From fossil to renewable feedstocks

Methusalem Advisory Board meeting, Ghent, 17 June 2011

1

From fossil to

renewable feedstocksKevin M. Van Geem


2

Outline

• Introduction

• Fast pyrolysis of biomass

• Pyrolysis of renewable fuels: model components

• Biomass to ethylene routes

• Conclusions


3

Introduction

P6: From fossil to renewable feedstocks

Multi-scale Modeling and design of chemical Reactions and Reactors


4

Introduction

algae

waste bagasse

wood

corn

sugar

cane

short-rotation crops

wood wastes

etc.

Transition from fossil to renewable resources

Biomass


5

Outline

• Introduction




• Conclusions


6

Lignocellulosic biomass

Composition strongly depends on origin biomass

plant biomass

fats, waxes, starches, terpenes

etc…

low molecular weightsubstancesmacromolecular substances

hemi-cellulose

organicmolecules

inorganicspoly-

saccharideslignin

extractivescellulose


7

Biomass: cellulose


8

Biomass: hemicellulose


9

Biomass : lignin

Genetic engineering allows to modify the lignin structure and fraction of lignin


10

Biomass: pyrolysis products


11

Biomass: pyrolysis process

plant biomass

bio oilgas char

CO2, CO, CH4, H2, lower amounts of

C2’s

aldehydes, ketones, phenol

ethers, alkylphenols,

polyaromaticsetc…

pyrolysis

active carbon

15% 15%70%


12

Experimental set-up

Venderbosch and Prins, 2010

AUGER reactor Fluidized bed reactor


13

Auger reactor


14

Bio oil: main componentsPine wood Bio-oil

Fast Pyrolysis

300 – 600 C

0.5 – 2s

Gas & Char

GC GC Aldehydes, Furans,

Ketones & Alcohols

Carboxlylic Acids

Phenols & Phenons

Guaicols, Syringols &

Catechols

Anhydrosugars

Hydroxy Acids


15

GC×GC set-up

TOF-MS

GC×GC

Heated

Transfer-

line

FID

OVEN

TOF-MS

He

Rtx-1 PONA

BPX-50

BPX-50

injector

Liquid CO2

(1)

(2)

(3)

(3)

(6)

(5)

(4)

(7)


16

GC×GC set-up

Initial objective

Maximal agreement

between

FID and TOF-MS

chromatograms

modulator

FID

Quantitative results

TOF-MS

Peak identification

Van Geem, Pyl, et al. J. Chrom. A. 2010


17

GC×GC: Data Processing

4s 4s 4s 4s 4s 4s 4s 4s

1st dimensionseparation

Modulation 2nd dimensionseparation

Detection

Enhanced Resolution

Enhanced Signal/Noise Ratio


18

GC×GC: Data Processing


19

Bio oil: main components

O

OH

O

HO

OH

O

O

O

HO

levoglucosan

vanilin

eugenol

methyl-

guaiacolcycloteneO

O

furfural

OO

2-furanone

HO

HOO

O

OH

O

HO

guaiacol

190 components

GCxGC-FID & GCxGC-TOF-MS

analysis

LigninCellulose

Anhydrosugar13%

Ketone8%

Furan13%

Guaiacol20%

Phenol2%

Alcohol5%

Syringol2%

Catechol1%

Cyclo-ketone8%

Aldehyde9%

Carboxylic acid19%


20

Bio oil: main components

levoglucosan

OH

HO

OCH3

vanilin


21

Bio oil: untreated


22

Bio oil: hydrotreated


23

Outline

• Introduction




• Conclusions


24

Methodology


27

Validation: pyrolysis in laminar flow reactor

1: butanol vessel, 2: water vessel, 3: electronic balance, 4: pump, 5: valve, 6: evaporator, 7: mixer,8: heater, 9: air, 10: pressure regulator, 11: mass flow controller, 12: nitrogen, 13: reactor, 14: nitrogen internal standard, 15: oven, 16: GC for formaldehyde and water, 17: GC×GC

