PSE v80i3 Seminar JAReyesLabarta CAPD CMU2012

7/24/2019 PSE v80i3 Seminar JAReyesLabarta CAPD CMU2012

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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







Outline


2/43


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)


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


3/43



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



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


4/43



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)




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


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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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



mixtures

DSC results (1st runs) for the mixtures studied with various ADC contents:1, 2 and 4 phr.

Auto-acceleratingeffect



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



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


6/43


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


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




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 + +



7/43




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==+=


n-order kineticsand Arrheniustype behaviour


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


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


8/43


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


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



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


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


9/43



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


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


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


10/43


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 )


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)



11/43


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 ))



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 ))


coherent and robust equilibrium calculations


12/43


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


Marcilla et al. Fluid Phase Equilibria (2010)

http://dx.doi.org/10.1016/j.fluid.2009.12.026


b) Using an unambiguous definition of the plait point (pp) of the solubility curve

in ternary systems

NEW STRATEGIES


Determinant of the

Hessian matrix of

the GM function

=0)

LL

L


pp

Marcilla et al. IEC&R 51(13), 5098-

5102 (2012).http://dx.doi.org/10.1021/ie202793r


13/43



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.


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)


((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


14/43


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



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


15/43


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)


16/43


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



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


Marcilla et al. Fluid

Phase Equilibria 281,

87-95 (2009) .


Olaya et al. Fluid

Phase Equilibria

265, 184-191

(2008).



17/43


using the NRTL

binary parameters

published in theDECHEMA

Chemistry Data

Series

Consistent

Inconsistent



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

Reyes-Labarta et al.

Fluid Phase Equilibria278, 9-14 (2009).



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 =



18/43


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


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


There is nosolution(NRTL)


19/43


Phase Equilibrium calculations. More limitations of the actual models

C) LVE: water + 1-propanol at 760 mmHg

37


(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


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


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?


20/43


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).


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

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


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)


(Logarithmic eq.)


21/43


Marcilla et al. IEC&R 38(8), 3083-3095 (1999).


+

+

++

+

+=

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



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


Marcilla et al. VIII Iberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design

(2009). http://hdl.handle.net/10045/14276


22/43


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



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)


23/43


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




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).


3195


24/43




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




3. OPTIMAL DESIGN OF MULTICOMPONENT LL EXTRACTION COLUMNS

(using tray by tray methods)

Marcilla et al. IEC&R, 38(8), 3083-3095 (1999).



25/43




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


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


26/43


The selection of the stages in the optimal extraction cascade will be performed

using the following stage existence disjunction.

51


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).



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).


27/43


COMPLEX EXTRACTOR DESIGN (GDP)

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



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)


28/43


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)




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


29/43


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



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)


30/43


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



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



Reyes-Labarta et al. I&ECR, 50(12), 7462-7466 (2011). http://dx.doi.org/10.1021/ie101873g


31/43


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



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


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)


Ternary DistillationBoundary (curve)

Quaternary Distillation

Boundary (surface)

Quaternary DistillationBoundary (curve)

(1)

(2)(3)

(4)

BA3,4

BA1,2


32/43


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


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)


33/43


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



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])


34/43



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



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

Environmental Impact category



PossibleHeatIntegration!!

Conventional distillation column

Feed

Distillate

Residue

LD

...

...

n=1

n=N

LD+DQD

QRQ B

(bottom)


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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



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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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)



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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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.!!


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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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)


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



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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



-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).


-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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-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)


-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

Biography (II. Phase Equilibria)


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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


-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)


-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

Biography (III. Unit operations)


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Thanks very much for your attention

Any question?

Juan A. Reyes-Labarta. PSE Seminar, CAPD-CMU. October, 2012. Pittsburghweb: http://iq.ua.es/~jareyes/

PSE v80i3 Seminar JAReyesLabarta CAPD CMU2012

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