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STEAM-CRACKING: FROM MOLECULE TO INDUSTRIAL PROCESS
Kevin M. Van Geem and Guy B. Marin (keynote)
8TH ASIAN-PACIFIC CHEMICAL REACTION ENGINEERING (APCRE 2017) SYMPOSIUM EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY, SHANGHAI, CHINA, NOV. 12-15, 2017
Laboratory for Chemical Technology
Ghent University History13-Nov-17
2/172
2017
Furnace revamp
8th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
COILSIM1D13-Nov-17
3/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Steam cracking: hot section
D
A
C
A: Radiation section
B: TLE
C: Steam drum
D: Convection section
Endothermic process 1050–1150 K
Preheat feed and other utility streams
Rapidly
quenching
of reactor
effluent
B
45%
50%800K
700K
1050–1150 K
5%
1450 K
FPH
Saturated steam
BFWECO
Feed
Dilution steam
SSH
HTC
Steam
13-Nov-17
4/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Developing of a model for steam cracking
Simulation
model
Goal Reactor geometry
Operating conditions
Feedstock
properties
Product
specs
Modeling Microkinetic
model
Reactor
model
Fundamental
reactor model
Detailed
feedstock
composition
Detailed
product
composition
13-Nov-17
5/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor
• Process
• Conclusions
13-Nov-17
6/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock: characterization
• Kinetics
• Reactor
• Process
• Conclusions
13-Nov-17
7/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
1st dimension retention time (min)
0 4020
2n
d d
ime
nsio
n r
ete
ntio
n tim
e (
s)
0
5
8060
indene
naphthalene
acenapthylene
phenanthrene
pyrenetoluene
benzeneethyl-Bz
(b)
xylenes
1st dimension retention time (min)(a)
styrene
methyl-naphthalenesvinyltoluene
anthracene
biphenyl
tri-methyl-Bz
methyl-indenes
acenapthene
mono-
aromatics
di-
aromatics
naphtheno-
aromatics
naphtheno-
di-aromatics
tri-aromatics
tretra-aromatics
GCGC chromatogram: 2 parts
Conventional 1D part C4-
Comprehensive 2D part C5+
3D view
methane
propene
1.3-butadiene
ethene
ethane propane1-butene
propadiene
8
Pyl, S.P. et al.,Journal of Chromatography A, 1218, 3217-3223, 2011On-line GC × GC
13-Nov-17
8/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
• Average molecular
weight
• Elemental composition
• Specific density
• Global PINA analysis
• Boiling point data
(e.g. D2887 simdist)
• Aromatic Sulfur
SIMCO: Maximization of Shannon Entropy
Feedstock properties Detailed composition
• Species identity
Feedstock
reconstruction
± 20 properties More than 100 unknown
mole fractions
Shannon
entropy
maximization
MM N
i
i
N
i
iii yyyyS11
1 with ln MAX
Constraints from mixing rules (example):
MN
i iii
ii
y
y
1exp Mwd
Mw
d
1
MN
i
iiy1
exp MwMw
• Mole or mass fractions
S.P. Pyl et al., AIChE Journal, 56, 12, 3174-3188, 2010
13-Nov-17
9/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
SIMCO results: Hydrocarbonsn-paraffins i-paraffins
Naphthenes Aromatics
13-Nov-17
10/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor
• Process
• Conclusions
13-Nov-17
11/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
CRACKSIM: steam cracking kinetics
Simulation
model
Goal Reactor geometry
