pse v80i3 seminar jareyeslabarta capd cmu2012
TRANSCRIPT
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
PSE Seminar
Chemical Engineering Department
Center for Advanced Process Design-making (CAPD)
Carnegie Mellon University
October, 2012. Pittsburgh (USA)
Juan A. Reyes-Labarta ([email protected])
Some Examples of Modeling in Chemical Engineering:
Thermal treatment of polymers, Phase equilibrium
calculations and Process design
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 2
Problems and limitations of the phase equilibrium calculations (complex
condensed systems: LV, LL, LS, LLS, LLSh)
Problems and limitations of the phase equilibrium calculations (complex
condensed systems: LV, LL, LS, LLS, LLSh)
Analysis and simulation (kinetic modeling) of thermal treatments and
thermal degradations of polymer mixtures
Analysis and simulation (kinetic modeling) of thermal treatments and
thermal degradations of polymer mixtures
Simulation-optimization approaches for process design Simulation-optimization approaches for process design
Some Examples of Modeling in Chemical Engineering:
Thermal treatment of polymers, Phase equilibrium
calculations and Process design
Some Examples of Modeling in Chemical Engineering:
Thermal treatment of polymers, Phase equilibrium
calculations and Process design
Outline
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 3
Analysis and simulation of thermal treatments and thermal degradations
of polymer mixtures
Analysis and simulation of thermal treatments and thermal degradations
of polymer mixtures
Crosslinking process (formation of chemical bonds between adjacent molecularchains, to form a three-dimensional network, that improve the mechanical properties of the
final product, reducing also the possible migration of some components)
Foaming process (to produce low-density polymeric materials: such as soles ofsport shoes, toys, nautical buoys, gymnasium floors, hygienic stable floors, etc. =>
reducing the weight of the final product obtained)
Thermal treatment of foamed and crosslinked polymer mixtures (studied
by DSC: differential scanning calorimeter)
Combustion (presence of oxygen)
Pyrolysis (catalytic or non-catalytic; inert atmosphere: e.g. nitrogen)
Thermal degradation (studied by TGA: Themogravimetric analysis)
(kinetic modeling)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 4
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC):
(kinetic modeling)what process do we want to reproduce?
D S C P E p uro
0
1
2
3
4
5
6
7
5 0 1 0 0 1 5 0 2 0 0T e m p e ra t u ra ( C )
dQ/dT(J/gK
d Q / d T e x p .
d Q / d T c a l .
d Q / d T c a l . s i n
c o n t r i b u c i n d e C p
[ ]n
CHCH22
Temperature (C)
PE (Polyethylene)
dQ/dT without Cp
contribution
Variation of heatcapacities withtemperature
Evolution of the heat exchanged along the process
Asymmetric(n
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 5
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC):[ ]
nCHCH
22
mCHCH
O
OC
CH
=
2
3(kinetic modeling: multiple peaks and processes)
EVA (ethylene vinyl acetate copo lymer)
0
0.5
1
1.5
2
2.5
3
0 25 50 75 100 125 150 175 200 225 250
Temperature (C)
dQ(dT(J/gK)
TMAX= 49 C
TMAX= 72 C
TMAX= 113C
Marcilla et al. Polymer
(2004) 45(14), 4977-
4985.
http://dx.doi.org/10.1016
/j.polymer.2004.05.016
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 6
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC):
D S C A g e n te E s p u m a n te p uro
-5 0
-4 0
-3 0
-2 0
-1 0
0
1 0
2 0
1 2 5 1 5 0 1 7 5 2 0 0 2 2 5 2 5 0 2 7 5
T e m p e ra t u ra ( C )
dQ/dT(J/gK
d Q / d T e x p
d Q / d T c a l
ADC (azodicarbonamide: foaming agent)
Temperature (C)
(kinetic modeling: multiple peaks and processes)
Reyes-Labarta and Marcilla. Journal of Applied Polymer Science (2008) 107(1), 339-346.
http://hdl.handle.net/10045/24682
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 7
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE
mixtures (components: ADC, CA, EVA, PE)
CA,DCA,DCA,DCA,D
CA,D G)s1(Rsk
CA +
(M)PEk
PE
(M)EVAk
(T)EVAk
EVA
PEM,
EVAM,EVAT,
General scheme of reactions in DSC experiments.
ADC thermal decomposition:
2 H4N4C2O2 H6N4C2O2 + 2 HNCO + N2 (r.1)2 H4N4C2O2 H3N3C2O2 + 2 HNCO + NH3 + N2 (r.2)H4N4C2O2 + 2 HNCO H4N4C2O2(HNCO)2* (r.3)H
4
N4
C2
O2
(HNCO)2
* H6
N4
C2
O2
+ N2
+2 CO (r.4)
H3N3C2O2 Gr.5 (r.5)H6N4C2O2 Gr.6 (r.6)
D SC PE pur o
0
1
2
3
4
5
6
7
5 0 1 0 0 1 5 0 2 0 0Te m pe r a t ur a ( C )
dQ/dT(J/gK
d Q / d T e x p .
d Q / d T c a l .
d Q / d T c a l . s i n
c o n t r i b u c i n d e C p
EVA (ethylene vinyl acetate)
0
0.5
1
1.5
2
2.5
3
0 25 50 75 100 125 150 175 200 225 250
Temperature (C)
dQ
(dT(J/gK)
TMAX= 49C
TMAX= 72C
TMAX= 113C
D S C A g e n t e E sp u m a n t e p u r o
-50
-40
-30
-20
-10
0
10
20
1 2 5 1 5 0 1 7 5 2 0 0 2 2 5 2 5 0 2 7 5
T e m p e r a t u r a ( C )
dQ/dT(J/gK)
d Q / d T e x p
d Q / d T c a l
Auto-acceleratingeffect
-14
-12
-10
-8
-6
-4
-2
0
2
3 0 0 3 1 5 3 3 0 3 4 5 3 6 0 3 7 5 3 9 0 4 0 5 4 2 0 4 3 5 4 5 0 4 6 5 4 8 0 4 9 5 5 1 0 5 2 5 5 4 0
Temperature (K)
dQ/dT(J/gK)
CA(TBPPB)
(kinetic modeling: multiple peaks and industrial processing)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 8
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE
mixtures (components: ADC, CA, EVA, PE)
PMSm,ADC
DSC
ADC
m,CA
DSC
CA
m,PE
DSC
PE
m,EVA
DSC
EVA
PSS
DSC
m C)w1(dT
dQ
dT
dQ
dT
dQ
dT
dQCw
dT
dQ+++++=
cTbTaC 2P
++=
= =
= 4
1m
2
N
1i.calc
DSC
m
.exp
DSC
m
dT
dQ
dT
dQ.F.O
( )100
D
PN.F.O
(%)RSD.av.exp
=
=
==
ref
jn
j
H
j,ref
j
j
H
jj
j
j
T
1
T
1
R
Eaexpw
kH
dt
dwH
dT
dwH
dT
dQi
(kinetic modeling: multiple peaks and processes)
n-order kinetics andArrhenius type behaviour
Reyes-Labarta and Marcilla. I&ECR (2011) 50(13), 7964-7976.http://dx.doi.org/10.1021/ie200276v
Reyes-Labarta and Marcilla. Journal of Applied Polymer Science
(2008) 110(5), 3217-3224. http://hdl.handle.net/10045/13312
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.
