CAPEC 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
Dec 18, 2015
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: