Modern catalytic technologies for converting …...Carlson et al., Green Gasoline by Catalytic Fast...

Catalysis Center for Energy Innovation

Modern catalytic technologies for converting biomass to fuels

An supported by the

,,

Presented by Dion Vlachos, Director

www.efrc.udel.eduwww.efrc.udel.edu


Objectives and ApproachObjectives and ApproachObjectives and ApproachObjectives and Approach

ObjectivesD l h bli i l di i d di ll Develop the enabling science leading to improved or radically new (heterogeneous) catalytic technologies for viable and economic operation of biorefineries from various (lignocellulosic) biomass feed stocksfeed stocks

Develop technology and enable technology transfer

Educate the workforce needed to further develop and implement Educate the workforce needed to further develop and implement these new technologies, which in turn will lead to further sustainable economic growth and reduced energy dependence of the U.S.

ApproachDevelop paradigms for major technologies of biorefineries by picking prototype platforms


picking prototype platforms


R h ThR h ThResearch ThrustsResearch Thrusts

Hierarchical MultiscaleMaterials

Multiscale Modeling

Characterization Techniques

Crosscutting Research

Thrust

Chemicals Catalytic Degradation/ Direct Carbon FCsTechnological

Platform

ReformingHH22 y g

Oil UpgradePlatform

ChemicalsChemicals FuelsFuels ElectricityElectricity

Reaction Pathways, Kinetics, Structure-Property RelationshipsScience

Process Innovation OptimizationProcessing


Process Innovation, OptimizationProcessing


R h ThR h ThResearch ThrustsResearch Thrusts

Hierarchical MultiscaleMaterials

Multiscale Modeling

Characterization Techniques

Crosscutting Research

Thrust

Chemicals Catalytic Degradation/ Direct Carbon FCsTechnological

Platform

ReformingHH22 y g

Oil UpgradePlatform

ChemicalsChemicals FuelsFuels ElectricityElectricityCO+2H2/FT

Reaction Pathways, Kinetics, Structure-Property RelationshipsScience

Process Innovation OptimizationProcessing


Process Innovation, OptimizationProcessing


ThermochemicalThermochemical transformation of transformation of lignocellulosic biomasslignocellulosic biomass

Traditional paths entail high temperatures and suffer from Traditional paths entail high temperatures and suffer from carbonCPOX forms no carbon

il F l

Cat. upgrade

Pyrolysis

OilCharTar

Fuel

Biomass

y yHigh T Syngas

CharGasification MethanolSynfuel




Traditional paths entail high temperatures and suffer from Traditional paths entail high temperatures and suffer from carbonCPOX forms no carbon

il F l

Cat. upgrade

Pyrolysis

OilCharTar

Fuel

Biomass

y yHigh T Syngas

CharGasification MethanolSynfuel

CPOX SyngasVery high T




Sugar conversion via fermentation established Oil Fuel

Cat. upgradefermentation established

Low rates, expensive enzymes Pyrolysis

Hi h T

OilCharTar

Fuel

Biomass

High T SyngasChar

GasificationMethanolSynfuel

CPOX S ngasVery high T CPOX SyngasVery high T

Ethanol, butanolBiological,Enzymes

drol

ysis

Chemicals

Hyd Sugars




Thermochemical route exhibits faster rates and Oil Fuel

Cat. upgradeexhibits faster rates and could be tuned

PyrolysisHi h T

OilCharTar

Fuel

Biomass

High T SyngasChar

GasificationMethanolSynfuel

CPOX S ngasVery high T CPOX SyngasVery high T

Ethanol, butanolBiological,Enzymes

drol

ysis

Chemicals

Hyd Fuels:

SyngasH2Alkanes

Transportation fuelsEthyl levulinateDimethylfuran

Sugars

Thermochemical


Alkanes HMFFurfural

yγ-valerolactone

Thermochemical


l i l i / il i l i / i il dil d

Overarching Goal: Develop the science-based to

Catalytic Fast Pyrolysis/BioCatalytic Fast Pyrolysis/Bio--Oil UpgradeOil Upgrade

Overarching Goal: Develop the science based to enable the conversion of cellulose to fuels

