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Steam Cracking - COnnecting REpositories · Raw natural gas Steam cracker Crude oil Petroleum...
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Laboratory for Chemical Technology, Ghent University
http://www.lct.UGent.be
Steam Cracking:from Feedstock Analysis to Plant Optimization
Stoomkraken:van voedingsanalyse tot fabrieksoptimalisatie
Thomas Dijkmans
Public defence, Ghent, Belgium, 26/09/2014
1
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The heart of a petrochemical plant
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Public defence, Ghent, Belgium, 26/09/2014
Steam crackerRaw natural gas
Crude oil
Petroleum refining
Natural gas processing
Ethane
Propane
Butane
Methane
Condensate
Naphtha
Kerosene
Gas oil
Other products
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The heart of a petrochemical plant
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Public defence, Ghent, Belgium, 26/09/2014
Steam crackerRaw natural gas
Crude oil
Petroleum refining
Natural gas processing
Ethane
Propane
Butane
Methane
Condensate
Naphtha
Kerosene
Gas oil
Other products
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The heart of a petrochemical plant
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Public defence, Ghent, Belgium, 26/09/2014
Ethylene
Propylene
Butadiene
Benzene
Steam cracker
Polyolefin plants,…
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Crash course hydrocarbon chemistry
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Hydrocarbons is a chain of carbon atoms linked to hydrogen
Carbon Hydrogen
Carbon number = Number of carbons in the chainElemental composition = Relative amount of H, C, … on a 100% scale (weight
based or mole base)Branched hydrocarbons = Carbons with branches instead of a straight chain
Cracking = Breaking of those chains to form smaller unsaturated hydrocarbonsNew bonds can off course also be formed during the process
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Crash course hydrocarbon chemistry
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Unsaturated hydrocarbons have a double bond between two carbon atoms
Ethylene Propylene
It is this double bond that provides the reactivity needed for the downstream processes and makes these molecules special
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Crash course hydrocarbon chemistry
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Radical are species that have a missing bond
This missing bond makes them very reactive and unstable
These are important intermediate species for steam cracking
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Developing of a model for steam cracking
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Simulation model
Goal Reactor geometryOperating conditions
Feedstock properties
Product specs
Modeling Microkinetic model
Reactor model
Fundamental reactor model
Detailedfeedstock
composition
Detailedproduct
composition
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Plug flow reactor model
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Molecules and radicals move as a plug through the reactor and each individual plug does not influences other plugs
Mass balances (Nspecies)
����� = � ����
�
�� ٠� ����,�
�����
�
�� = �� + Ω � � . (−Δ��)
�
��
���,��� = − 2"
�# − 2�$+ %
&'(�)�* − (�)�
�)���
Momentum balance (1)
Energy balance (1)
Energy (heat) can go in or out of the reactor
Feed Productsheat
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Developing of a model for steam cracking
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Public defence, Ghent, Belgium, 26/09/2014
Simulation model
Goal Reactor geometryOperating conditions
Feedstock properties
Product specs
Modeling Microkinetic model
Reactor model
Fundamental reactor model
Detailedfeedstock
composition
Detailedproduct
composition
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Main reaction families
Bond dissociation and radical recombination
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R1 R2 R1 R2• •
+
Hydrogen abstraction (inter- and intramolecular)
R1 H R1R2••
R2 H++
Radical addition and β-scission (inter- and intramolecular)
R1 R2 R3R1•
R2 R3•+
Reaction Families:
Need to limit the reaction size
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R1 H R1R2••
R2 H++R2-R1 H•
R2-R1H•
intramolecular)(inter- and
R1 R2 R1 R2• •
+
R1 R2 R3R1•
R2 R3•+ R1 R2 R3R1
•R2 R3
•+
R1 R2 R1 R2• •
+
Radical addition and β-scission
µ radical hypothesis
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µ hypothesis = Monomolecular reactions dominate for long chain radicals (#C>5)
Bond dissociation
Hydrogen abstraction
R1
R2R3
•R1-R2 R3 •
and radical recombination
intramolecular)(inter- and
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Decomposition scheme: hexane
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RH
β molecules
QSSA species
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Decomposition scheme: hexane (2)
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( ) ( )RHR +
+
→+ ∑
∑∑
∑ββradol n
1=l3
1=ii
pseudo
j
n
1j=3
1=ii
jpseudo
146
k
kO
k
OkHCn .