Operating conditions
Feedstock
properties
Product
specs
Modeling Microkinetic
model:CRACKSIMReactor
model
Fundamental
reactor model
Detailed
feedstock
composition
Detailed
product
composition
13-Nov-17
12/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics: reaction network
• Reactor
• Process
• Conclusions
13-Nov-17
13/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Network generators
●●
●●
●●●
●
●
●
●
●
●
●
●
●
●
RING
Daoutidis
Minneapolis
Genesys
PRIM(-O)
ReNGeP
LCT, Ghent, Belgium
RMG
Green
Cambridge
NetGen
Broadbelt
Delaware
EXGAS
Battin-Leclerc
Nancy, France
RDL
Mavrovouniotis
Evanston
RDL++
Vankatasubramanian
West Lafayette
CASB
Porollo
Josjkar-Ola, Russia
MAMOX(+)(++)
Ranzi
Milan, Italy
REACTION
Blurock
Lund, Sweden
COMGEN
Truong
Salt Lake City
MECHGEN
Héberger
Budapest, Hungary
KING
Di Maio
Cosenza, Italy
RAIN
Ugi
Munich, Germany
GRACE, Yoneda
KUCRS, Miyoshi
Tokyo, Japan
RNG
Lederer
Prague, Czech RepublicMECHEM
Valdes-Perez
Pittsburgh
13-Nov-17
14/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
GENESYS : GENEration of reacting SYStems
PatternRecognition
MoleculeIdentifiers
Reactant -> product
Vandewiele, N.M. et al., Chemical Engineering Journal, 207-208, 526-538, 2012
Van de Vijver, R. et al. International Journal of Chemical Kinetics, 47 (4), 199-231, 2015
Vandewiele, N.M. et al., Journal of Computational Chemistry, 36 (3), 181-192, 2015
“Kinetics of Chemical Reactions : Decoding Complexity”
G.B. Marin and G.S. Yablonsky,Wiley-VCH Verlag, 446 pages, 2011
13-Nov-17
15/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Families of elementary reactions
Bond dissociation and radical recombination
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
•+
13-Nov-17
16/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
CRACKSIM: μ and β networks
β network μ network
CRACKSIM
Bi- and monomolecular
reactions for β radicals
Monomolecular reactions
for μ radicalsR1 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 reactions
51 molecules
43 radicals
13584 schemes
676 molecules
13-Nov-17
17/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
Introduction
Feedstock
Kinetics: ab initio
Reactor
Process
Conclusions
66th Canadian Chemical Engineering Conference “Sustainability & Prosperity” October 16-19 (2016) Québec City (Canada) 13-Nov-17
18/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Conventional Transition State Theory (high pressure limit)
The CBS-QB3 ab initio method is used.
Electronic barrier ΔE0
• Ideal gas approximation
• Hindered Rotor (1D-HR)
Partition functions q
• Eckart
Tunneling coefficient κ
RT
E
m
BA
B eVqq
q
h
Tk)T()T(k
0‡
‡E
A + B [AB]‡ C
Transition state
Δ‡Eelectronic
Reaction coordinate
‡
Reactants
Products
Kinetics: computational approach13-Nov-17
19/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Objective: data base 13-Nov-17
Reactor model
Solver
Reaction network
Kinetic and thermodynamic data
Develop a consistent data set based on ab initio
calculations
Reactor simulation for hydrocarbon radical chemistry
? Larger speciesusing group additivity
Van de Vijver, R. et al., Chemical Engineering Journal, 278, 385–393, 2015
