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Chemical Process Engineering Research Chemical Process Engineering Research Institute (CPERI)/Center for Research and Institute (CPERI)/Center for Research and Technology Hellas (CERTH) Technology Hellas (CERTH) EUROBIOREF Summer School EUROBIOREF Summer School September 18 September 18-24, 2011 24, 2011 Castro Marina Lecce, Italy Castro Marina Lecce, Italy Conversion of Biomass to Fuels and Chemicals via Conversion of Biomass to Fuels and Chemicals via Thermochemical Processes Thermochemical Processes Angelos A. Lappas Angelos A. Lappas Research Director CPERI/CERTH Research Director CPERI/CERTH P.O. Box 361 GR P.O. Box 361 GR-570 01 570 01 Thermi Thermi-Thessaloniki, Greece Thessaloniki, Greece

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Page 1: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

Chemical Process Engineering Research Chemical Process Engineering Research Institute (CPERI)/Center for Research and Institute (CPERI)/Center for Research and

Technology Hellas (CERTH)Technology Hellas (CERTH)

EUROBIOREF Summer School EUROBIOREF Summer School September 18September 18--24, 201124, 2011

Castro Marina Lecce, ItalyCastro Marina Lecce, Italy

Conversion of Biomass to Fuels and Chemicals via Conversion of Biomass to Fuels and Chemicals via Thermochemical ProcessesThermochemical Processes

Angelos A. LappasAngelos A. LappasResearch Director CPERI/CERTHResearch Director CPERI/CERTH

P.O. Box 361 GRP.O. Box 361 GR--570 01570 01ThermiThermi--Thessaloniki, GreeceThessaloniki, Greece

Page 2: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

OUTLINEOUTLINE

IntroductionIntroduction--Biomass/BiofuelsBiomass/Biofuels BiomassBiomass PyrolysisPyrolysis ProcessProcess BiomassBiomass CatalyticCatalytic PyrolysisPyrolysis ProcessProcess

ProcessProcess DescriptionDescription ExperimentalExperimental resultsresults andand discussiondiscussion CatalystCatalyst effectseffects ConclusionsConclusions

UpgradingUpgrading thethe BioBio--oiloil byby downstreamdownstream catalyticcatalytic routesroutes UpgradingUpgrading byby HPHP UpgradingUpgrading byby FCCFCC UpgradingUpgrading byby CoCo--processingprocessing

Page 3: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Feedstocks

Conversion Process

Heat

Electricity

Fuel

Chemicals

Biomass UtilizationBiomass Utilization

Page 4: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Sustainability – Energy Security Reduction of Greenhouse gas (GHG)

emissions Reinforce agricultural economy

– Introduction of competitive energy crops

– Development of new job openings– Support other industries (sugar,

paper etc)

Why Biofuels? Motivation Why Biofuels? Motivation ......

Page 5: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Source: European Biofuels Technology Platform (WG3) Report: 02.08.2007

European Roadmap for FuelsEuropean Roadmap for Fuels ((EUCAR)EUCAR)

Page 6: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

1st Generation Biofuels1st Generation Biofuels

Well tested technology High quality products with

excellent burning characteristics– High octane number, small

cetane number

High production cost– Limited type of biomass

employed Competition with food-crops Dependence on legislation Questions regarding

sustainability

Biodiesel from transesterification of vegetable oils Bioethanoll from sugars

Advantages Disadvantages

Page 7: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

2nd Generation Biofuels2nd Generation Biofuels

Feedstock: Non-edible part of biomass

Compatible products with today’s fuels

Utilization of existing units

High conversion of carbon into final product

Small operational cost

High investment cost Necessity to construct

large scale units of significant capacity

Essential availability of large amounts of biomass

Biofuels from thermo-chemical processes

Advantages Disadvantages

Page 8: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

BIOMASS FAST PYROLYSIS PROCESSBIOMASS FAST PYROLYSIS PROCESS

Biomass pyrolysis: a basic biomass thermo-chemical process for the production of liquids, solids and gaseous products

For biomass heating a solid heat carrier is used

Page 9: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Biomass pyrolysis: use of all biomassBiomass pyrolysis: use of all biomass

Oils

Sugars

Cellulose

Hemi - Cellulose

Lignin

~ 16 €/GJ

~ 20 €/GJ

~ 8 €/GJ

< 3 €/GJ

Brazil

Crude Oil100$/bbl ~ 13 €/GJ75 $/bbl ~ 10 €/GJ60 $/bbl ~ 8 €/GJ15 $/bbl ~ 2 €/GJ

“Biomass Waste”~70%

Page 10: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

PYROLYSIS CHARACTERISTICS

Slow pyrolysis (mainly in fixed beds): Heating rates: 5-7 K/min Less liquids (30-40%wt) and more char (30-40%wt)

Fast pyrolysis: High temperature process in the absence of air Very high heating rates (>300°C/min) and heat transfer(requires ground of biomass) Carefully temperature control Rapid cooling Liquid: 70%, gases:15%, char:15%

Bio oil has an energy density of 20 GJ/m3 compared to 4 GJ/m3 for wood chips and the oil's ash content is 100 times lower than

that of biomass.

Page 11: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Low Temp < 400oC < High Temp

Fast < 0.1sec < Slow

Low P < 75kPa < High P

Biomass(s Primary Tar(L)

Secondary Tar(L)

Char Coal(S)CO2, H2O

Low T

Low TSlow

High P

Low TSlowHigh P

Primary Tar(V)

Transient Oxygenated Fragments(V)

Vapor Phase Derived Tar(V or L)

High TFast

Low P

High TFast

Low P

High TSlowLow P

High TSlowHigh P

Biomass(s Primary Tar(L)

Secondary Tar(L)

Char Coal(S)CO2, H2O

Low T

Low TSlow

High P

Low TSlowHigh P

Primary Tar(V)

Transient Oxygenated Fragments(V)

Vapor Phase Derived Tar(V or L)

High TFast

Low P

High TFast

Low P

High TSlowLow P

High TSlowHigh P

Olefins

Carbon Black(S)

Water Soluble Oxygenated

Compounds(V)

High TFast

Low P

High TSlowLow P

Med. TSlowMed. P

COCH4H2CO2

High TSlowHigh P

High TSlow

High P

Pyrolysis Reactions

(reproduced with the permission of J. Diebold of the Solar Energy Research Institute)

Page 12: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

O CHOHOH2C

COOH

OO

H

HO

OH

HH

HOHH OH

OH

Cellulose

Oligomers

Glucose5-hydromethylfurfural HMF

Levulinic Acid

H2O H2O

OO

O

HydrolyzationO

2-methylcyclopentanone

O CH2OHHOH2C

O CH2OHHOH2C

2,5-dimethylfuranhexane-2,5-dione

O

tetrahydro-2,5-dimethylfuran

OH

2-methylcyclopentanol

H+

H+

H+

H+

Cellulose conversion pathway

Page 13: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Hemicellulose

Oligomers

Pentoses(Xylose)

H+

H+

O CHO

Furfural

H+

H2O

O CH2OH

H2

Furfuryl alcohol

H2

O CH2OH Tetrahydrofurfuryl alcohol

H2O

O CH32-Methylfuran

H2

O CH3Tetrahydro-2-methylfuran

O

Cyclopenta-one

OHCyclopentan

ol

H2O

Hemicellulose conversion pathway

Page 14: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

FAST PYROLYSIS SYSTEMS

Biomass feed: Reception and storage, Drying, Grinding,

Reactor configurations:

Fluid beds, Ablative, Transported bed, Entrained flow

CFB, Rotating cone

Char and ash separation

char catalyses secondary reactions

cyclones, filters

Vapor residence time<2:

avoid secondary cracking reactions

Liquid collection

Fast quenching (i.e contact with cooled liquid, HE etc.)

Page 15: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

A Fast Pyrolysis Process for Making BioOil

Source: http://www.dynamotive.com/biooil/technology.html

Page 16: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

BTG REACTOR

Page 17: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Bio-oil Characteristics

Negarive

Very high oxygen content (40-50%wt)

High water content (might be two phase)

Non catalytic: 15-30%wt

Vey low PH

Limited storage stability (accelerated at high T)

Minor miscibility with petroleum fuels

Cannot be used directly as transportation fuel

HHV: Around 15-17 MJ/Kg at 25%wt H2O

Bio-oil needs upgarding

Positive

Liquid transportable fuel

Higher energy density than solid biomass

High added value chemicals source (phenol)

Could be handled within a conventional refinery

Page 18: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

TECHNOLOGY DEVELOPED IN CPERI/CERTH

Heterogeneous Catalysis for the Conversion of Solid Biomass into Renewable Fuels and Chemicals

Biomass Catalytic Pyrolysis: Use a solid catalyst as heat carrier for the

in-situ upgrading of the pyrolysis products aiming at the production of liquids with

better quality

Page 19: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Biomass Catalytic Pyrolysis or Biomass Catalytic Pyrolysis or Cracking conceptCracking concept

Crude + Bio Crude Refinery of the future

Oil Refinery

Biomass Catalytic Cracking(BCC process)

“Bio Crude”

Crude + Bio Crude Refinery of the future

Oil Refinery

Biomass Catalytic Cracking(BCC process)

“Bio Crude”

Page 20: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Improve Bio-oil stability

Improve Bio-oil acidity

Co-processing bio-oil with conventional oil

fractions

Processing into refinery processes (FCC & HPC)

Biomass Catalytic Pyrolysis Biomass Catalytic Pyrolysis objectivesobjectives

Page 21: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Bio–Oil

De-Carboxylated-Bio–Oil

Biomass Catalytic PyrolysisBiomass Catalytic Pyrolysis

K1,dK2,c

C C

Page 22: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Lignocellulosic biomass derived productsLignocellulosic biomass derived products

LigninLignin

CelluloseCellulose

HemicelluloseHemicellulose

Phenolic Phenolic monomer, dimermonomer, dimer

Phenolic Phenolic monomer, dimermonomer, dimer

Phenolic Phenolic trimer, tertmertrimer, tertmer

Phenolic Phenolic trimer, tertmertrimer, tertmer

Phenolic polymer Phenolic polymer Phenolic polymer Phenolic polymer

Alcohol, aldehyde,Alcohol, aldehyde,small moleculessmall molecules

Alcohol, aldehyde,Alcohol, aldehyde,small moleculessmall molecules

MonosaccharideMonosaccharideMonosaccharideMonosaccharide

OligomerOligomerOligomerOligomer

Catalyticpyrolysis

Catalyticpyrolysis

GasGasGasGas GoodGoodcarboncarbonbalancebalance

GoodGoodcarboncarbonbalancebalance

CharCharCharChar

Page 23: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

TO PRODUCTRECOVERY

FLUIDIZINGGAS

SCREWFEEDER

BIOMASSFEEDTANK

SLIDEVALVE

SLIDEVALVE

INJECTOR

LIFT GAS

HEAT CARRIERVESSEL

RISER

STRIPPER/DISENGAGER

STRIPPINGGAS

CYCLONEFILTER

CPERI CPERI CFB Pilot Plant UnitCFB Pilot Plant Unit for Biomass Pyrolysis for Biomass Pyrolysis and Catalytic Pyrolysis Studiesand Catalytic Pyrolysis Studies

LIFT GAS

Page 24: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

CPERI CPERI CFB Pilot Plant UnitCFB Pilot Plant Unit for Biomass for Biomass Pyrolysis and Catalytic Pyrolysis StudiesPyrolysis and Catalytic Pyrolysis Studies

Pilot Plant UnitPilot Plant Unit•Biom.: Up to 6 kgs,15 g/min•Catalyst: 250 g/min•Cat/Biomass=5-25•Temp.: up to 600 °C•Duration: Continous•Kgs of biooil production•Mass balances 95-98 wt%

Page 25: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

CPERI BENCH SCALE FACILITIESCPERI BENCH SCALE FACILITIES(for catalyst pre(for catalyst pre--screening)screening)

Bench Scale UnitBench Scale UnitBiomass: 0 - 1,5 g.Catalyst: 0 - 0,7 g.Operation Temperature: up to 650 °CExperiment duration: 15 minutes

Page 26: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Product AnalysisProduct Analysis

Gas AnalysisHP 6890 GC, equipped with four columns for cracked gas analysis

Total Liquid Paper (TLP) Analysis Characterization by ASTM techniques

ASTM 4052 (density), ASTM D1744 (H2O), ASTM D445 (viscosity at 50oC) ASTM D4530 (MCRT), ASTM D97 (pour point) ASTM D93 (flash point) ASTM D4809 (calorific value)

Separation in organic and aqueous phase using ether Leco 2DGC-TOFMS for detailed qualitative analysisOrganic Phase Analysis HP 5989 GC/MS for detailed qualitative analysis HP 5890 GC for phenols quantitative analysis

Aqueous phase analysis HP 5890 GC for water soluble quantitative analysis (acetic acid, methanol etc.)

Page 27: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

EXPERIMENTAL RESULTS FROM EXPERIMENTAL RESULTS FROM BIOMASS THERMAL AND CATALYTIC BIOMASS THERMAL AND CATALYTIC PYROLYSIS BASED ON PILOT PLANT PYROLYSIS BASED ON PILOT PLANT

TESTSTESTS

Page 28: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

EXPERIMENTAL PROCEDUREEXPERIMENTAL PROCEDURE

Types of biomass feeds used:Types of biomass feeds used:Wood biomass: Beech Wood biomass: Beech

•• Particle size=150Particle size=150--600 600 μμmm•• bulk density (b.d)= 0.3 g/mlbulk density (b.d)= 0.3 g/ml

Energy crop: MischantusEnergy crop: Mischantus•• particle size = 100particle size = 100--500 500 μμmm•• b.d= 0.3 g/mlb.d= 0.3 g/ml

Solid heat carriersSolid heat carriers Silica sandSilica sand ZSMZSM--5 catalysts5 catalysts Other catalystsOther catalysts FCC catalyst:FCC catalyst:

BeechC, %wt 49.41H, %wt 6.73N, %wt 0.16O, %wt 42.96Ash, %wt 0.53H2O, %wt 8.25Na, ppm 43.8K, ppm 326GHV, MJ/Kg

18.2

Page 29: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

EXPERIMENTAL RESULTSEXPERIMENTAL RESULTS

High liquid yields are produced (about 75% on biomass) using silica sand (thermal)

The use of an active catalyst (like FCC) causes a significant decrease in the production of liquids and an increase in the water in the bio-oil in both temperatures

The presence of catalyst favors the secondary cracking of vapors and especially the de-oxygenation reactions

Temperature change from 450 to 500 °C has a small positive effect on total liquid yield in primary pyrolysis but it increases the secondary reaction rates giving less liquids.

0

10

20

30

40

50

60

70

sand FCC

Wat

er (w

t%on

bio

-oil)

T=450C

T=500C

Page 30: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Gas and Solid YieldsGas and Solid Yields

Char and gases from thermal pyrolysis are around 10%wt and are T depended: Higher temperatures give less char and more gases

In the presence of a catalyst the secondary reactions lead to high yields of gases and coke:

• Catalytically produced coke is about 15%wt

• Catalytically produced gases are about 8-10%wt and consist mainly of CO

• High pyrolysis T favors gases from secondary cracking reactions than coke

Page 31: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Catalysts promote Coke and Gas production while

suppress that of Bio-Oil.

The ZSM-5/4 & ZSM-5/5 are the catalysts that

produce the larger amounts of Bio-Oil.