Develop an understanding of the catalytic fastDevelop an understanding of the catalytic fast pyrolysisDevelop and characterize suitable catalystsDevelop and characterize suitable catalystsDevelop models for diffusion and reaction inside and outside microporous materialsand outside microporous materialsPerform kinetic studies



Catalytic Fast Pyrolysis Catalytic Fast Pyrolysis

G. Huber/UMass

Catalytic Fast Pyrolysis Catalytic Fast Pyrolysis Solid biomass converted into aromatics in a single reactor at h t id tishort residence times:

Liquid fuel that fits into existing infrastructureL t l bl lit Low cost, recyclable zeolite catalystsChallenge is controlling chemistrychemistry


Carlson et al., Green Gasoline by Catalytic Fast Pyrolysis of Solid Biomass-derived Compounds, ChemSusChem, 1, 397-400 (2008)


Catalytic Fast Pyrolysis: Overall yieldsCatalytic Fast Pyrolysis: Overall yieldsCatalytic Fast Pyrolysis: Overall yieldsCatalytic Fast Pyrolysis: Overall yields

90%

100% UndefinedCoke

60%

70%

80%

eld

(%)

CokeCO2COAromatics

Reaction Conditions: Temperature 600oC; ZSM-5; Catalyst/Feed 30%

40%

50%

Car

bon

Yie

; y /Ratio 19

0%

10%

20%

Maximum Yield:

0%Xylitol Glucose Cellobiose Cellulose

www.efrc.udel.eduwww.efrc.udel.eduCarlson, Vispute, and Huber, Green Gasoline by Catalytic Fast Pyrolysis, ChemSusChem.

C6O6H12 → 12/22 C7H8 (63 % Yield) + 48/22 CO (36 % Yield) + 84/22 H2O


Cellulose Pyrolysis in TGA at fast Cellulose Pyrolysis in TGA at fast heatingheating

G. Huber/UMass

y yy y ggon

(α

)

• Cellulose can be 100% pyrolyzed

onve

rsio • Cellulose pyrolysis to

anhydrosugars is endothermic

Ki i d h f ff

⎛ ⎞ulos

e Co • Kinetics and heat transfer effects

both need to be taken into account

( ) ( ) 01 , exp As

s

d Ek k T kdt RTα α

⎛ ⎞= − = −⎜ ⎟

⎝ ⎠Cellu

Cellulose pyrolysis at three different heating ates in TGA

( ) ( ) Hdtdm

dtdT

cmTThA spser Δ+−=−

αα 00 1

Energy Balance


heating rates in TGALin et al., Kinetics and Mechanism of Cellulose Pyrolysis, J. Phys. Chem. C (2009) 113, 20097-20107


Cellulose Pyrolysis ChemistryCellulose Pyrolysis Chemistry

G. Huber/UMass

OO

OHHOO

HO

O

OHHOO

HO

OHO OH

O

OH

Anhydro oligosaccharidesO

OH

Cellulose

O

n

Anhydro-oligosaccharidesn = 0: Cellobiosan (DP2)n = 1: Cellotriosan (DP3)....n = 7: Septaosan (DP7)

O

OH

OHOO

OHOH

OH

OO

HOOH

OH

HO

O

O

OH

O

O

HOOH

O

HOOO OH

OHHO

LGA

AGF

H2O

2H2O

Rearrangement

O

O

O LGO

DGP

dehydrationfragmentationand retro-aldol

CO, CO2, H2O

H2O 2H2O

Cellulose pyrolysis to anhydro-O

OO

OHO

HO OH

O

HO O

OH

OHOHO

O

dehydration

CO, CO2, H2O

py y ysugarsComplicated gas chemistryCoke can form from gas reactions


CharCoke can form from gas reactions

Lin et al., Kinetics and Mechanism of Cellulose Pyrolysis, J. Phys. Chem. C (2009) 113, 20097-20107


Gasoline Range AromaticsGasoline Range Aromatics

G. Huber/UMass

45

50

Glucose C ll bi

• Octane number of aromatics is 110

30

35

40

y (%

)