2006.09.054
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
DSC first run (variation of ADC content)
0
0.5
1
1.5
2
2.5
300 325 350 375 400 425 450 475 500 525 550
Temperature (K)
dQ/dT(J/gK)
0
1
2
3
4
5
6
dQ/dT(J/gK)[purePE]
EVAEP(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
Ethylene
domains
Vinyl acetate
domains
ADC
p3
p1+p2
pure PE
9
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE
mixtures
DSC results (1st runs) for the mixtures studied with various ADC contents:1, 2 and 4 phr.
Auto-acceleratingeffect
(kinetic modeling: multiple peaks and processes)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
DSC (first run)
-0.75
-0.25
0.25
0.75
1.25
1.75
2.25
300 325 350 375 400 425 450 475 500 525 550
Temperature (K)
dQ/dT(J/gK)
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
ADC
EVA(M)
EVA(T)
CpMCpS
PE(M)
Vinyl acetate domains
Ethylene domains
CA
10
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal treatment (studied by DSC): Crosslinked and foamed EVA-PE
mixtures
Experimental and calculated DSC curves (first run)
with the diff erent contribution of each component f or the mixture the mixture EP(10)C(3)A(2)Z(1.5)
(kinetic modeling: multiple peaks and industrial processing)
Reyes-Labartaand Marcilla.
I&ECR (2012)
51(28), 95158-
9530.
http://dx.doi.org
/10.1021/ie300
6935
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
300 350 400 450 500 550 600 650 700 750 800
Temperature (K)
Weightfraction
PE
EVACA
ADC
11
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal degradation (studied by TGA): Crosslinked and foamed EVA-PEmixtures
Experimental TGA curves for the pure components: CA (TBPPB), ADC (azodicarbonamide), EVA and PE
Evolutionof theweight
lostalong theprocess
One reactionTwo decomposition
reactions
Multiple decomposition
reactions
(kinetic modeling: multiple peaks and processes)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 12
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal degradation (studied by TGA): Crosslinked and foamed EVA-
PE mixtures
ADC thermal decomposition:
2 H4N4C2O2 H6N4C2O2 + 2 HNCO + N2 (r.1)2 H4N4C2O2 H3N3C2O2 + 2 HNCO + NH3 + N2 (r.2)H4N4C2O2 + 2 HNCO H4N4C2O2(HNCO)2* (r.3)H4N4C2O2(HNCO)2* H6N4C2O2 + N2 +2 CO (r.4)H3N3C2O2 Gr.5 (r.5)H6N4C2O2 Gr.6 (r.6)
CA,DCA,DCA,DCA,D
CA,D G)s1(RskCA +
DP1DP1
*
DP1DP1 G)s(1EVAsk
EVA +
DP2DP2DP2DP2DP2* G)s(1RskPEEVA + +
(kinetic modeling: multiple peaks and processes)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 13
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal degradation (studied by TGA): Crosslinked and foamed EVA-
PE mixtures
m,ADC
TGA
*ADCm,CA
TGA
CAm,PE
TGA
PEm,EVA
TGA
EVA
TGA
m
dtdwdtdwdtdwdtdwdtdw +++=
=
+
+
+
=
2DP
R
2DP
EVA
1DP
EVA
1DP
EVA
TGA
EVA
dt
dw
dt
dw
dt
dw
dt
dw
dt
dw ED
**
( ) ( )2DP
n
*EVA2DP1DP
n
EVA1DP s1wks1wk 2DP1DP =
( ) ( ) 2DP2DP nPE2DP2DP
PE2DP
RPE
TGA
PE wks1dt
dws1
dt
dw
dt
dw
dt
dw==+=
( ) ( )
==
+=
r
n
CACA,D,refCAD,
CA
CAD,
RCA
TGA
CA
T
1
T
1
R
Eaexpwks1
dt
dws1
dt
dw
dt
dw
dt
dw CA,DCA,DCA,D
( ) ( ) *ADC,D***ADC,D** n *ADC*ADC,D*ADCD,ADC,DADC,DRADC
TGA
ADC wks1dt
dws1
dt
dw
dt
dw
dt
dw==+=
(kinetic modeling: multiple peaks and processes)
n-order kineticsand Arrheniustype behaviour
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
300 350 400 450 500 550 600 650 700 750 800
Temperature (K)
Weightfraction
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)
14
Analysis and simulation of thermal treatmentsand degradations of polymer mixtures
Thermal degradation (studied by TGA): Crosslinked and foamed EVA-
PE mixtures
(kinetic modelling)
Experimental TGA curves for the mixtures studied with various ADC contents: 1, 2 and 4 phr
0.95
0.955
0.96
0.965
0.97
0.975
0.98
0.985
0.99
0.995
1
300 350 400 450 500 550 600 650
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
TGPYROLYSIS
0
0,2
0,4
0,6
0,8
1
1,2
200 250 300 350 400 450 500 550 600 650Temperature (C)
w/wo
TGExp. 5 K/min
TGcal. 5K/min
TGExp. 10K/min
TGCal. 10 K/min
TGExp. 25 K/min
TGCal. 25 K/min
15
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal degradation (studied by TGA):
TGCOMBUSTION
0
0,2
0,4
0,6
0,8
1
1,2
200 250 300 350 400 450 500 550 600 650
Temperature (C)
w/wo
TGExp. 5 K/min
TGcal. 5K/min
TGExp. 10K/min
TGCal. 10 K/min
TGExp. 25 K/min
TGCal. 25 K/min
Pyrolysis and Combustion
of polycoated cartons(tetra bricks) recycling
(kinetic modeling: multiple processes)
Chemicals and new fuels from biomass pyrolysis!!
