C A P E C

Model-based hybrid reaction-separation process design

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

Funded by PRISM (EC)

CAPEC

Department of Chemical Engineering

Technical University of Denmark

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Outline

• Motivation & Objectives

• Methodology

• Case study

• Conclusion

• On going work…

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Motivation

Motivation

Objectives

Methodology

Case study

Conclusion

Future work

Hybrid process is a combination of at least two processes which influence each other and the optimisation 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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Motivation

Motivation

Objectives

Methodology

Case study

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 study

Conclusion

Future work

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

of hybrid processes

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Methodology: Design Algorithm

Introduction

Objectives

MethodologyCase study

Conclusion

Future work

Hybrid ProcessModel

Separation/Reactor Model

Step 4: State process conditions

SeparationModel

Step 3: Find f easible separation method

Step 2: Defi ne/ 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

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Methodology: Design Algorithm

Introduction

Objectives

MethodologyCase study

Conclusion

Future workHybrid Process

Model

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

MethodologyCase study

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

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

Step 1a: Enzymatic esterification of cetyl alcohol with oleic acid [1]

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

[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

332.3; 353T KR 0.11wa

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Case study: Process scenarios

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

Batch operation• different initial conditions

Hybrid processes• various rates of addition of components• various component fluxes and Am

• various operational parameters in membranes

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Case study: ModelStep 4: Hybrid process model

Process 1: ReactionProcess 2: Pervaporation

2i

i m i

dnJ A V r

dt

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

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

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Constitutive equations:

where: 1,..., 4i

Mass balance:

Case study: Model

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

1

ni i

i i

n MWV

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

w w wJ P x

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)

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Case study

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

Am

Step 4: Feasible design: Hybrid process with pervaporation

• polyvinyl alcohol membrane (PERVAP1001, GFT)•Am = 0.0288m2

• tbatch = 5h• tswitch= 0h

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

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

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Case study

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

Step 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

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Case study

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

Step 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

25

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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 case study

The main difficulty is the availability of data, property models and application (performance) 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 study

Conclusions

Future work

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On-going work…

• Investigation of other hybrid processes – 4 case studies done

• Experimental verification of methodology with esterification of Propionic Acid with 1-Propanol (collaboration with University of Dortmund, Chair of Fluid Separation)

• Further development of membrane database

Introduction

Objectives

Methodology

Case study

Conclusion

Future work

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Thank you for your attention!!!

All questions are welcome

•PRISM - 6th Framework EU project•CAPEC co-workers•PRISM co-workers

Acknowledgement: