXTRACTOR DESIGN (GDP)


http://newton.cheme.cmu.edu/interfaces/extractor/main.html

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

53

Introduction: Topology Azeotropic Liquid-Vapour Equilibrium


LV Equilibria (P = cte). Homogeneous Ternary Azeotropic Systems
A

E
E

A
E

E B

B
A

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

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)

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

55

Optimal design of separation process


EMPIRICAL EQUATIONS APPLICATIONS

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

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

56

5. DESTILLATION BOUNDARIES CALCULATION

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

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

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

58

5. DESTILLATION BOUNDARIES CALCULATION


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

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

0,50

0,60

0,70

0,80

X1

0,90

1,00

59

5. DESTILLATION BOUNDARIES CALCULATION


NUMERICAL EXAMPLES: Ternary Distillation Boundaries (LV)
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


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

60

5. DESTILLATION BOUNDARIES CALCULATION


NUMERICAL EXAMPLES: Ternary Distillation Boundaries (LV)
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
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

61

5. DESTILLATION BOUNDARIES CALCULATION


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

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

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

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

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

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

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])

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

xD

s.t.

hI (x, u, xD ) = 0
hE (x, u, xD ) = 0

gE (x, u, xD ) 0
66

Optimal design of absorption systems including LCA


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

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

67

Optimal design of absorption systems including LCA


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

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

68

Optimal design of absorption systems including LCA


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

Environmental Impact category


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

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

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

70

Design of Internally Heat-Integrated Distillation Columns (HIDiC)

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

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

71

Design of Internally Heat-Integrated Distillation Columns (HIDiC)

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

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

zF

xD
72

Design of Internally Heat-Integrated Distillation Columns (HIDiC)

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

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

73

Design of Internally Heat-Integrated Distillation Columns (HIDiC)

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

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

74

Design of Internally Heat-Integrated Distillation Columns (HIDiC)

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

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

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

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

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

77

Biography (I. Kinetic modelling)


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).

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

78

Biography (I. Kinetic modelling)

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
http://hdl.handle.net/10045/10130

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

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).
http://dx.doi.org/10.1021/ie0705610
-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).
http://hdl.handle.net/10045/24681
-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).
http://hdl.handle.net/10045/13314
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

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.
http://hdl.handle.net/10045/2687
-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).
http://hdl.handle.net/10045/24677
-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).

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

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).
http://hdl.handle.net/10045/14276
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.

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
http://hdl.handle.net/10045/10023
-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).
http://dx.doi.org/10.1021/ie9900723
-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).
http://dx.doi.org/10.1021/ie9907021
-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

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

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

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

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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?

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

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