Reyes et al. JAAP (2001) 58-59, 747-763.
http://dx.doi.org/10.1016/S0165-2370(00)00123-6
Conesa et al. JAAP (2004) 71, 343-352.
http://dx.doi.org/10.1016/S0165-2370(03)00093-7
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 16
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal degradation (studied by TGA): catalytic pyrolysis of EVA and
PP with MCM41, ZSM5, E-cat
1*k G)s1(EVAsEVA 1 +
22k* GEVA
CcGCEVA)c1(CcEVA 34k*vk* +++
dt
dG
dt
dG
dt
dG
dt
C*dEVA
dt
dC
dt
*dEVA
dt
dEVA
dt
dw 321 =+++=
1n
1EVAk
dt
dEVA= 4
3n2n1 n*
v
*
2
n
1
*
CEVAkEVAkEVAskdt
dEVA=
543n n*
4
n*
v CEVAckCEVAck
dt
dC+= 543
n n*
4
n*
v
*
CEVAk)c1(CEVAk)c1(dt
CdEVA++=
==
ref
ii,refoii,oi
T
1
T
1
R
Eexpk)RT/Eexp(kk
oF
o3
vCK
Ckk
+
=constant
initial amountof catalyst
(kinetic modeling: multiple processes)
Marcilla et al. JAAP (2003)
http://dx.doi.org/10.1016/S0165-2370(03)00036-6
Marcilla et al. Trends in Polymer Science (2003)
http://dx.doi.org/10.1002/chim.200601239
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 17
Analysis and simulation of thermal treatmentsand thermal degradations of polymer mixtures
Thermal degradation (studied by TGA): catalytic pyrolysis of EVA with
MCM41Sample 1
0
20
40
60
80
100
500 550 600 650 700 750 800 850
Temperature (K)
Weightloss(%) 40 K/min-9.33% M CM -41, exp.
40 K/min-9.33% M CM -41, cal.
10 K/min-9.10% M CM -41, exp.
10 K/min-9.10% M CM -41, cal.
40 K/min-No M CM -41 exp.
40 K/min-No M CM -41 cal.
10 K/min-No M CM -41 exp.
10 K/min-No M CM -41 cal.
TG curves at two heating rates and for the thermal and catalytic processes
(kinetic modeling: multiple processes)
Differentheatingrates
Differentamount
of catalyst
Marcilla et al. Polymer Deg. and Stability (2003)
http://dx.doi.org/10.1016//S0141-3910(02)00403-2
Marcilla et al. Polymer (2001)
http://dx.doi.org/10.1016//S0032-386(01)00277-4
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 18
Calculation of phase equilibrium (complex systems: LV, LL, LS, LLS, LLSh) Calculation of phase equilibrium (complex systems: LV, LL, LS, LLS, LLSh)
Empirical equations
Limitations of the actual models (e.g. NRTL)
LVE inconsistencies
GAP where solutions for homogeneous binary behavior are not found
Typical problems in complex LL and LLS equilibrium calculations
New strategies for coherent and simultaneous correlation
Topology of the Gibbs energy of mixing function
Applications: Optimal design of separation processes: distillation column and LL
extraction sequences, calculation of distillation boundaries
Multicomponent LLE and non-ideal LVE
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 19
Calculation of complex LL and LLS phase equilibrium
RT
GM
M
C
D
M
G
H
M
EF
ix
Global Mixture
ABM
Liquid phases in equilibrium
1) Possibility of different false solutions
RT
GM
0
xIi xII
i
2) Uncertainty in the final solution
xIi xIIi
TYPICAL PROBLEMS LLE!!TYPICAL PROBLEMS LLE!!
Topology of the Gibbs EnergyFunction (binary LLE)
(minor common tangent plane criterion )
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 20
Tangent
Planes
Solid
Solid
Tie
Lines
((minor common tangent plane criterionminor common tangent plane criterion ))
Topology of the Gibbs Energy Surface (ternary LLSE)
Solid
Inog.
Salt
Organic
Solvent
(A)
Water (B)
Calculation of complex LL and LLS phase equilibrium
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 21
Solid
Inog.
Salt
Organic
Solvent
(A)
Water (B)
Topology of the Gibbs Energy Surface (ternary LLSE)((minor common tangent plane criterionminor common tangent plane criterion ))
Calculation of complex LL and LLS phase equilibrium
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
1L
Solid
Tangent planes tothe GM surface
Only 1 tangentpoint each plane
22
Solid
Inog.
Salt
Organic
Solvent
(A)
Water (B)
2L
Tie line
Solid
1L+1S
Tie line
Solid
2 common points
2L+1S
Tie
Triangle
Solid
3 common points
Topology of the Gibbs Energy Surface (ternary LLSE)((minor common tangent plane criterionminor common tangent plane criterion ))
Calculation of complex LL and LLS phase equilibrium
coherent and robust equilibrium calculations
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 23
a) Using the second derivative of the GM function
NEW STRATEGIES to avoid typical convergence problemsNEW STRATEGIES to avoid typical convergence problems
Advantages:
Less time consuming
Trivial solution is avoided
Limit the equilibrium composition space for the LLE root determination
1x
g M
2
1
2
x
gM
Mg
A1x
B1x
I1x
II
1x1x
g M
2
1
2
x
gM
Mg
0 1
+
-A1x
B1x
I1x
II
1x
Restricted regions forequilibrium compositions
searching
Minimum common
tangent
Calculation of complex LL and LLS phase equilibrium
Marcilla et al. Fluid Phase Equilibria (2010)
http://dx.doi.org/10.1016/j.fluid.2009.12.026
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 24
b) Using an unambiguous definition of the plait point (pp) of the solubility curve
in ternary systems
NEW STRATEGIES
Limit the equilibrium composition space for the LLE root determination
Determinant of the
Hessian matrix of
the GM function
=0)
LL
L
Calculation of complex LL and LLS phase equilibrium
pp
Marcilla et al. IEC&R 51(13), 5098-
5102 (2012).http://dx.doi.org/10.1021/ie202793r
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 25
Limit the equilibrium composition space for the LLE root determination
NEW STRATEGIES
c1) Using a geometrical approach very good approximation to the ELL solution
MAXIMUM DISTANCE
PLANE -SURFACE
Plane generation points Maximum distance points
PREVIOUS
TIE -LINE
ESTIMATED
TIE -LINE
gM
x2
x3
((sequential series of minor cutting planes)sequential series of minor cutting planes)
Correlation of complex LL and LLS phase equilibria
1. Starting with the binary LLE, twoseparated zones, where the
conjugated compositions must be
located, are found by intersection
between an adequate plane and the
GM surface.
