systematic analysis and design of hybrid processes p. t. mitkowski, g. jonsson, r. gani capec...

C A P E C

Systematic analysis and design of hybrid processes

P. T. Mitkowski, G. Jonsson, R. Gani

CAPEC

Department of Chemical Engineering

Technical University of Denmark

EUROPEAN CONGRESS OF CHEMICAL ENGINEERING – 6

COPENHAGEN, 16 – 21 SEPTEMBER 2007

2/20European Congress of Chemical Engineering – 6

C A P E C

Motivation

• Motivation & Objectives

Outline

Motivation

Objectives

Methodology

Case studies

Conclusion

Future work

• Methodology

• Case studies

• Conclusion

• Future work…

Hybrid process is a combination of at least two processes which influence each other and the optimization of the design must take into account this interdependency.

Process 1 Process 2

Hybrid process

Raw materials Products

Chemical ProcessRaw materials Products

Process 1 Process 2

Hybrid process

Separator

Distilation

Membrane

Extraction

...

Reactor

Separator

Distilation

Membrane

Extraction

...

Raw materials Products

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European Congress of Chemical Engineering – 6

Motivation

Motivation

Objectives

Methodology

Case studies

Conclusion

Future work

Hybrid processes are finding increasing use in pharmaceutical

and biochemical manufacturing providing better alternatives

(sometimes only alternatives) in cases where:

• reaction(s) kinetically or equilibrium controlled - low process yield

• difficult separation task - low driving force

Current design/analysis techniques are largely experiment-based, therefore, there is a potential for reducing time & costs for process development through systematic computer-aided techniques

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Objectives

Needs & Issues

Algorithm for design-selection of processes that may be

considered in the hybrid process (systems integration) Generic model of the hybrid process through a computer

aided modelling tool (modelling) Databases of solvents, membranes, reactions and

chemicals (use of available knowledge) Case studies for validation of models, methods & tools

(validation)

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Develop systematic computer aided methods & tools for design & analysis of a wide range of hybrid

processes

5/20

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Methodology: Design Algorithm

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Feasible design

Hybrid ProcessModel

Separation/Reactor Model

Step 4: State process conditions

SeparationModel

Step 3: Find f easible separation method

Step 2: Define/ determine processdemands

Kinetic Model

Step 1b: Choose appropriate solvent

Step 1a f or R-S:Reaction data

analysis

Step 1a f or S-S:Separation task

analysis

CapecDB Manager

Membrane data

Solvent data

Reactionkinetics data

Property dataI CAS-ProPred

I CAS-TML

I CAS-MoT

I CAS-ProCAMD

I CAS-PDS

MemData

I CAS-MoT

I CAS-Sim

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Methodology: Generic Model

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Process 2Process 1Feed

Product 2

Product 1

T, Pnt, x

i

T, Pnt, x

i

)

)

)

)

1 1 1 1 2 2 2 2

1 1 1 1 2 2 2 2 1

1

F R R R R R R R RHFh F h F h F h F hi i i it

NKRP P P P P P P P RF h F h F h F h r H Qi i i i k kk

1 1 2 2 1 1 2

2 1 1 1,

1

R R R R P P Pni F F F F F F F Fi i i i i i i it

NKRPF r Vi i k k

k

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Case study: Reaction - Separation

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Step 1a: Esterification of cetyl oleate over Novozym 435 (Canadia anatarctica on acrylic resin) [1].

[1] T. Garcia, A.Coteron, J.Aracil, ,Chem. Eng. Science 55,(2000), 1411-1423

43516 33 17 33 34 66 2 2

NovozymC H OH C H COOH C H O H O

Step 2: Increase productivity of cetyl oleate by removing of water. X > 80 mol% .

Step 1b: Solvent free system

Step 3: Pervaporation with hydrophilic polymeric membranes to remove water

332.3; 353T KR 0.11wa

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Case study: ModelStep 4: Hybrid process model

Process 1: Reaction

Process 2: Pervaporation

2i

i m i

dnJ A V r

dt

Process 2Process 1Feed

Product 2

Product 1

T, Pnt, x

i

T, Pnt, x

i

)

)

)

)

1 1 2 2 1 1 2

2 1 1 1,

1

R R R R P P Pni F F F F F F F Fi i i i i i i it

NKRPF r Vi i k k

k

mcat

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

9/20

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Constitutive equations:

where: 1,..., 4i

Mol balance:

Case study: Model

DAE model: 4 ODEs and AEs 52 ;No. of variables: 117

1

ni i

i i

n MWV

w w wJ P xEster

Acid

nX

n

,max ,max 2 1 3 42 2

2

,max ,max ,max3 3 31 2 12 ,2 ,2 2 ,1 2 2 ,2 1' ' ' " ' '

,2 ,3 ,2 ,3 ,1 ,3

,max ,max2 ,4 3 2 ,3 4 ,max

2 2

1 1 1

f r

eq

r r ri m m m

i i i i i i

f fm m r

eq eq

C C C Cr r

Kr

C C CC C Cr K K r K C r K C

K K K K K K

r K C r K Cr C C

K K

,max ,max,max

2 ,4 2 3 2 ,2 1 42 3 41

,2 ,4

,max ,max2 2 1 3 2 1 3 4

,3 ,1

r rrm m

eq i eq i

r f

i i eq

r K C C r K C Cr C C

K K K K

r C C C r C C C

K K K

+ Modified UNIFAC (Lyngby)