CellobioseCelluloseXylitol

• Aromatics can be blended at 25% level in gasoline

15

20

25

Sel

ectiv

ity

• Aromatics can be hydrogenated to other fuels

0

5

10other fuels

• BTX is more valuable than

li0Benzene Toluene Xylenes, Ethyl-

benzeneMethyl-ethyl-

benzene,trimethyl-benzene

Indanes Napthalenesgasoline



Reaction MechanismReaction Mechanism

G. Huber/UMass

Reaction MechanismReaction MechanismCoke

OHO

OH

O

HO

O

OH OO

H2O CO, CO2, H2O

OH

OH

O

OH

OHO

HO O

OHO

cellulose

Pyrolysis acid catalyzeddehydration

anhydro sugarsDehydratedProducts

OH

OH

OO

H

acid catalyzedoligimerization,decarboxylation,decarbonilation

AromaticsHydrocarbonPool

Desired Chemistry:Pyrolysis (homogeneous)Dehydration (heterogeneous & homogeneous)Oligomerization & decarbonylation (heterogeneous)

Undesired Chemistry:

Olef ins


Undesired Chemistry:Homogeneous and Heterogeneous coke formation


Effect of Heating Rate on Catalytic Fast Effect of Heating Rate on Catalytic Fast

G. Huber/UMass

Effect of Heating Rate on Catalytic Fast Effect of Heating Rate on Catalytic Fast PyrolysisPyrolysis

40

45Aromatics Carbon monoxideCarbon dioxide coke

25

30

35

ield

(%)

15

20

Car

bon

yi

0

5

10

Reaction Conditions: Temperature 600oC; ZSM-5; F d Gl C t l t t F d R ti 19

01 10 100 1000

Nominal heating rate (°C s-1)


Feed: Glucose; Catalyst to Feed Ratio 19C6O6H12 → 12/22 C7H8 (63 % Yield) + 48/22 CO (36 % Yield) + 84/22 H2O


Catalytic Partial Oxidation (CPOX)

Fuel and O2 enter at the top

y ( )

Valuable chemicals produced: syngas (H2 & CO), olefins, oxygenates, etc.

R t th llRuns auto-thermally

Short contact times Short contact times (Milliseconds)

www.efrc.udel.eduwww.efrc.udel.eduDauenhauer (UMass) and Schmidt (UMN)


CPOX of Cellulose

www.efrc.udel.eduwww.efrc.udel.edu3 mm

Dauenhauer (UMass) and Schmidt (UMN)


Catalytic Reforming of Cellulose

1200

y g

1000

T10

T

800

T30

T(oC)

400

600( )

No Carbon

Al t

200

400

0 6 0 7 0 8 0 9 1

Carbon

Always operate predicting no carbon


0.6 0.7 0.8 0.9 1C/O

P.J. Dauenhauer, B.J. Dreyer, N.J. Degenstein, L.D. Schmidt, Angewandte ChemieDauenhauer (UMass) and Schmidt (UMN)


Catalytic Reforming of Cellulosey g

Produce equilibrium qsynthesis gas

Higher C/O = more H2 + CO

Less than 1% methane

At C/O < 1.0, no oxygenates

www.efrc.udel.eduwww.efrc.udel.eduP.J. Dauenhauer, B.J. Dreyer, N.J. Degenstein, L.D. Schmidt, Angewandte ChemieDauenhauer (UMass) and Schmidt (UMN)


Comparison of CPOX to Gasificationp

Faster – 10 to 100XPossibly smaller (portable); Faster more flexible start up• Possibly smaller (portable); Faster, more flexible start-up

Cleaner – Catalyst breaks down volatile organics• Possibly eliminates downstream clean up stages• Possibly eliminates downstream clean-up stages

Provides WGS capabilities• Can add steam to adjust H2/CO ratio for desired outputCan add steam to adjust H2/CO ratio for desired output• Possibly eliminates separate shift stage

Remaining IssuesRemaining Issues• Ash handling• Mechanism / Modeling


g• Bio-oill upgrade

Dauenhauer (UMass) and Schmidt (UMN)

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