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. 26
Limited composition space for the LLLE root determination
NEW STRATEGIES
c2) Using a geometrical approach very good approximation to the LLLE solution
A B
C
LL LL
LL
LLL
L
L
L
a
b
c
tie-triangle
((sequential series ofsequential series of
minor cutting planes)minor cutting planes)
e.g. 1-nonanol + nitromethane + water (23 C)1-hexanol + nitromethane + water (21 C)
Calculation of complex LL and LLS phase equilibrium
((minor common tangent plane criterionminor common tangent plane criterion ))
Marcilla et al. Fluid Phase Equilibria 281, 87-95 (2009). http://dx.doi.org/10.1016/j.fluid.2009.04.005
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 27
Empirical constraints for NRTL binary parameters
NEW STRATEGIES
766.908A1.20662A2.9574510A4.4656410)f(AA ji2
ji
43
ji
8
jiij +++==
Border line between L and LL regions for the NRTL model
-2000
-1000
0
1000
2000
3000
-2500 -1500 -500 500 1500 2500 3500
Aji
Aij
MISCIBLE (1L)
PARCIALLY MISCIBLE
)f(AA jiijHeterogeneous (LL)
LType island systems:
A12+ A210
A23+ A32>0
Calculation of complex LL and LLS phase equilibrium
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 28
Different objective functions
NEW STRATEGIES
a) Minimum of the overall Gibbs Energy of mixing
=
c
1i
LiL
i
Sliquid
MSMoverall
RTxs1
RTs
RT
G
RT
G
RT
G
1L+1S
*Line defined by a constantratio xOrganicSolvent/xwater
-0,8
-0,75
-0,7
-0,65
-0,6
-0,55
-0,50 0,05 0,1 0,15 0,2
s
GMoverall
Calculation of the Minimum of the overallGibbs Energy of mixing, along a concreteline* for each experimental point.
Correlation of complex LL and LLS phase equilibria
Reyes et al. IEC&R 40,902-907 (2001).
http://dx.doi.org/10.1021/ie000435v
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 29
Different objective functions
NEW STRATEGIES
( ) 0).(.23
1
== =i
II
i
I
i aaaFOa) Isoactivity criterium
c) Isoactivity + Minor common tangent condition
d) A modification of the initial vector method
M
1 3
2
I
II
gTL
a
a b
a, b
I, II
liquid phases of thebinary 1-3
liquid phases ofa potential tie line
0.0E+00
1.0E-05
2.0E-05
3.0E-05
4.0E-05
5.0E-05
6.0E-05
7.0E-05
8.0E-05
3.13 3.14 3.15 3.16 3.17 3.18 3.19
-angle
Obje
ctivefunction
O.F.(a)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 31
NEW STRATEGIE RESULTS:
CORRELATION OF (uncorrelated) COMPLEX LL SYSTEMS (NRTL)
TYPE I
Calculation of complex LL and LLS phase equilibrium
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. 32
NEW STRATEGIE RESULTS:
CORRELATION OF (uncorrelated) COMPLEX LL SYSTEMS (NRTL)
30,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
2
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
experimental ( )
calculated ( )
water Tetrahydrofuran
Dimethyl sulfoxide
T=20C
30,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
2
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
experimental ( )
calculated ( )
experimental ( )
calculated ( )
water Tetrahydrofuran
Dimethyl sulfoxide
T=20CTYPE 0
TYPE II
TYPE III
Calculation of complex LL and LLS phase equilibrium
Marcilla et al. Fluid
Phase Equilibria 281,
87-95 (2009) .
http://hdl.handle.net/10045/13315
Olaya et al. Fluid
Phase Equilibria
265, 184-191
(2008).
http://hdl.handle.net/10045/24681
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 33
using the NRTL
binary parameters
published in theDECHEMA
Chemistry Data
Series
Consistent
Inconsistent
Calculation of complex LL and LLS phase equilibrium
NEW STRATEGIE RESULTS:
CORRECTION OF SOME (NRTL) INCONSISTENCIES IN LL (type I-II) SYSTEMS
Reyes-Labarta et al.
Fluid Phase Equilibria278, 9-14 (2009).
http://hdl.handle.net/10045/24683
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 34
Illustrating example of a clear limitation for NRTL (constant alpha)
If we realize a systematic study on the GM function for a totally miscible binary system,
there exist a GAP where solut ions for homogeneous binary behavior are not found.
(with ij =0.2)
LIMITATIONS OF THE ACTUAL MODELSLIMITATIONS OF THE ACTUAL MODELS
-5.5
-4.5
-3.5
-2.5
-1.5
-0.50 0.2 0.4 0.6 0.8 1
x2
gM
gap
400.gMmin =
-5.5
-4.5
-3.5
-2.5
-1.5
-0.5 0 0.2 0.4 0.6 0.8 1
x2
gM
450 .gMmin =
Calculation of complex LL and LLS phase equilibrium
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 35
Illustrating example of a clear limitation for NRTL (constant alpha )
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.0 0.2 0.4 0.6 0.8 1.0
x3
x2
interpolated experimental data
interpolated among the calculated compositions
calculated compositions
experimental data
opposite slopes!
A12=873.57 =0.2
A21=-1245.0 =4.08
A13=578.07
A31=578.07
A23=-987.32
A32=-856.11
Data and parameters from Dechema. Sorensen and Artl, W.Chemistry Data Series; Vol. V/2, DECHEMA, 1980. Page 129.
A) LLE: Methanol(1) + difenilamine(2) + cyclohexane(3) at 298K
Phase Equilibrium calculations. Limitations of the actual models
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
T(x,y)
0
20
40
60
80
100
120
0 0.2 0.4 0.6 0.8 1
x,y
T
exp
Selected VLE
data point
Calculated
VLE data point
Lexp Vcal Vexp
T
GM
Lexp Vexp
GM vapor
GM liq
gap
(DECHEMA,Vol 1,Part 1a,p.256)
1 data All data (DECHEMA)
A12 = -53.57 K A12 = -136.05
A21 = 293.90 K A21 = 402.92
=3.0 =2.8
+=i i
iioi
i
V,M
ylny)T(p
Plny
RT
G
650
4721
.RT/G
.dx
)RT/G(d
expx
L,M
expx
L,M
=
=
Vcal
GMliqDECHEMA
Phase Equilibrium calculations. Limitations of the actual models
B) LVE: water + 1,2-propanediol at 25 mmHg
36
it is impossible to obtain a good
correlation and also to correlate
only one LVE point
Illustrating example of a clear limitation for NRTL (constant alpha )
There is nosolution(NRTL)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Phase Equilibrium calculations. More limitations of the actual models
C) LVE: water + 1-propanol at 760 mmHg
37
Illustrating example of a clear limitation for NRTL (constant alpha )
(DECHEMA,Vol 1,Part 1a,p.286292)
7dataseriesat 760mmHg,with different
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
Type
3+type5
Type
3+type5
Just one set of these data pass the
thermodynamic test of consistency,
however, the corresponding NRTL
parameters predict an incoherent
behavior
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
PITFALLS OF THE TERMODINAMIC CONSYSTENCY TESTS
D) LVE: SOME CONSISTENCY TEST USE THERMODYNAMIC MODELS AS NRTL TOVALIDATE THE VLE EXPERIMENTAL DATA, e.g. Frenkel-NIST point-to-pointtest (van Ness)
38
Illustrating example of a clear limitation for NRTL (constant alpha )
Acetone (1) + water (2) at 2570 mmHg
(DECHEMA, Vol. I-1a Sup. 1, p. 197)
Metilvinilcetone (1) + water (2) at 743 mmHg
(DECHEMA Vol . I-1, p. 355).