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

ICAS - MoT

10/20

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Step 4: Feasible design: Hybrid process• polyvinyl alcohol membrane (PERVAP1001, GFT)• Am = 0.0288m2

• tbatch = 5h• tswitch= 0h• V = 0.6 dm3

• IC Equimolar• Cw

in = 0.005mol/dm3

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 50 100 150 200 250 300 t [min]

X [

mol

/mol

]

RCPV5

RCPV4

RCPV3

RCPV2

RCPV1

Batch

Case study

Am

Batch RCPV1 RCPV2 RCPV3 RCPV4 RCPV4 RCPV5 Am [m2] - 0.0036 0.0144 0.0288 0.0432 0.0144 0.0576 t [min] 300 300 300 300 300 900 300 X [-] 0.841 0.872 0.917 0.927 0.929 0.967 0.930

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work [min]

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Case studyStep 4: Influence of addition of the catalyst on

the batch time

0

20

40

60

80

100

120

140

160

180

0 20 40 60 80 100

w% of catalyst addition

t bat

ch [

min

]

X = 0.9

X = 0.85X = 0.8

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

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Case studyStep 4: Influence of tswitch at overall process

performance in t batch = 5h

0.86

0.87

0.88

0.89

0.9

0.91

0.92

0.93

0.94

0 1 2 3 4 5

t switch [h]

X [

-]

5w% catalysttbatch = 5h

25w%

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

13/20

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Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Case study: Conclusion

Batch reaction combined with pervaporation give

promising results.

Process conditions:

– Amount of catalyst increase up to 30 w%

– Start coupled operation within first hour

– PERVAP1001, GFT

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Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Case study: Separation-Separation

Step 1a: Separation of equimolar mixture of acetic acid (HAc) and water (100 kmol/hr)

• Experimental VLE data fitted to Mod. UNIFAC (Lyngby)

Step 2: Two streams with a purity of 99.5 mol% of HAc and water

Step 3: Distillation + Pervaporation with hydrophilic polymeric membrane

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

x H2O

y H

2O

P = 760 mmHg; Gmehlind et. al.Mod. UNIFAC (Lyngby)

ICAS - TML

15/20

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Introduction

Objectives

Methodology

Case studies

Conclusion

Future work


-1.5

-1

-0.5

0

0.5

1

1.5

2

2.5

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x i

d(

DF

i ) /

d(x

i)

VLE @P = 101.3 kPa

Doped Polyaniline Mem. - PV [8]

Step 4: Identification of sequence of processes - Driving Force approach.

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x i

FD

i

Doped Polyaniline Mem. - PV [8]Undoped Polyaniline Mem. - PV [8]VLE @P = 273.7 kPaVLE @P = 101.3 kPaVLE @P = 53.3 kPa

99.5 mol% H2O80mol% H2O

99.5 mol%HAc

99.5 mol% H2O

99.5 mol% HAc

100 kmol/hr

100 kmol/hr

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Introduction

Objectives

Methodology

Case studies

Conclusion

Future work


35000

37000

39000

41000

43000

45000

47000

49000

0 0.2 0.4 0.6 0.8q [mol/mol]

QR

eb -

QC

on

d [

MJ/

hr]

0.0

0.2

0.4

0.6

0.8

1.0

x H

2O (

of

tota

l fe

ed)

[mo

l/m

ol]

Total heat dutyBase case, QxH2O (R )

0

10000

20000

30000

40000

50000

0 0.2 0.4 0.6 0.8q [mol/mol]

QR

eb -

QC

on

d [

MJ/

hr]

0

0.2

0.4

0.6

0.8

1

x H

2O (

of

tota

l fe

ed)

[mo

l/m

ol]

Total heat dutyBase case, QBase case, x H2Ox H2O of total feed

Step 4: Feasible design: Heat requirement in terms of membrane module characteristic

• selectivity

•cut

2 1

1 2

1

1

Pi i

Pi i

F F

F F

2

1

PF

F

q

= 50

= 2.25

ICAS - MoT

ICAS - Sim

17/20

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Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Case study: Conclusion

Distillation combined with pervaporation gives

process improvment

Distillation followed by pervaporation

– required high selective membrane

– possible doped pollyaniline membrane

Distillation with side pervaporation

– can give improvment even with low selective

membrane

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Conclusions

Systematic computer-aided methods and tools for hybrid process analysis & design has been developed and has been presented along with two case studies The main difficulty is the availability of data and

property models

Computer aided tools help to reduce time and

resources needed for hybrid process development Identifies a small set of alternatives where the

experimental effort might be concentrated on

Introduction

Objectives

Methodology

Case studies

Conclusions

Future work

19/20

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Future work

Introduction

Objectives

Methodology

Case studies

Conclusion

Future work

Investigation of other hybrid processes

- 4 case studies done

Further development of membrane database

20/20European Congress of Chemical Engineering – 6

C A P E C

Thank you for your attention !Questions are welcome !

• Supervisors: Prof. G. Jonsson, Prof. R. Gani• PRISM - 6th Framework EU project• CAPEC co-workers

Acknowledgement:

systematic analysis and design of hybrid processes p. t. mitkowski, g. jonsson, r. gani capec...

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