The ZSM-5/3 produces the greater amount of

gases

C rack ed G ase s

0

5

10

15

20

25

30

35

No n C a t ZS M -5 /4 ZS M -5 /5 ZS M -5 /3 F C C

%w

t of B

iom

ass

T= 4 5 0 o C _ S /B =1 0 -1 5T= 5 0 0 o C _ S /B =1 5 -2 0

C o k e & C h a r

0

5

1 0

1 5

2 0

2 5

N o n C a t ZS M -5 /4 ZS M -5 /5 Z S M -5 /3 F C C

%w

t of B

iom

ass

T= 4 5 0 o C _ S /B = 1 0 -1 5T= 5 0 0 o C _ S /B = 1 5 -2 0

B io -O il

01 02 03 04 05 06 07 08 0

N o n C a t ZS M -5 /4 ZS M -5 /5 Z S M -5 /3 F C C

%w

t of B

iom

ass

T= 4 5 0 o C _ S /B = 1 0 -1 5T= 5 0 0 o C _ S /B = 1 5 -2 0

EXPERIMENTAL RESULTS WITH ZSMEXPERIMENTAL RESULTS WITH ZSM--55

Page 32: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

EXPERIMENTAL RESULTS WITH OTHER EXPERIMENTAL RESULTS WITH OTHER CATALYSTS (BENCH SCALE TESTS)CATALYSTS (BENCH SCALE TESTS)

Biooil is reduced with catalysis Coke and gas yields increase Different catalysts achieve different degrees of cracking depending on

characteristics such as surface area, acidity

0.00%

10.00%

20.00%

30.00%

40.00%

50.00%

60.00%

70.00%

TLP Gas Yield Coke Yield

Yiel

d (w

t %

on

biom

ass)

Sil ica Sand (0)

Titania (8)

Tetragonal Zirconia (156)

ZSM-5/4 (61)

ZSM-5/5 (90)

Magnesite (40)

FCC (180)

ZSM-5/3 (131)

Nickel Monoxide (30)

Alumina (100)

Sil ica Alumina (>400)

Magnesite (50)

Zirconia Titania (80)

Alumina (200)

Page 33: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

40

45

50

55

60

65

70

75

80

0 20 40 60 80 100 120 140 160 180 200Catalyst SA, m2/g

Raw

liqu

id y

ield

, %w

t on

biom

ass

10

14

18

22

26

30

34

0 20 40 60 80 100 120 140 160 180 200

Catalyst SA, m2/g

Raw

H2O

yie

ld, %

wt o

n bi

omas

s

Catalyst Properties (TSA) EffectsCatalyst Properties (TSA) Effects--11

4

8

12

16

20

24

28

0 20 40 60 80 100 120 140 160 180 200Catalyst SA, m2/g

Raw

cha

r yi

eld,

%w

t on

biom

ass

10

12

14

16

18

20

22

24

0 20 40 60 80 100 120 140 160 180 200Catalyst SA, m2/g

Raw

gas

yie

ld, %

wt o

n bi

omas

s

Page 34: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

0

2

4

6

8

10

12

14

0 20 40 60 80 100 120 140 160Catalyst SA, m2/g

Raw

CO

& C

O2

yiel

d, %

wt o

n bi

omas

s

COCO2

TSA increases significantly the CO yield and to a smaller extent the CO2 yield.

TSA decreases heavy compounds

0.00

0.50

1.00

1.50

2.00

2.50

0 20 40 60 80 100 120 140 160 180 200Catalyst SA, m2/g

Raw

HC

yie

ld, %

wt o

n bi

omas

s

0

2

4

6

8

10

12

0 20 40 60 80 100 120 140 160 180 200Catalyst SA, m2/g

Raw

hea

vy y

ield

, %w

t on

biom

ass

Catalyst Properties (TSA) EffectsCatalyst Properties (TSA) Effects--22

Page 35: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Catalyst Properties (acidity) EffectsCatalyst Properties (acidity) Effects

A.AHO ET AL.TRANS ICHEM E,PART B,PROCESS SAFETY AND ENVIRONMENTAL PROTECTION,2007, 85(B5):473-480

Page 36: Chemical Process Engineering Research Institute (CPERI ... · PDF fileChemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas ... 1st Generation

CPERI/CERTHCPERI/CERTH

Under both reaction temperatures:i. Catalysts increased H2O concentration in Bio-Oil and decreased its HV and MCRT

ii. The ZSM-5/5 is the catalyst that produces the Bio-Oil with the lower amount of MCRT

When reaction temperature increases the H2O concentration in Bio-Oil also increases while the Bio-Oil

Heating Value decreases.

It appears that the HV of the organic Bio-Oil improves when ZSM-5 catalysts of increased TSA are used or

when increased reaction temperatures are employed.