18: cyclone, 19: condenser, 20: dehydrator, 21: GC for C4-, 22: data acquisition

9

MFC MFC

T1

T2

T3

T4

T5

T6

T7

T8

19

17

21

16

1

2

3

3

4

4

5

5

6

6

7

8

5

5

10 10

12

11 11

13

14

15

18 20

22

VENT


28

GCxGC Tof-MS methyldecanoate

Pyl et al., 2011


29

Influence COT MD pyrolysis


30

Influence COT MD pyrolysis


31

Influence COT: MD pyrolysis


32

Influence dilution: MD pyrolysis


33

Mechanism validation


34

Mechanism validation

0

2

4

6

8

10

12

14

0 20 40 60 80 100

CH

4Y

ield

[w

t%]

Conv. [wt%]

Zhaoyu Luo et al.

Herbinet et al. (Red.)

Herbinet et al. (Full)

Experimental

0

5

10

15

20

25

30

0 20 40 60 80 100

C2H

4Y

ield

[w

t%]

Conv. [wt%]

Zhaoyu Luo et al.



Experimental

0

1

2

3

4

5

6

7

8

9

10

0 20 40 60 80 100

CO

2Y

ield

[w

t%]

Conv. [wt%]

Zhaoyu Luo et al.



Experimental

0

2

4

6

8

10

12

14

16

18

0 20 40 60 80 100

CO

Yie

ld [

wt%

]

Conv. [wt%]

Zhaoyu Luo et al.



Experimental


35

Reaction path analysis

0

5

10

15

20

0 20 40 60 80 100

C3

:1-2

Yie

ld [

wt%

]

Conv. [wt%]

Zhaoyu Luo et al.



Experimental


36

Butanol work

Oxygenated fuels

Improve octane rating

impede sooting and particulate formation

Promote formation of toxic byproducts

Examples of oxygenated fuel additives

1979 (US): MTBE (H2O decontamination)

Late 70’s (US): Ethanol (21.2 MJ/L)

2000’s (Dupont/BP): 1-Butanol (29.2 MJ/L)

2015: 2-methyl-1-propanol or 2-butanol?

Van Geem et al., 2010; Harper et al. 2011


37

Acetone/butanol/ethanol pyrolysis/combustion

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0 20 40 60 80 100

Yie

ld (w

t%)

Conversion [%]

BUT12

nButenes

0.0

5.0

10.0

15.0

20.0

25.0

0 20 40 60 80 100

Yie

ld (w

t%)

Conversion [%]

C2H4

C2H4

0.0

5.0

10.0

15.0

20.0

25.0

30.0

0 20 40 60 80 100

Yie

ld (w

t%)

Conversion [%]

CH4

CH4

CH4 C2H4

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

0 20 40 60 80 100

Yie

ld (w

t%)

Conversion [%]

C3H6

C3H6

C3H6 nC4H8

0

5

10

15

20

25

30

35

40

45

0.50 1.00 1.50 2.00

flam

e s

pe

ed

[cm

/s]

equivalence ratio

Acetone - Burluka et al. (2010)

Acetone - Pichon et al. (2009)

Acetone

ABE

T=298K


38

Outline

• Introduction



• Biomass to ethylene routes: from fats en greases

• Conclusions


39

Biomass to hydrocarbon routes

Feedstock

Process

Diesel, Jet, Naphtha

• Biomass to hydrocarbons

– Gasification and enzyme routes not commercial

– Hydrotreated Vegetable Oil (e.g. Bio-Synfining™) commercialized

• Economics based on diesel and jet fuel

• Naphtha co-product tested as feedstock for conventional steam crackers


40

Feedstock

Brown grease

Seed oils

Yellow grease

Waste animal fats

Seaweed oils

Tall oil

fatty acid

Algal oils

U.S. sources ~ 360,000 BPD (16 million tonne/y) hydrocarbon equivalent …and increasing