20/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
O
O
OH
2-methoxy-2-methylbut-3-enoic acid additive groups
Cd-(H)2
C-(C)( Cd)(O)(CO)
Cd-(C)(H)
O-(C)2
C-(O)(H)3
C-(C)(H)3
CO-(C)(O)
O-(CO)(H)
O
O
OH
Additivity
= + + + +
+ + + +
O
OH
Atoms in large molecules
Atoms in small molecules
with similar surroundings
Group additivity
O
From small to large species with group additivity13-Nov-17
21/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Hydrogen abstraction (ethyl + ethenyl methylether)
CH=CH2
resEEEE EYGAVXGAVCGAVCGAVTETE ,a1o
1o
2o
1o
refa,a )()()()()()(aaaa
C1 H C2
H
H
H
H
‡
• OCH3+CH2 CH3 CH3
OCH2
CH3 CH3 + CH2
OCH2
+4.7 kJmol-1 +0 kJmol-169.7 kJmol-1 -18.2 kJmol-1
Ea, ab initio= 62.0 kJmol-1Ea,GA = 62.6 kJmol-1
C1-(C)(H)2 C2-(O)(H)2CH3 + CH4
-0.866 +0.4805.268 +0
logAab initio= 5.203log(AGA /m3 mol-1s-1)= 5.095
-0.053
O-(C2)(Cd)C-(C1)(H)3 H-
+6.8 kJmol-1 -0.4 kJmol-1
C1-(C)(H)2 C2-(O)(H)2CH3 + CH4 O-(C2)(Cd)C-(C1)(H)3 H-
-0.512
Paraskevas, P. et al.,Journal of Physical Chemistry A, 119 (27), 6961-6980, 2015
Kinetics: data base of ΔGAVo13-Nov-17
22/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Kinetics: validation of group additivity
0
2
4
6
8
10
0 2 4 6 8 10
log
kG
A
log(kAI/m³mol-1s-1;s-1)
H additions
H β scission
C addition
C β scission
H-abstraction
1000 K
Sabbe et al. ChemPhysChem 2008, 9 (1), 124-140
Sabbe et al. ChemPhysChem, 2010, 11(1), 195-210
Sabbe et al. PhysChemChemPhys, 2010, 12 (6), 1278-1298
13-Nov-17
23/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor
• Process
• Conclusions
13-Nov-17
24/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Steam Cracking Pilot PlantGas-Fired Furnace + Reactor
Online Analysis
Section
Control “Room”
High temperature
sampling system
HC
Feed
H2O
13-Nov-17
25/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Pilot results: C1/C2/C3/C4Process conditions
Feed 3 wt% C1
67 wt% C2
22 wt%C3
8 wt% C4
COT 1005-1119 K
COP 0.152-0.157 MPa
Steam dilution 0 kg/kg
0
10
20
30
40
50
60
70
0 10 20 30 40 50 60 70
Ab
init
io p
red
icte
d y
ield
(w
t%)
Experimental yield (wt%)
methane
ethene
ethane
propene
propane
0
1
2
3
4
5
6
7
0 1 2 3 4 5 6 7
Ab
init
io p
red
icte
d y
ield
(w
t%)
Experimental yield (wt%)
1,3-butadiene
1-butene
n-butane
benzene
H2
without a single
adjusted parameter
13-Nov-17
26/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Industrial ethane/propane cracker
Satisfactory agreement for all major product yields,
based on ab initio data only.
0
10
20
30
40
50
60
Pro
du
ct
yie
ld (
w%
)
experimental
simulated
CH4
13-Nov-17
27/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor: 3D alternatives
• Process
• Conclusions
13-Nov-17
28/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Coke formation
Optimization by
- Feed additives
- Metallurgy & surface technology
- 3D reactor technology
Deposition of a carbon layer on the reactor surface
Thermal efficiency
Product selectivity
Decoking procedures
Estimated annual cost to industry: $ 2 billion
2L. Benum, "Achieving Longer Furnace Runs at NOVA Chemicals," in AIChE Spring National Meeting, 14th Annual Ethylene Producers’ Conference, New Orleans, Louisiana, 2002.