Applying QSSA reduces this reaction scheme to:
• Drastic reduction of the number of species to need to be considered in the final ODE’s
• Drastic reduction of the number of reactions
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Microkinetic network
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β network µ network
CRACKSIM
Bi- and monomolecularreactions for β radicals
Monomolecular reactionsfor µ radicals
R1 R2 R1 R2• •
+
R1 H R1R2••
R2 H++
R1 R2 R3R1•
R2 R3•+
R1 R2 R1 R2• •
+
R2-R1 H•
R2-R1H•
R1 R2 R3R1•
R2 R3•+
R1
R2R3
•R1-R2 R3 •
1324 reversible reactions51 molecules43 radicals
13584 schemes676 molecules
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Validation radiant coil
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Ethylene Propylene
Feedstocks:
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Detailedfeedstock
composition
Simulation model
Goal Reactor geometryOperating conditions
Product specs
ModelingMicrokinetic
modelReactor model
Fundamental reactor model
Detailedproduct
composition
Feedstock properties
Fundamental modeling approach
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GC×GC
Analytical techniques
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1-dimensional chromatography
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DetectorInjector
Time
Signal
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GC × GC
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DetectorModulatorInjector
Time
Signal
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1D to 2D chromatogram
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Dallüge et al., J. Chrom. A 2003
Raw 2D chromatogram
Transformation
Visualisation
3D plot
Color plot
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GC × GC – FID/TOF-MS
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Qualitative, difficult to quantify
Quantitative but no direct identification possible
Paraffins
Diaromatics
Aromatics
Triaromatics
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SCD
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Diaromatics
C12 C13 C14
• Roof tile structure helps identification
• Overlap of sulfur containing hydrocarbons with pure hydrocarbons
• Not all sulfur containing hydrocarbons can be found with TOF-MS due to high differences in concentration
C11 benzothiophene
C12 benzothiophene
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GC × GC – SCD
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Again no direct identification is possible
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GC × GC – SCD (2)
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Calibration mixture
Shale oil
Thiols
Benzothiophenes
Dibenzothiophenes
0 9045First dimension retention time (min)
Sec
ond
dim
ensi
on r
eten
tion
time
(s)
0
7
0
7
3.5
3.5
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GC × GC – NCD
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Again no direct identification is possible
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SPE -GC ×GC - TOFMS
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Hexane
Dichloromethane
Acetone
Shale oil sample
1) Load SampleHexane flushDichloromethane flushAcetone flush
Pyridines
Pyridines
Anilines
Anilines
Indoles
Quinolines
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GC × GC – NCD
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GC × GC – FID/SCD/NCD
Public defence, Ghent, Belgium, 26/09/2014
#C P I MN DN MA NA DA NDA TA Pd An Q In Ac Ca T BT NBT DBT Ph Total5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.24 0.00 0.00 0.00 0.00 0.256 1.62 2.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.25 0.00 0.00 0.00 0.00 4.217 2.26 1.48 0.00 0.00 0.11 0.00 0.00 0.00 0.00 0.11 0.02 0.00 0.00 0.00 0.00 0.16 0.00 0.00 0.00 0.07 4.198 2.20 1.98 0.00 0.00 0.70 0.00 0.00 0.00 0.00 0.26 0.05 0.00 0.01 0.00 0.00 0.10 0.02 0.00 0.00 0.11 5.419 2.36 2.24 0.57 0.00 1.68 0.00 0.00 0.00 0.00 0.47 0.07 0.01 0.06 0.00 0.00 0.07 0.14 0.00 0.00 0.12 7.79
10 2.33 1.53 0.86 0.00 1.78 0.39 0.05 0.00 0.00 0.15 0.11 0.08 0.17 0.00 0.00 0.04 0.33 0.00 0.00 0.05 7.8711 2.33 1.18 1.09 0.00 1.36 0.33 0.40 0.01 0.00 0.18 0.11 0.17 0.28 0.00 0.00 0.03 0.33 0.00 0.00 0.00 7.7712 2.36 0.98 1.21 0.01 0.95 0.26 1.01 0.16 0.00 0.12 0.08 0.19 0.30 0.00 0.00 0.03 0.20 0.01 0.01 0.00 7.8413 2.31 1.41 1.14 0.13 0.88 0.42 1.08 0.20 0.00 0.18 0.03 0.12 0.16 0.00 0.02 0.02 0.06 0.00 0.03 0.00 8.1914 2.28 1.09 1.06 0.14 0.62 0.34 0.76 0.40 0.03 0.17 0.00 0.03 0.14 0.01 0.02 0.00 0.03 0.00 0.08 0.00 7.2015 2.24 1.06 0.91 0.26 0.81 0.26 0.41 0.33 0.17 0.13 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.00 0.04 0.00 6.6516 2.22 0.71 0.78 0.18 0.50 0.16 0.24 0.16 0.40 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.4317 2.09 0.85 0.88 0.10 0.49 0.11 0.14 0.10 0.14 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.9418 2.00 0.81 0.92 0.09 0.30 0.09 0.03 