41

Process

FEED

JET

Hydro-

deoxygenatorHydrocracker

Water

C5-C9

C10-C15

C15-C18+

C3-C18+

Recycle

Compressor

LPG

Naphtha

C3-C4

Fractionation

Hydrogen

Makeup

Simple, low capital cost process


42

Chemistry

O

O

O

O

O

OHC

+ 6 H2O + C3H8

+ 15 H2

3 (1a)

(n-octadecane)

(typical triglyceride with linoleic, oleic, and stearic acids)

H2C

H2C

HO

O

+ 4 H2

+ 2 H2O (1b)

NiMo cat

(isoparaffinic

hydrocarbons)

NiMo cat

Bi-functionalcatalyst

(2)(typical)

+ + H2

Paraffinic hydrocarbons from bio oils via hydrodeoxygenation(Eqs 1a-b) and hydrocracking (Eq 2)


43

Renewable kerosene vs Petroleum kerosene

GC×GC-FID analysisPetrochemical

Kerosene

n-paraffins12%

iso-paraffins86%

Naphthenes2%

C10 – C18

Aromatics free

paraffines24%

isoparaffines26%

naphthenes33%

aromatics17%

Paraffinic

Kerosene


44

GC GC analysis renewable naphtha

10 40200

4

benzene

30

toluene

ethyl-

benzene

n-C13n-C12n-C11

n-C10n-C9

n-C8

n-C7

n-C6

propyl-

benzene

butyl-

benzene

Hydrodeoxygenation

Hydrocracking

Naphtha

Kerosenen-Paraffins

32.4%

iso-Paraffins59.9%

Olefins0.4%

Naphthenes6.5%

Aromatics0.8%

Pyl et al., accepted


45

Follow up story

Paraffinic

Kerosene

C10 – C18 Aromatics free

Hydro-

deoxygenation

Hydrocracking

nC16

C18 olefines

nC18

nC15

nC14

nC17

nC19

nC20

nC10

nC11nC12

nC13

nC14nC15 nC16

nC17


46

Simulation results

Product Yield (wt%)

COT = 820°C COT = 850°C COT = 880°C

hydrogen 0.9 1.0 1.1methane 8.2 9.7 10.9ethylene 37.3 39.9 40.4ethane 3.0 2.9 2.8propylene 14.6 14.0 12.4propane 0.3 0.3 0.3isobutene 0.2 0.3 0.32-butene 0.7 0.7 0.61-butene 3.9 1.9 0.71,3-butadiene 7.3 6.6 5.6n-butane 0.1 0.1 0.1benzene 6.7 8.6 9.5toluene 2.5 3.3 3.8Et-benzene 0.2 0.4 0.7xylene 0.1 0.1 0.1styrene 0.4 1.0 1.9indene+ vinyl toluene 0.3 0.5 0.7naphthalene 0.1 0.4 1.2


47

Outline

• Introduction



• Biomass to ethylene routes: from talloil

• Conclusions


48

Talloil: byproduct of Kraft process


49

Pilot plant set-up


50

Pilot plant set-up

cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7

air

oil

N2

flare

DHA

FURNACE & REACTOR TLE ANALYSIS

H2O

hyd

roca

rbo

ns

FEED

IR-GA

preheating & mixing reactor zone

P P P PP

condensate

co

ole

r

GC×GC

RGAPGA

water

oven


51

Pilot plant set-up

Nitrogen is used as internal standard

Methane functions as a second internal standard

RGA (TCD)

RGA (FID)

PGA (TCD)

DHA (FID)

GC×GC (FID)

H2 CO2 C2H4 C2H6 C2H2 CH4 CON2

C2 C3 C4CH4

CO2 C2H4 C2H6 C2H2 CO CH4

C2 C3 C4CH4 C5 C6 ...