BUT. WHAT HAPPENDS IF WE CANNOT FIND A GOOD CORRELATION?
ARE THE DATA INCONSISTENT OR IS THE MODELUNCAPABLE OF REPRESENTING THE
EXPERMIENTAL BEHAVIOUR?
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 39
Phase Equilibrium calculations
A) Possib le modif ication for NRTL model:
=
i
l lli
j
jjiji
ii
E
xG
xG
xFRT
G
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 0.2 0.4 0.6 0.8 1
x1
gM
-3.000
-3.200
-3.5
-4
-2.98
-0.25
-0.22
-0.35
-0.38
-0.4
-0.500
-1
-1.5
-2
-2.5
-2.8
The init ial GAP is completed!The init ial GAP is completed!
Experimental data
correlation is
considerably improved
for several sys tems, evenisland types!
Experimental data
correlation is
considerably improved
for several systems, even
island types!
But What can we do in the meanwhile?But What can we do in the meanwhile?New factors
Effective molecular weights
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. 40
B.1) EMPIRICAL EQUATIONS
LLE FOR QUATERNARY SYSTEMS (TYPE 1)
and are the composition (components i,j,k) and transformed enthalpy (l) of vapor and liquid phase,respectively, and C=cte.
LVE FOR TERNARY SYSTEMS (including composition and enthalpy data)
Aqueous phase(x)
Organic phase(y)
Calculation of complex LL and LLS phase equilibrium
(Logarithmic eq.)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 41
Marcilla et al. IEC&R 38(8), 3083-3095 (1999).
http://dx.doi.org/10.1021/ie9900723
+
+
++
+
+=
1
2
2
2
4,
2
4,,
2
2
4,
2
4,,
'
'log
'
'
'
'
'
'
'
'
'
'log
x
x
x
xf
x
xed
x
xc
x
xba
y
ypkpkpkpkpkpk
p
k
+
++
2
1
2
2
2
4,
2
4,,
'
'log
'
'
'
'
x
x
x
xi
x
xhg pkpkpk
Four equations with four variables !!
Ciyiy += )()('
1)2('
)3('log k
y
y=
2
)1('
)2('log k
y
y=
3
)3('
)4('log k
y
y=
Cyyyy +=+++ 41)4(')3(')2(')1('
EMPIRICAL CORRELATIONS
Calculation of complex LL and LLS phase equilibrium
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 42
B.2) EMPIRICAL EQUATIONS (Polynomial eq.)
LVE FOR NON-IDEAL AND AZEOTROPIC TERNARY SYSTEMS (y vs x)
=
=
=
= c
1qc
1jjj,q
q
c
1jjj,i
i
i
xa
x
xa
x
y
where xi and yi are the composition of the conjugated liquid and vapourphases in equilibrium, and the subscripts i,j and q refer to the differentcomponent of the mixture. ai,j represent the correlation parameters of theequation, which are independent of the composition. Such parameters mustbe obtained by correlation of the experimental data.
=
++
+
++
+
+++
+++
= c
1q1c
qj1jjj2c2,q
c
qjjqj1c,q
c
ijjj,qq
q
1c
ij1jjj2c2,i
c
ijjij1c,i
c
ijjj,ii
i
i
xxaxxaxax
x
xxaxxaxax
x
y
Calculation of complex LL and LLS phase equilibrium
Marcilla et al. VIII Iberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design
(2009). http://hdl.handle.net/10045/14276
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 43
LVE FOR NON-IDEAL AND AZEOTROPIC TERNARY SYSTEMS (T vs x)
==
+=3
1i3
1j
jj,i
ii0
xa
xTTT
=
++
+
+++
+=c
1i1c
ij
1jjj2c2,i
c
ij
jij1c,i
c
ij
jj,ii
ii0
xxaxxaxax
xTTT
It is necessary to introduce the mathematical constraints corresponding tothe azeotropic points!!!
B.2) EMPIRICAL EQUATIONS (Polynomial eq.)
( ) )ln()ln())(()()( 22112
2
1
12111,2,1, xxDxxCxxxxBAxTTTT nn
bbb +++=
( )( ) ( )
( ) ( )
=
az,2az,12
2
2
az,2az,1
12
2
az,2az,1
21
2
az,2az,12
1
2
az,2az,1
x,xx
Tx,x
xx
T
x,xxx
Tx,x
x
T
x,xH
Calculation of complex LL and LLS phase equilibrium
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
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
In this case, it is important to remark that it is necessary to introduce the mathematical
restrictions corresponding to the azeotropic points:
Binary azeotropes: yi,az= xi,az and
44
Phase Equilibrium calculations
LVE FOR NON-IDEAL TERNARY SYSTEMS (T vs x)
( ) 0xdx
dTaz
1
=
( ) 0x,xx
Taz,2az,12
1
2
( ) ( ) ( )
( ) ( )
=
az,2az,12
2
2
az,2az,1
12
2
az,2az,1
21
2
az,2az,12
1
2
az,2az,1
x,xx
Tx,x
xx
T
x,xxx
Tx,xx
T
x,xH
AT with maximum boiling temperature: H(x1,az, x2,az) > 0 and
AT with intermediate boiling temperature: H(x1,az, x2,az)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 45
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
GOAL: to
avoid theoptimaldesign ofdistillationcolumns byrepeatedsimulations
Marcilla et al. Latin American Applied Research International Journal 27(1-2), 51-60
(1997). http://hdl.handle.net/10045/24679
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 46
Optimal design of separation process
EMPIRICAL EQUATIONS APPLICATIONS
1. EXTENTION OF THE GRAPHICAL METHODS
McCABE-THIELE AND HENGSTEBECK METHOD FOR THE DESIGN OF
MULTICOMPONENT DESTILLATION COLUMNS
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1EQUILIBRIUM (y vs x) AND McCABE DIAGRAM (MOLAR)
x
y
yeq
diagonal
Eq.pisos
BM-Roperat.