H 2O

010203040506070

No n C a t ZS M -5 /4 ZS M -5 /5 ZS M -5 /3 F C C

%w

t in

Bio

-Oil

T=4 5 0 o C _ S /B =1 0 -1 5T=5 0 0 o C _ S /B =1 5 -2 0

M C R T

02468

101214161820

No n C a t ZS M -5 /4 ZS M -5 /5 ZS M -5 /3 F C C

%w

t in

Bio

-Oil T=4 5 0 o C _ S /B =1 0 -1 5

T=5 0 0 o C _ S /B =1 5 -2 0

G H V

02468

1012141618

No n C a t ZS M -5 /4 ZS M -5 /5 ZS M -5 /3 F C C

MJ/

Kg

T= 450o C _ S /B =10 -15T= 500o C _ S /B =15 -20

G H V o rg an ic

05

101520253035

ZS M -5 /4 ZS M -5 /5 ZS M -5 /3

MJ/

Kg

T=45 0o C _ S /B =10 -15T=50 0o C _ S /B =15 -20

Effect of catalyst on BioEffect of catalyst on Bio--Oil quality Oil quality -- 1 1

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CPERI/CERTHCPERI/CERTH

For both pyrolysis temperatures:i. The ZSM-5/3 & ZSM-5/5 catalysts produced Bio-Oil with higher concentration of

Hydrocarbons.

ii. When TSA increases Carbonyls and Heavy & Unidentified compounds decreases.

iii. Catalysts effect on Phenols concentration is probably negative.

HY DROCARBONS

0

2

4

6

8

1 0

Non Cat ZSM -5/4 ZSM -5/5 ZSM -5/3 FCC

%w

t in

Bio

-Oil

T=450oC _S/B=10-15T=500oC _S/B=15-20

PHE NOLS

02468

101214

Non Cat ZSM -5/4 ZSM -5/5 ZSM -5/3 FCC

%w

t in

Bio

-Oil

T =450oC_S/B=10-15T =500oC_S/B=15-20

H EAV Y & U N IDE N TIFIE D

0

10

20

30

40

50

Non Cat ZSM -5/4 ZSM -5/5 ZSM -5/3 FCC

%w

t in

Bio

-Oil T=450oC _S/B =10-15

T=500oC _S/B =15-20

CARBONYLS

02468

101214

Non Cat ZSM -5/4 ZSM -5/5 ZSM -5 /3 FCC

%w

t in

Bio

-Oil T=450oC _S /B=10 -15

T=500oC _S /B=15 -20

Effect of catalyst on BioEffect of catalyst on Bio--Oil quality Oil quality -- 2 2

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0.00%

5.00%

10.00%

15.00%

20.00%

25.00%

30.00%

35.00%

40.00%

45.00%

0.00% 5.00% 10.00% 15.00% 20.00% 25.00% 30.00% 35.00% 40.00% 45.00%

Organic Yield (wt% on biomass)

Oxy

gen

Cont

ent (

wt%

on

orga

nic)

Silica Sand

FCC (180)

Magnesite (40)

Nickel Monoxide (30)

ZSM-5/4 (61)

ZSM-5/5 (90)

ZSM-5/3 (131)

Alumina (100)

Alumina (200)

Tetragonal Zirconia (156)

Titania (8)

Silica Alumina (>400)

Zirconia Titania (80)

Biooil cracking leads to less oxygen content in biooilBiooil cracking leads to less oxygen content in biooil Different quality biooils can be produced with different catalystsDifferent quality biooils can be produced with different catalysts Enhanced cracking yields less organic oil and more coke, CO, COEnhanced cracking yields less organic oil and more coke, CO, CO22

and waterand water

Catalyst Effects on Deoxygenation Catalyst Effects on Deoxygenation (bench scale runs)(bench scale runs)

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Organic liquid yield vs Oxygen content

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

0.00 10.00 20.00 30.00 40.00 50.00 60.00

Organic liquid, wt% on biomass

Oxy

gen

cont

ent o

f org

anic

liqu

id, w

t%

Pilot PlantBench Scale

Bench Bench -- Pilot Scale CorrelationPilot Scale Correlation

Same Deoxygenation Same Deoxygenation –– Cracking trend for both scalesCracking trend for both scales

