production of bio-ethylene : alternatives for green ... · production of bio-ethylene :...
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Production of Bio-Ethylene :
Alternatives for Green Chemicals and
PolymersKevin M. Van Geem1, Thomas Dijkmans, Jinto M. Anthonykutty2,
Steven P. Pyl1,Ali Harlin2, Guy B. Marin1
1 Laboratory for Chemical Technology, Ghent University, Belgium2 VTT Technical Research Center, Finland
Steven P. Pyl, Kevin M. Van Geem, Ramin AbhariMarie-Françoise Reyniers, Guy B. Marin
Member of Research funded by
Ethene
Propene
1,3-Butadiene
BTXBiomass
Natural Gas
Crude Oil
Heat
1 ton/ton *
CO2
15 GJ/ton *
Ghent University - Laboratory for Chemical Technology 2
Steam Cracking
* T. Ren et al., Energy (2008)
Ethane
LPG & NGL
Naphtha
Gas Oil
Public Defense, 04/10/2012
Green OlefinsISGC 2013, La Rochelle, Fr, Mau 2013
3Ghent University - Laboratory for Chemical Technology
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Green OlefinsISGC 2013, La Rochelle, Fr, Mau 2013
4Ghent University - Laboratory for Chemical Technology
Public Defense, 04/10/2012
Ghent University - Laboratory for Chemical Technology 5
Biomass to Fuels and Olefins
Green Fuels
Triglyceride and Fatty Acid based Biomass
Hydrocarbon Liquids
Green Olefins
CO, CO2, H2O
Hydrodeoxygenation
SteamCracking
Fluid Cat. Cracking
Hydro-Cracking
Renewable Feeds for Conventional CrackersISGC 2013, La Rochelle, Fr, Mau 2013
6Ghent University - Laboratory for Chemical Technology
HDO – FAT HDO – TOFA& HDO – DTO
Poultry Fat & Yellow Grease
Tall Oil Fractions
(TOFA & DTO)
GREEN OLEFINS & AROMATICS
Steam Cracking
ISGC 2013, La Rochelle, Fr, Mau 2013
7
Outline
Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass
Feedstock analyses
Effect of feedstock on product yields
Effect of feedstock on run-length
Introduction: Green Olefins
Ghent University - Laboratory for Chemical Technology
Conclusions
Reactor and Kinetic modeling
Effect of Coil Outlet Temperature on product yields
Ghent University - Laboratory for Chemical Technology 8
Renewable Pilot Plant Feedstocks
Poultry Fat &Yellow Grease
HDO - FAT1
RenewableNaphtha
Hydrotreatment+ Hydrocracking
2
Hydrotreatment
Public Defense, 04/10/2012
Pine Wood
HDO - TOFA3
Kraft Pulping + Hydrotreatment
ISGC 2013, La Rochelle, Fr, Mau 2013
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Detailed feedstock analyses
Ghent University - Laboratory for Chemical Technology
Using comprehensive 2D gas chromatography
HDO-DTO
Hydrodeoxygenated Tall Oil FractionsHDO-TOFA
HDO-DTO
GC×GC-FID
ISGC 2013, La Rochelle, Fr, Mau 2013
10
Group-type AnalysesHDO-FAT
Ghent University - Laboratory for Chemical Technology
HDO-TOFA HDO-DTO
Naphtha Gas Oil Natural Gas Condensate
0
10
20
30
40
50
60
70
80
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
Wei
ght F
ract
ion
[wt%
]
ISGC 2013, La Rochelle, Fr, Mau 2013
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Carbon Number Distributions
C3 – C12
C17
Ghent University - Laboratory for Chemical Technology
Naphtha
C7 – C31 Gas Oil
C18
HDO-TOFA
C17 C18C16
HDO-FAT
ISGC 2013, La Rochelle, Fr, Mau 2013
12
Outline
Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass
Feedstock analyses
Effect of feedstock on product yields
Effect of feedstock on run-length
Introduction: Green Olefins
Ghent University - Laboratory for Chemical Technology
Conclusions
Reactor and Kinetic modeling
Effect of Coil Outlet Temperature on product yields
Steam Cracking Pilot PlantISGC 2013, La Rochelle, Fr, Mau 2013
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Gas Fired Furnace + Reactor
Online Analysis Section
Control Room
High temperaturesampling system
HCFeed
H2O
CH4 PAHs
Ghent University - Laboratory for Chemical Technology
HDO-FAT: On-line Effluent AnalysisISGC 2013, La Rochelle, Fr, Mau 2013
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VOLATILITY
PO
LAR
ITY
-BA
SE
D
PYROLYSIS GASOLINE12.2 wt%
PYROLYSIS FUEL OIL0.93 wt%
C4-86.9 wt%
COT = 850°C
15
Effect of feedstock on product yields
Yields [wt%]θ ≈ 0.3s, δ = 0.45kg/kg
Full Range Naphtha
HDO-FAT HDO-TOFA
Methane 15.9 11.0 10.4
CO 0.08 0.15 0.11
CO2 0.01 0.07 0.08
P/E = 0.50
COT 870°C =1600°F 835°C = 1535°F 820°C = 1510°F
Fuel Oil 1.54 0.56 11.3
Ghent University - Laboratory for Chemical Technology
ReferenceFeedstock
Renewable Feedstocks
ISGC 2013, La Rochelle, Fr, Mau 2013
Benzene 9.74 5.23 4.35
Toluene 4.59 1.49 1.42
Xylenes 1.35 0.18 0.26
Ethylene 26.5 38.4 35.4
Propylene 13.1 19.5 17.5
1.3-butadiene 5.41 7.77 4.48
16
Effect of feedstock on product yields
Yields [wt%]θ ≈ 0.3s, δ = 0.45kg/kg
LightNaphtha
+15% HDO-TOFA +15% HDO-DTO
Methane 15.6 14.8 15.4
CO 0.03 0.05 0.04
CO2 0.01 0.01 0.02
P/E = 0.55
COT 850°C =1560°F 850°C = 1560°F 850°C = 1560°F
Fuel Oil 1.34 2.50 2.51
Ghent University - Laboratory for Chemical Technology
ReferenceFeedstock
Co-cracking with Renewable Feeds
ISGC 2013, La Rochelle, Fr, Mau 2013
Benzene 6.05 6.03 6.14
Toluene 2.47 2.49 2.50
Xylenes 0.60 0.68 0.55
Ethylene 29.9 30.0 29.6
Propylene 16.5 17.1 16.5
1.3-butadiene 5.32 5.19 5.29
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Effect of feedstock on run-length COT = 850°C
Ghent University - Laboratory for Chemical Technology
ISGC 2013, La Rochelle, Fr, Mau 2013
ReferenceFeedstocks
Pilot plant cokes test Cokes formation during 6-h steady state operation
0
1
2
3
4
5
6
7
HDO-TOFA Ethane PetroleumNaphtha
Natural GasCondensate
g co
kes
/ 6 h
RenewableFeedstocks
ISGC 2013, La Rochelle, Fr, Mau 2013
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Outline
Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass
Feedstock analyses
Effect of feedstock on product yields
Effect of feedstock on run-length
Introduction: Green Olefins
Ghent University - Laboratory for Chemical Technology
Conclusions
Reactor and Kinetic modeling
Effect of Coil Outlet Temperature on product yields
Reactor and Kinetic Modeling
Concentration Profiles & Product YieldsTemperature and Pressure Profile
System of Differential Equations
Microkinetic Model
Feedstock Composition
Reactor Geometry
Operating Conditions
Free RadicalMechanism
•• +↔− 2121 RRRR
HRRRHR 2121 −+↔+− ••
321321 RRRRRR −−↔+= ••
ISGC 2013, La Rochelle, Fr, Mau 2013
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numerical integration
Ω
υ= ∑=
k
n
1kkj
j rdz
dF r
( )∑ ∑ ∆−Ω+ω=j k
krkV,pjj Hrq dzdT
c F
zu
u u r d
f 2zdpd
g2
g
bt
t
∂∂ρα+ρ
πζ+α=−
Plug flow
Reactor Model
0
5
10
15
20
25
30
35
40
45
760 780 800 820 840 860 880
Yie
ld [w
t%]
Coil Outlet Temperature [ C]
propylene
ethylene
1.3-butadiene
HDO-FAT: Effect of Coil Outlet TemperatureISGC 2013, La Rochelle, Fr, Mau 2013
20Ghent University - Laboratory for Chemical Technology
0
1
2
3
4
5
6
7
8
760 780 800 820 840 860 880
Yie
ld [w
t%]
Coil Outlet Temperature [ C]
toluene
styrene
benzene
0
2
4
6
8
10
12
14
16
760 780 800 820 840 860 880
Yie
ld [w
t%]
Coil Outlet Temperature [ C]
propane
ethane
methane
Model Validation
simulated yields (lines) vs.pilot plant yields (symbols)
θ ≈ 0.3 s,δ = 0.45 kg/kg
COT: 775°C 865°C
ISGC 2013, La Rochelle, Fr, Mau 2013
21
Outline
Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass
Feedstock analyses
Effect of feedstock on product yields
Effect of feedstock on run-length
Introduction: Green Olefins
Ghent University - Laboratory for Chemical Technology
Conclusions
Reactor and Kinetic modeling
Effect of Coil Outlet Temperature on product yields
• Oil does a lot more than provide fuels for transportation
• Triglyceride based biomass is a promising starting materialfor the production of ‘green olefins’
• Hydrodeoxygenation of waste fats as well as tall oilsproduces highly paraffinic liquids
• Steam cracking of these liquids results in high light olefin yields
• Single-event microkinetic modeling provides a rigorous fundamental basis for industrial reactor models
ConclusionsISGC 2013, La Rochelle, Fr, Mau 2013
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AcknowledgementISGC 2013, La Rochelle, Fr, Mau 2013
Thank you foryour attention!
Long Term Structural
Methusalem Funding of
the Flemish Government
Maarten Sabbe, Laboratory for Chemical Technology, Gent, Belgium
Ramin Abhari, Syntroleum, Tulsa (OK), USA
Ghent University - Laboratory for Chemical Technology 23