XD,XB
R.Op.1
R.Op.2
R.Op.3
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0 .1 0 .2 0 .3 0 .4 0 .5 0 .6 0 .7 0 .8 0 .9 1
Marcilla et al. Review and
extension of the McCabe-
Thiele method covering
multiple feeds, products and
heat transfer stages (2012).
http://hdl.handle.net/10045/2
3195
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 47
Optimal design of separation process
EMPIRICAL EQUATIONS APPLICATIONS
2. GRAPHICAL CONCEPTS TO ORIENTATE THE MINIMUM REFLUX RATIO
CALCULATION
GOAL: tosimplify therigorouscalculation ofthe minimumreflux ratio
Reyes-Labarta et al. IEC&R 39(10),3912-3919 (2000).http://dx.doi.org/10.1021/ie9907021
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 48
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), 3083-3095 (1999).
http://dx.doi.org/10.1021/ie9900723
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Optimal design of separation process
EMPIRICAL EQUATIONS APPLICATIONS
E1
R0 Rdef
1 2 n-1
j
n
ELn=E0
R1
E2Initial Solvent Feed
Initial
Raffinate
Feed
Final
Raffinate
Product
Final ExtractProduct
EL1 EL2 ELn-1
Side Solvent Feeds
R0,byp
Bypass
R0,ext
RLk,byp
RLk
Side
Feed
Streams PLq
Side
Product
Streams
4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS using
MINLP Techniques or Generalized Disjunctive Programming (GDP)
49
Reyes-Labarta & Grossmann,
AIChE 47(10), 2243-2252 (2001).http://dx.doi.org/10.1002/aic.690471011
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Rdef
E11
R1o R1n1
EL11 EL1n1-1
1 2 n1-1 n1i
E1o
R2o
E21 E2o
EL21 EL2n2-1
1 2 n2-1 n2i
R2n2
Multiple Interconnected Extractors
4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS usingGeneralized Disjuntive Programming (GDP)
Reyes-Labarta & Grossmann,
Computer Aided Chem.Eng.
(2001).
http://dx.doi.org/10.1016/S1570-
7946(01)80076-650
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
The selection of the stages in the optimal extraction cascade will be performed
using the following stage existence disjunction.
51
4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS usingGeneralized Disjuntive Programming (GDP)
stageexistingnonstageexisting
j
Rj-1
Ej Ej+1
equilibriumRj
Rj-1= Rj
Ej= Ej+1
j
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).
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 52
4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS usingGeneralized Disjuntive Programming (GDP)
Zj
is a boolean variable which can be true or false depending if the stage j is
selected or not.
=
=
=
=
=
=
=
+
+
0;0
0;0
0;0
;
;
;
:
0),(:
,
,,,
,,,
,1,,1
,1,,1
,1,,1,
,,
,,
cjj
cjqjq
cjkjk
cjcjcjj
cjcjcjj
cjcjcjcj
j
cjjcj
cjcj
j
ELEL
PLPL
RLRL
RRRR
EEEE
yyxx
Z
uFFtermsBilinear
xymEquilibriu
Z
j
NT
c
COMP
k
K
q
Q
F
{R, E, PLq
,
RLk, EL, Rdef}
u = {x or y}
To avoid equivalent solutions that are due to the multiplicity of representation
for a given number of trays, the following logic constraints are added:
1jj ZZ
j
NINT
Solution strategy: an logic-based OuterApproximation algorithm (NLPsubproblems-MILP master problem).
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 53
COMPLEX EXTRACTOR DESIGN (GDP)
http://newton.cheme.cmu.edu/interfaces/extractor/main.html
4. OPTIMAL SYNTHESIS OF LIQUID-LIQUID MULTISTAGE EXTRACTORS usingGeneralized Disjuntive Programming (GDP)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 54
LV Equilibria (P = cte). Homogeneous Ternary Azeotropic Systems
A
BE
BA
E
A B
E
B
A
AAA
AAA
BBB
BBB
E
EEE
EEE
Introduction: Topology Azeotropic Liquid-Vapour Equilibrium
Gmez et al. Ingeniera
Qumica, 379, 253-262
(2001)
-
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 55
x,y
T
Heterogeneous
lquids at boiling
temperature
L
V
LL
Solubility
surface
Heterogeneous
azeotropic
binaryLLV
PP
V-Lhet CurveLast V-Lhet
point
..
.
Ternary system with:
1 heterogeneous binary azeotrope
1 LLV region (tie triangles)
3
21
Introduction: Topology Azeotropic Liquid-Vapour Equilibrium
Gmez et al. Ingeniera Qumica, 377, 219-229 (2001)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 56
Optimal design of separation process
EMPIRICAL EQUATIONS APPLICATIONS
5. DESTILLATION BOUNDARIES CALCULATION
-0.2 0 0.2 0.4 0.6 0.8 1 1.2-0.2
0
0.2
0.4
0.6
0.8
1
1.2System Methanol-Acetone-Hexane. Distillation curves
Methanol (1)
Acetone(2)
*
AB13min
AB12min
AB23min
ATmin
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 57
Topological concept used:
when there exists , the trajectory of a
distillation boundary continuously
contains not only the composition of theliquid phase, but also the composition
of the vapor phase in equilibrium
x0
y0x
1
y1
x2
y2x
3 y3
x4
L-V tie lines
distillation boundary trajectory
5. DESTILLATION BOUNDARIES CALCULATION
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 58
Mathematical algorithm:
Endyes
no
Singular points
Trajectory: origin/end, nipt and function (nincs or n )
Independent variable (e.g. x2)
Compositions: x2,k(k=1,2,,nipt)
Initial values for parametersAj (or cs nodes, x1,k)
ycal1,k=yceq
1,k?
New values for parameters Aj or (cs nodes: x1,kk=1,2,, nincs)
Compositions: xcal1,k(k=1,2,,nipt)
Compositions: yeq1,k(k=1,2,,nipt)
Compositions: ycal1,k(k=1,2,,nipt)
DISTILLATION BOUNDARIES CALCULATION
X1,k(k=1,2,, nincs)
X2,k (k=1,2,nipt)
Stable node
*
*
*
*
-
-
-
-
--
-
-yeqi,k
ycal1,k^
y1,kcal=f(y2)
Unstable
node
trajectory to test
x1,kcal=f(x2)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 59
NUMERICAL EXAMPLES: Ternary Distillation Boundaries (LV)
Benzene(1)-Cyclohexane(2)-Toluene(3) System at 760 mm Hg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00x1
x2
Ethanol(1)-Benzene(2)-Water(3) System at 760 mmHg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00
X1
X2
Dietilether(1)-Ethanol(2)-Water(3) System at 2156.3 mmHg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00
x1
x2
2-Butanol(1)-2-Butanone(2)-Water(3) System at 760 mm Hg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,20 0,40 0,60 0,80 1,00x1
x2
5. DESTILLATION BOUNDARIES CALCULATION
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 60
Water(1)-Ethanol(2)-Toluene(3) System at 760 mmHg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00
x1
x2
Methanol(1)-Acetone(2)-Chloroform(3) System at 760 mmHg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,20 0,40 0,60 0,80 1,00
X1
X2
2-Propanol(1)-Benzene(2)-Water(3) System at 760 mmHg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00
x1
x2
Acetone(1)-Meth anol(2)-Cyclo hexane(3) System at 760 mmHg
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
0,00 0,20 0,40 0,60 0,80 1,00
X1
X2
NUMERICAL EXAMPLES: Ternary Distillation Boundaries (LV)
5. DESTILLATION BOUNDARIES CALCULATION
Reyes-Labarta et al. I&ECR, 50(12), 7462-7466 (2011). http://dx.doi.org/10.1021/ie101873g
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 61
Heterogeneous ternary system with:
1 heterogeneous azeotropic binary composition
2 homogeneous azeotropic binary compositions
1 homogeneous azeotropic ternary composit ion
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Benzene
Isopropanol
NUMERICAL EXAMPLES: Ternary Distillation Boundaries (LV)
5. DESTILLATION BOUNDARIES CALCULATION
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
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 62
Acetone
Methanol
Water
i-propanol
Acetone
Methanol
Water
i-propanol
Homogeneous quaternary system with:
2 homogeneous azeotropic binary compositions
The quaternary distillation boundary curve is formed by the two different distillation
boundary surfaces, that intersect in one curve.