13-Nov-17
29/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Coke formation: 3D reactor technologies13-Nov-17
~ 15 °C
~100 °C
Reduce convective heat resistance
Better mixingIncrease surface area
Cokes formed here
T ↑ coking rate ↑↑
~60 °C
*Borealis.com, kubota.com, Technip.com
30/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
CFD and Coking kinetics: Coke layer growth
SOR (0 hrs)
48 hrs
Fin c-Rib
SOR
10 days
13-Nov-17
31/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Millisecond propane cracker
• Feedstock 118.5 kg/h propane
• Propane conversion 80.15 % (± 0.05%)
• Steam dilution 0.326 kg/kg
• CIT 904 °C
• COP 170 kPa
• Different geometries simulated• Same reactor volume
• Same axial length
• Same minimal wall thickness
Bare c-RibFin
13-Nov-17
32/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Millisecond propane cracker: run length simulation
SOR 96h48h
Increasing run length
13-Nov-17
33/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Tube Metal Temperature
Max. TMT increasesThermal resistance coke layer
Bare
c-Rib
Fin
13-Nov-17
34/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor
• Process
• Conclusions
13-Nov-17
35/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor
• Process: furnace
• Conclusions
13-Nov-17
36/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Coupled reactor-furnace simulation
External coil temperature
Heat flux to reactors
Reactor(COILSIM1D)
Furnace simulationconvergenceFURNACE/
COILSIM1D
Hu, G. et al.,Industrial & Engineering Chemistry Research, 54 (9), 2453-2465, 2015
13-Nov-17
37/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Full furnace simulation
Ultra Selective Conversion (USC)
100% floor burner Fuel composition mol%: CH4(89%)-
H2(11%) U coil Feedstock: Naphtha
Coupled modeling
3D CFD furnace model 1D reactor model (COILSIM1D) Detailed cracking kinetics (CRACKSIM)
Zhang, Y. et al.,AIChE Journal 61 (3), 936-954, 2015
13-Nov-17
38/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Flue gas: velocity and concentration fields
Detailed case• Stronger turbulence• Faster reaction
detailed simplified
Methane mole fraction
13-Nov-17
39/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Tube wall temperature field: local hot spots
This information is key for run length
13-Nov-17
40/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Outline
• Introduction
• Feedstock
• Kinetics
• Reactor
• Process
• Conclusions
13-Nov-17
41/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Conclusions
• Shannon Entropy maximization to reconstruct feedstocks in
terms required for a microkinetic model (SIMCO)
• Consistent data set for thermochemistry and kinetics of
hydrocarbon radical chemistry (CRACKSIM)
• Ab initio simulation of steam cracking of C2/C3/C4
• Emergence of 3D reactor technologies: CFD as tool
• Integration of reactor/convection section/furnace (COILSIM1D)
integration of computational chemistry methods with
engineering tools, e.g. CFD, at larger time and length
scales and experimental validation provides a
powerful tool for the optimization and/or design of
industrial units
13-Nov-17
42/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
Acknowledgments
• Profs. Marie-Françoise Reyniers,Maarten Sabbe, Feng Qian
(ECUST)
• Drs. Steven Pyl, Nick Vandewiele,Thomas Dijkmans, Paschalis
Paraskevas, Marko Djokic, Ruben Van de Vijver,David Van
Cauwenberge, Andres Munoz (AVGI),Yu Zhang (ECUST)
• PhD students Pieter Reyniers, Laurien Vandewalle, Nenad Ristic,
Florence Vermeire, Moreno Geerts, Aleksandar Bojkovic,
Muralikrishna Khandavilli
13-Nov-17
43/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017
LABORATORY FOR CHEMICAL TECHNOLOGY
Technologiepark 914, 9052 Ghent, Belgium
T 003293311757
https://www.lct.ugent.be
GLOSSARY
• SFT: Swirl Flow Tube, a tube with a helicoidal centerline.
The helix amplitude is smaller than or equal to the tube
radius.
• Swirl flow: a whirling or eddying flow of fluid.
• Swirl number: ratio of tangential over axial momentum
transfer
• Wall shear stress: component of stress parallel with the wall.
It is the product of the viscosity and the derivative of axial
velocity with respect to the radial coordinate.
13-Nov-17
45/1728th Asian-Pacific Chemical Reaction Engineering (APCRE 2017) Symposium
East China University of Science and Technology, Shanghai, China, Nov. 12-15, 2017