Production of Bio-Ethylene : Alternatives for Green ... · Production of Bio-Ethylene : Alternatives for Green Chemicals and ... Steam Cracking * T. Ren et al. , ... Renewable Naphtha

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

?

Green OlefinsISGC 2013, La Rochelle, Fr, Mau 2013




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


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


Renewable Pilot Plant Feedstocks

Poultry Fat &Yellow Grease

HDO - FAT1

RenewableNaphtha

Hydrotreatment+ Hydrocracking

2

Hydrotreatment


Pine Wood

HDO - TOFA3

Kraft Pulping + Hydrotreatment


9

Detailed feedstock analyses


Using comprehensive 2D gas chromatography

HDO-DTO

Hydrodeoxygenated Tall Oil FractionsHDO-TOFA

HDO-DTO

GC×GC-FID


10

Group-type AnalysesHDO-FAT


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%

]


11

Carbon Number Distributions

C3 – C12

C17


Naphtha

C7 – C31 Gas Oil

C18

HDO-TOFA

C17 C18C16

HDO-FAT


12

Outline


Feedstock analyses





Conclusions



Steam Cracking Pilot PlantISGC 2013, La Rochelle, Fr, Mau 2013

13

Gas Fired Furnace + Reactor

Online Analysis Section

Control Room

High temperaturesampling system

HCFeed

H2O

CH4 PAHs


HDO-FAT: On-line Effluent AnalysisISGC 2013, La Rochelle, Fr, Mau 2013


VOLATILITY

PO

LAR

ITY

-BA

SE

D

PYROLYSIS GASOLINE12.2 wt%

PYROLYSIS FUEL OIL0.93 wt%

C4-86.9 wt%

COT = 850°C

15


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


ReferenceFeedstock

Renewable Feedstocks


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


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


ReferenceFeedstock

Co-cracking with Renewable Feeds


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

17

Effect of feedstock on run-length COT = 850°C



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


18

Outline


Feedstock analyses





Conclusions



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 −−↔+= ••



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


0

1

2

3

4

5

6

7

8

760 780 800 820 840 860 880

Yie

ld [w

t%]


toluene

styrene

benzene

0

2

4

6

8

10

12

14

16

760 780 800 820 840 860 880

Yie

ld [w

t%]


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


21

Outline


Feedstock analyses





Conclusions



• 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


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


Documents

Production of Bio-Ethylene : Alternatives for Green ... · Production of Bio-Ethylene : Alternatives for Green Chemicals and ... Steam Cracking * T. Ren et al. , ... Renewable Naphtha