NUMERICAL EXAMPLES: Quaternary Distillation Boundaries (LV)
5. DESTILLATION BOUNDARIES CALCULATION
Ternary DistillationBoundary (curve)
Quaternary Distillation
Boundary (surface)
Quaternary DistillationBoundary (curve)
(1)
(2)(3)
(4)
BA3,4
BA1,2
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 63
Simulation-optimization approaches for process design Simulation-optimization approaches for process design
Optimal design of absorption systems including LCA
Optimal design of generalized distillation columnsn=i
EV
cond
RSSS
Compp-H
Reb
F
IHER
D
QD
QR
Ln,RS
V1,SS
Ws
QIHT
-QIHT
Ln,RS
(high pressure)
(low pressure)
Design of Internally Heat-Integrated Distillation Columns (HIDiC)
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
Reyes-Labarta et al. Computer Aided Chemical Engineering.
2011, 29, 301-305. http://dx.doi.org/10.1016/B978-0-444-
53711-9.50061-4
Reyes-Labarta et al. AIChE Meeting 2012.https://aiche.confex.com/aiche/2012/webprogram/Paper267732.html
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 64
Generalized scheme of a distillation column Generalized scheme of a distillation column
n=i
Optimal design of generalized distillation columns
Lk,n+1
Vk,n+1-(VGFk)
Vk,n+2
(LGFk)
Lk,n(=Lk,NTk) (Lk+1,0)
k= k (or k+1)
Hysys Flowsheet (tray by tray calculations)
Multiple side streams (feeds,products or intermediate
heat exchangers)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Schematic representations of the internal existing
streams at the zone connecting consecutive sectors in
the case of a generalized feed side stream (GFk).
65
Optimal location of all the side streams:
Optimal design of generalized distillation columns
Intermediate Heat exchanger
Side product stream (liquid or vapor)
(two phases) Side feed stream
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.
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. 66
Optimal design of absorption systems including LCA
Water-Ammonia Absorption CycleWater-Ammonia Absorption Cycle
Novel framework for theoptimal design ofsustainable thermodynamiccycles
The problem is mathematically formulated as a multi-objective mixed-integer non-linear programming (moMINLP) problem (that simultaneouslyaccounts the minimization of the total annualized cost and the totalenvironmental performance of the cycle)
Combined the use of A)rigorous process simulationtools, B) optimizationsoftware and C) LCA (Lifecycle assessment)
DistillationColumn
(binary variables)
{ }
=
=
=
0),,(
0),,(
0),,(..
),,(),...,,,(1min
DE
DE
DI
DnD
x
xuxg
xuxh
xuxhts
xuxfxuxfzD
Solution strategy: an logic-based OuterApproximation algorithm (MILP master problem[Gams]-NLP subproblems[Matlab-Aspen])
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 67
Optimal design of absorption systems including LCA
Water-Ammonia Absorption Cycle: Flowchart of the proposed algorithm
Brunet, R. et al.
Computers and
ChemicalEngineering, 2012,
46, 205-216.
http://hdl.handle.net/
10045/24678
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 68
Optimal design of absorption systems including LCA
Water-Ammonia Absorption Cycle: Objective Functions
=b
bbdd LCIdfdamagetalEnvironmen
opPkeDkqpHXSDopc t)WCQC(fcr)CCC(CCTAC == ++++=+=
Environmental
Impact category
Unit Steam [kg] Electricity [kWh] Steel [m2]
1 Carcinogencis Points/Unit 1.1810-4 4.3610-4 7.8310-1
2 Climate change Points/Unit 1.6010-3 3.6110-6 1.70
3 Ionising radiation Points/Unit 1.1310-3 8.2410-4 3.3010-2
4 Ozone depletion Points/Unit 2.1010-6 1.2110-4 1.0010-3
5 Respiratory effects Points/Unit 7.8710-7 1.3510-6 10.2
6 Acidification Points/Unit 1.2110-4 2.8110-4 1.24
7 Ecotoxicity Points/Unit 2.8010-3 1.6710-4 2.40
8 Land occupation Points/Unit 8.5810-5 4.6810-4 3.1110-1
9 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
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 69
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. 70
Design of Internally Heat-Integrated Distillation Columns (HIDiC)
PossibleHeatIntegration!!
Conventional distillation column
Feed
Distillate
Residue
LD
...
...
n=1
n=N
LD+DQD
QRQ B
(bottom)
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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)
B
F 2
Q DL 1, 0+ D
2
3
L 1, 0
Q
1 QE1
xB xDB,xB
D,xD
y
zF
s1
s2
s3
xB
F
QEyF
xF
xopt,F
D
yQE
yQE
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 72
Design of Internally Heat-Integrated Distillation Columns (HIDiC)
Inter-Condenser and inter-reboiler benefits (McCabe-Thiele Method)
B
F 1
Q D
L 1, 0+ D
2
3
L 1, 0
Q
1
QA2
xQA zFxB xDB,xB
D,xD
y
s1
s2
s3
xB
F
QA
yF
xF
xopt,F
D
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 73
Design of Internally Heat-Integrated Distillation Columns (HIDiC)
General representation of an internally heat-integrated distillation columnGeneral representation of an internally heat-integrated distillation column
B,xBB
F 2
Q D
D
L 1, 0+ D
3
4
L 1, 0
Q
2
QA3
1 Q E1
DD,xD
InternalHeat
Integration
(high pressure)
(low pressure)
Rectifying sector
(light components)
Stripping sector
(heavy components)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 74
Design of Internally Heat-Integrated Distillation Columns (HIDiC)
EV
cond
RSSS
Comp
p-H
Reb
F
IHER
D
QD
QR
Ln,RS
V1,SS
Ws
QIHT
-QIHT
Ln,RS
(high pressure)
(low pressure)
General configuration of an internally heat-integrated distillation columnGeneral configuration of an internally heat-integrated distillation column
B
QB
PSO algorithm
Rectifying SectorStrippingSector
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 75
Design of Internally Heat-Integrated Distillation Columns (HIDiC)
Condenser and reboiler duties, and compressor shaft work vs overallinternal heat transfer (QIHT)
0 200 400 600 800 1000 1200 1400 1600 1800 20000
500
1000
1500
2000
2500
QIHT (kW)
Q(kW)
QDQR
WS
It is possibleto optimize the TAC!!!