Greater Deoxygenation and biooil yields for Pilot scale due to better heat Greater Deoxygenation and biooil yields for Pilot scale due to better heat transfer, residence times and C/BM ratiotransfer, residence times and C/BM ratio

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Organic liquid yield vs Oxygen content

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

0.00 10.00 20.00 30.00 40.00 50.00 60.00

Organic liquid, wt% on biomass

Oxy

gen

cont

ent o

f org

anic

liqu

id, w

t%

Pilot PlantBench Scale

Bench Bench -- Pilot Scale CorrelationPilot Scale Correlation

Same Deoxygenation Same Deoxygenation –– Cracking trend for both scalesCracking trend for both scales

Greater Deoxygenation and biooil yields for Pilot scale due to better heat Greater Deoxygenation and biooil yields for Pilot scale due to better heat transfer, residence times and C/BM ratiotransfer, residence times and C/BM ratio

achieved biooil

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BioBio--Oil Analysis (2DGC/TOFMS)Oil Analysis (2DGC/TOFMS)

Thermal Biooil Catalytic Biooil

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Biomass Catalytic Pyrolysis significantly changes bio oil chemical composition

Need for optimization of catalysts and operating conditions

Key to catalyst formulation are: Surface area, Acidity and Pore size distribution

ConclusionsConclusions: : Biomass Catalytic PyrolysisBiomass Catalytic Pyrolysis

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Upgrading the Biomass Fast Pyrolysis Liquids (BFPL)

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BioBio--oil UPGARDING PROCESSES oil UPGARDING PROCESSES

Hydroprocessing (HP) of BFPL– Catalytic Hydroprocessing (CHP) – Thermal Hydroprocessing (THP)

Catalytic Cracking of BFPL

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HYDROPROCESSING (HP) BFPLHYDROPROCESSING (HP) BFPL

Tests Performed in Veba Oil Use of an Eucalyptus Biooil feed Catalytic HP (CHP)

– Experimental Unit • Down flow Fixed bed Reactor (ID=3 cm, L=1123cm)• Catalyst tested: Commercially available NiMo, CoMo• Variables: T, WHSV

Thermal HP (Veba Combi Cracking Process)– Experimental Unit

• Slurry reactor (ID=4.5 cm, L=400cm)• T=327°C• Variables:T, WHSV

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Different severities of HP by varied T, WHSV Degree of deoxygenation (DeO) was measured:

– Thermal:78-85%– Catalytic:88-99.9%

Catalytic HP run time only 100 hrs (operating plugging problems)– This was fully confirmed in BIOCOOP

Thermal HP run time 1 week w/o operating problems

Results of BFPL HPResults of BFPL HP

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0

10

20

30

40

50

60

75 80 85 90 95 100Deoxygenation Rate [wt%]

Yie

ld [w

t%]

oil H2O gas H2 consumption

Effect of DEO rate on product Effect of DEO rate on product yield in THPyield in THP

THP CHP

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Effect of DEO rate on Product Effect of DEO rate on Product Properties in THPProperties in THP

0

2

4

6

8

10

75 80 85 90 95 100

Deoxygenation Rate [wt%]

C/H

[wt%

/wt%

], O

[wt%

]

0.6

0.7

0.8

0.9

1

1.1

dens

ity [g

/cm

3 ]

C/H oxygen content density

THP CHP

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Quality of Thermally HP BFPLQuality of Thermally HP BFPL

Light fraction Heavy fraction%wt of total product 70 30Elemental Analysis (%wt)C 82.2 84.4H 10.7 9.4S 0.01 0.01N 1.15 0.42O 6.4 4.9H2O 0.99Density 0.942 1.036Distillation (°C/%wt)<200 27200-350 55.3 23350-500 17.8 66>500 11

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Literature studies using:– HZSM-5 catalysts– FCC catalysts

Tests showed very high coking (around 20%wt) Blending very difficult due to minor miscibility

of BFPL/HC

BFPL CATALYTIC CRACKINGBFPL CATALYTIC CRACKING

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Co-Processing Upgraded Biomass Fast Pyrolysis Liquids-