N2

...CH4

ch

eck

C16

C25


52

TOFA GC

1st dimension retention time (min)

0 25

2n

d d

ime

nsi

on

re

ten

tion

tim

e (

s)

0

5 phenanthreneC1-triaro

50 75 100

nC16nC18

nC20

Norabitane

C12H14O

Norabitane-

aro

iC8

nC8

nC10nC12

nC14

nC22

nC24

nC26

C18:1

C16:1


53

DTO feedstock analysis


0 25

2n

d d

ime

nsi

on

re

ten

tion

tim

e (

s)

0


50 75 100

nC16

iC8

nC18

nC20

Norabitane

C12H14O

Norabitane-

aro


54

Naphtha/DTO


0 25

2n

d d

ime

nsi

on

re

ten

tion

tim

e (

s)

0


50 75 100

nC16nC18

nC20

NorabitaneC12H14O

Norabitane-

aro

benzene

toluene

xylenes

C2 arom

nC4

naphthenes

nC10


55

TOFA/DTO feedstock analysisComponent TOFA

Wt%

DTO

Wt%

C12H14O 0.053 0.802

C16:0 FAME 0.713 0.371

C18:1 FAME 2.280 0.243

C18:2 FAME 0.591 0.626

cyclo C18 0.912 0.117

decane 0.137 0.218

dodecane 0.084 0.150

eicosane 3.148 6.194

heneicosane 0.604 0.575

heptadecane 13.235 8.844

heptane 0.279 0.392

hexadecane 0.424 0.412

hexane 0.790 15.657

isoparaffin C16 0.062 0.046





nonadecane 1.164 1.829

nonane 0.113 0.145

norabietane 6.128 9.984

norabietane-1aro 1.592 3.521

octadecane 59.520 42.797

octane 0.136 0.180

olefin C18 2.247 2.016

olefin C20 0.781 0.644

paraffin C22 0.292 0.518

paraffin C23 0.250 0.235

paraffin C24 0.359 0.158

paraffin C25 0.282 0.122

paraffin C26 0.195 0.207

pentadecane 0.108 0.138

tetradecane 0.051 0.077

tridecane 0.075 0.156

undecane 0.152 0.220


56

DTO/naphtha feedstock analysis

0

5

10

15

20

25

30

35

40

45

50

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

Wei

ght f

ract

ion

%

Carbon number


57

GC×GC FID chromatogram TOFA5

080

benzene

ethyl-

benzene

C4-

mono-

aromatics

toluenedi-aromaticsstyrene

cyclopentadiene

naphthalene

acenapthylene

methyl-

naphthalenes

0 1st dimension retention time (min)

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

phenanthrene

unconverted

TOFA

nC18nC16

C18:1 ester

indene


58

Detailed effluent with GC×GC FID

Over 100 components are identified and quantified each run


59

Conslusions GC×GC analysis of bio-oils produced by fast pyrolysis of biomass allows to quantify more than 50

components qualitatively

Pyrolysis of model components for renewable fuels provides valuable information to validate the

combustion chemistry

Hydrodeoxygenation of waste fats and greases gives a highly paraffinic renewable feedstock

Excellent feedstock for conventional steam crackers

High Ethylene and Propylene yields

Low Coking tendency = long run lengths

Opportunity for petrochemical producers to transition to biorenewable feeds without modifying

process

Hydrodeoxygenated tall oil is also a valuable feed for producing light olefins, but smaller

ethylene and propylene yields are obtained compared to the DHO product of waste fats


60

Glossary

Lignin: a polyaromatic structure, part of cell walls of plants and algae

Cellulose: a polysaccharide consisting of a linear chain of several

hundred to over ten thousand β(1→4) linked D-glucose units

Hemicellulose: a polysaccharide consisting of include xylose, mannose,

galactose, rhamnose, and arabinose monomers

Bio-oil: oil produced from lignocellulosic biomass via pyrolysis

Tall oil: by-product of the Kraft process of wood pulp manufacture

Documents

From fossil to renewable feedstocks