But the solutiondepends stronglyon the cost of theelectricity and thesystem studied, purityof the final products,etc.!!
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 76
Design of sustainable processes
General configuration of a vapour recompression distillation column (VRC)General configuration of a vapour recompression distillation column (VRC)
EV
cond
Comp
Reb
F1
B
D
Qp-cond
Qp-H
QIHT
(high pressure)
(low pressure)
R=L1,0
Ws
F2
p-H
p-cond
Mainly for systems with smalltemperature difference between the top
and bottom products
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Reyes-Labarta, J.A.*; Marcilla, A. Thermal Treatment and Degradation of Crosslinked Ethylene VinylAcetate-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 ofCrosslinked 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 Treatmentof Ternary Mixtures of Ethylene Vinyl Acetate, Polyethylene and Azodicarbonamide. Journal of AppliedPolymer Science, 2008, 110(5), 3217-3224 (http://dx.doi.org/10.1002/app.28802). RepositorioInstitucional RUA: http://hdl.handle.net/10045/13312.
Reyes-Labarta, J.A.; Marcilla, A. Kinetic Study of the Decompositions Involved in the ThermalDegradation 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 AppliedPolymer Science, 2006, 102(3), 2015-2025 (http://dx.doi.org/10.1002/app.23969). RepositorioInstitucional 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 theThermal 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
Biography (I. Kinetic modelling)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Marcilla, F.J. Sempere y J.A. Reyes-Labarta. Differential Scanning Calorimetry of Mixtures of EVA andPE. 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 ThermalDecompositions. 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 ofPlasticized 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 polypropylenepyrolysis using ZSM-5 and an equilibrium fluid catalytic cracking catalyst. Journal of Analytical andApplied 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 pyrolysisof 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 MCM-41. Kinetic model. Polymer Degradation and Stability, 2003, 80, 233-240(http://dx.doi.org/10.1016/S0141-3910(02)00403-2).
78
Biography (I. Kinetic modelling)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh.
Marcilla, A.; Reyes, J. A.; Sempere, F. J. DSC Kinetic Study of the Transitions Involved in the ThermalTreatment 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. kineticmodel 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 deFormulaciones Industriales de Copolmeros de EVA y PE. Anlisis Cintico . Biblioteca Virtual Miguel deCervantes (Universidad de Alicante), 2003.
http://www.cervantesvirtual.com/FichaObra.html?Ref=9612http://hdl.handle.net/10045/10130
79
Biography (I. Kinetic modelling)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 80
-Marcilla, A.; Reyes-Labarta, J.A.; Olaya, M.M.; Serrano M.D. Simultaneous Correlation of LL, LS andLLS Equilibrium Data for Water + Organic Solvent + Salt Ternary Systems. Hydrated Solid PhaseFormation. 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 SolidPhase. Industrial & Engineering Chemistry Research, 46, 7030- 7037 (2007).http://dx.doi.org/10.1021/ie0705610
-Reyes, J.A.; Conesa, J.A.; Marcilla, A.; Olaya, M.M. Solid-Liquid Equilibrium Thermodynamics: checkingstability in multiphase systems using Gibbs Energy Function. Industrial & Engineering ChemistryResearch, 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-LiquidEquilibrium 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 Procedurefor the Correlation of Type 3 Ternary Systems Including a Three-Liquid Phase Region. Fluid PhaseEquilibria 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 Equilibriafor 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 CondensedPhase Equilibrium Calculations. Fluid Phase Equilibria 296(1), 15-24 (2010).http://hdl.handle.net/10045/13314
Biography (II. Phase equilibria)
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 81
-Reyes, J.A.; Olaya, M.M.; Gmez, A.; Marcilla, A. Calculation of liquid-vapor and liquid-liquid equilibriumin multicomponent systems using correlations of equilibrium data. V Iberoamerican Conference on PhaseEquilibria 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 PhaseEquilibria: An exercise to understand the nature of false solutions and how to avoid them. ChemicalEngineering 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. VIberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design. EQUIFASE 99Book of Proceedings, pag. : 3 10. Vigo (Espaa), 1999 (http://hdl.handle.net/10045/2482).
Biography (II. Phase Equilibria)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 82
-Reyes-Labarta, J.A.; Caballero, J.A.; Marcilla, A. Numerical Determination of Distillation Boundaries forMulticomponent 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 ofDistillation 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 PointConditions and their Application in Ternary Systems. Industrial & Engineering Chemistry Research51(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 CondensedPhase Equilibrium Data Regression in Ternary Systems: Limitations and Proposals. The OpenThermodynamics 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 thedevelopment 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 IberoamericanConference on Phase Equilibria and Fluid Properties for Process Design (2009).http://hdl.handle.net/10045/14276
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-Reyes-Labarta, J.A. Diseo de Columnas de Rectificacin Y Extraccin Multicomponentes. BibliotecaVirtual 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-liquidExtraction 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 MulticomponentMixtures. Latin American Applied Research and International Journal of Chemical Engineering, 27, 51-60 (1997). http://hdl.handle.net/10045/24679
-Reyes, J.A.; Gomez, A.; Marcilla, A. Graphical concepts to orient the minimum reflux ratio calculation onternary 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 Liquid-liquid 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 AidedProcess Engineering Center). ISBN: 0-444-50709-4 (Dinamarca, 2001). http://dx.doi.org/10.1016/S1570-7946(01)80076-6
Biography (III. Unit operations)
Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburgh. 84
-Reyes-Labarta, J.A.; Caballero, J.A.; Marcilla, A. A Novel Hybrid Simulation-Optimization Approach forthe 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 simulationand MINLP methods for the optimal design of absorption cooling systems. Computer Aided ChemicalEngineering. 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 Simulation-Optimization Methodology for the Design of Environmental Conscious Absorption Systems. Computersand 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, productsand 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 theDesign of Internally Heat-Integrated Distillation Columns. AIChE 2012 Annual Meeting (EnergyEfficiency by Process Intensification).https://aiche.confex.com/aiche/2012/webprogram/Paper267732.html
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Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburghweb: http://iq.ua.es/~jareyes/