BFPL

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TECHNOLOGY INVESTIGATED IN CPERITECHNOLOGY INVESTIGATED IN CPERIFOR NON CATALYTIC BIOOILFOR NON CATALYTIC BIOOIL

Low SeverityTHP

Hydrogen

BFPLSeparation

Light Oil

Heavy Oil

FCCU

VGO

Fuels

Concept: Replace Resid with BFPL in Conventional FCCUConcept: Replace Resid with BFPL in Conventional FCCU

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Experiments performed in bench and pilot scale

Use of THP-Bio-oil from low severity HP (80%DeO)

Bench scale studies – Catalyst evaluation

Pilot scale studies – Validation of the proposed technology

CO PROCESSING THPCO PROCESSING THP--BIOOIL IN BIOOIL IN FLUID CATALYTIC CRACKING UNITSFLUID CATALYTIC CRACKING UNITS

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Target: to select catalyst with low coke make Feedstock: THP-BFPL/LCO mixture (15/85 w/w):

– MCRT=0.4 Bench scale unit: fixed bed (modified MAT) Testing of 2 commercially available catalysts

with different Re content (ReUSY1, ReUSY2) Experimental conditions: T=500-550°C, C/O=3-6

BENCH SCALE TESTINGBENCH SCALE TESTING

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Bench Scale Experimental ResultsBench Scale Experimental Results

0.5

0.8

1.1

1.4

1.7

2

2.3

1 2 3 4 5 6 7Catalyst to Oil Ratio, (C/O)

Cok

e on

Cat

alys

t (w

t %)

Catalyst: ReUSY

10

15

20

25

30

35

40 44 48 52 56 60Conversion (wt %)

Gas

olin

e Yi

eld

(wt %

)

Catalyst: ReUSY

Very promising results from Bench scale studies– A ReUSY catalyst was the best for low coke selectivity– Coke on catalyst was less than 1.5%wt (coke yield 3-6%wt)– Gasoline yield 20-25%wt

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Tests in a fully circulating FCC pilot plant unit

Use of an Ecat from a Greek refinery (TSA=158m2/g)

Use of a conventional VGO as base feed

Co-processing: 85%VGO+15%(LCO+THP Bio-oil)

THP Bio-oil was 15% in the LCO Tests with only VGO+15%LCO for

comparison

PILOT SCALE TESTINGPILOT SCALE TESTING

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FCC Pilot Plant Experimental ResultsFCC Pilot Plant Experimental Results

3032343638404244464850

50 55 60 65 70 75 80Conversion, wt%

C 5-4

30°F

yie

ld, w

t%

VGO + 15% LCO

VGO + 15% (LCO+Biooil)10

15

20

25

30

35

50 55 60 65 70 75 80Conversion, wt%

LCO

yie

ld, w

t%

VGO + 15% LCO

VGO + 15% (LCO+Biooil)

Effect of Bio-oil co-processing– No operating problems in the pilot plant– Positive effect in gasoline and LCO selectivity– Coke increases 0.5%wt– Conversion decreases 2 units at the same C/O– Gasoline contains more aromatics

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TECHNOLOGY INVESTIGATED IN CPERITECHNOLOGY INVESTIGATED IN CPERIFOR CATALYTIC BIOOILFOR CATALYTIC BIOOIL

Hydroprocessing Catalytic Cracking Unpublished results (Acenet/Hecabio) show

very good performance of both processes

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Upgrading of bio-oil is a very complicated task and R&D on catalysis/process is required

For the conventional bio-oil hydtrotreating seems unavoidable to remove oxygen

Thermal hydrotreating has less operating problems

The use of a catalytic bio-oil helps to use less severe conditions in both HP and FCC

a catalytic biooil with less than 20% oxygen is now feasible

Research work is needed:

Fundamentals on biomass catalytic pyrolysis (mechanisms/kinetics)

Optimization of catalyst properties

Upgrading of catalytic bio-oil through HP/FCC/esterification

Advanced characterization of bio-oil

Separation of high added value chemicals chemicals

CONCLUSIONSCONCLUSIONS