0.07 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.3319 1.65 0.73 0.58 0.09 0.26 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.4020 1.55 0.48 0.76 0.06 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.0321 1.37 0.38 0.58 0.07 0.18 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.5922 1.36 0.37 0.43 0.05 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.3023 1.13 0.32 0.28 0.04 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.8124 0.90 0.25 0.20 0.01 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.3825 0.78 0.07 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.0026 0.60 0.08 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.7727 0.46 0.06 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.6028 0.31 0.05 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.4029 0.21 0.03 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.2730 0.13 0.03 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.1831 0.05 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.0932 0.03 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.0733 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03
Total 39.08 20.50 12.71 1.21 11.00 2.43 4.14 1.42 0.74 1.98 0.46 0.59 1.10 0.04 0.04 0.93 1.10 0.01 0.16 0.34 100.0028
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Fundamental modeling approach
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Simulation model
Reactor geometryOperating conditions
Feedstock properties
Product specs
Microkinetic model
Reactor model
Fundamental reactor model
Detailedfeedstock
composition
Detailedproduct
compositionGC×GC
Standard methods
GoalAnalytical techniques
Feedstockreconstruction
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• Average molecular weight
• Elemental composition• Specific density • Global PINA analysis• Boiling point data
(e.g. D2887 simdist)• Aromatic Sulfur
Feedstock reconstruction
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Feedstock properties Detailed composition• Species identity
Feedstock reconstruction
± 20 properties More than 100 unknown mole fractions
Shannon entropy
maximization
( ) ( ) ∑∑==
=−=MM N
ii
N
iiii yyyyS
11
1 with ln MAX
Constraints from mixing rules (example):
∑∑=
=MN
i iii
ii
y
y
1exp Mwd
Mw
d
1∑
=
=MN
iiiy
1exp MwMw
Molecular library
• Mole or mass fractions
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Results: Sulfur containing hydrocarbons
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Thiols/sulfides
Experimental
Old indices
New indices
Benzothiophenes
Dibenzothiophenes
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Results: Hydrocarbons
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n-paraffins i-paraffins
Naphthenes Aromatics
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Fundamental modeling approach
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Simulation model
Reactor geometryOperating conditions
Feedstock properties
Product specs
Microkinetic model
Reactor model
Fundamental reactor model
Detailedfeedstock
composition
Detailedproduct
compositionGC×GC
Standard methods
GoalAnalytical techniques
Feedstockreconstruction Computational
efficient
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• Mathematical techniques– Using a different solving technique (e.g. analytical
Jacobian)– Alternative calculation of functions that are difficult to
evaluate
• Computational techniques– Using a graphical card to perform certain calculations
• Mathematical techniques– Using a different solving technique (e.g. analytical
Jacobian)– Alternative calculation of functions that are difficult to
evaluate
• Computational techniques– Using a graphical card to perform certain calculations
Decreasing simulation time
• Chemical techniques= simplify kinetic mechanism by network reduction
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Total simulation time
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500
Base case
Tabulation
Analytical Jacobian
GPU
GPU +Analytical Jacobian
Tabulation +GPU +Analytical Jacobian
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Conclusions
• Development of a fundamental simulation tool requires the use of different state-of-the-art techniques such as:– Single-event microkinetic models to account
for all the reactions occurring between species
– GC × GC or feedstock reconstruction to obtain a detailed feedstock composition
• The models are however valid over a broad range of process conditions and for different feedstocks
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Conclusions (2)
• The simulation time of such fundamental reactor models can drastically be reduced by:– Tabulation– Calculating an Analytical Jacobian instead of
a finite-difference Jacobian– Using the graphical processing unit to handle
part of the calculations
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Questions
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