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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 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
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
CPERI/CERTHCPERI/CERTH
Feedstocks
Conversion Process
Heat
Electricity
Fuel
Chemicals
Biomass UtilizationBiomass Utilization
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 ......
CPERI/CERTHCPERI/CERTH
Source: European Biofuels Technology Platform (WG3) Report: 02.08.2007
European Roadmap for FuelsEuropean Roadmap for Fuels ((EUCAR)EUCAR)
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
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
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
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%
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.
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)
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
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
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.)
CPERI/CERTHCPERI/CERTH
A Fast Pyrolysis Process for Making BioOil
Source: http://www.dynamotive.com/biooil/technology.html
CPERI/CERTHCPERI/CERTH
BTG REACTOR
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
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
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”
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
CPERI/CERTHCPERI/CERTH
Bio–Oil
De-Carboxylated-Bio–Oil
Biomass Catalytic PyrolysisBiomass Catalytic Pyrolysis
K1,dK2,c
C C
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
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
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%
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
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.)
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
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
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
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
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
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)
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
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
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
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
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
CPERI/CERTHCPERI/CERTH
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)
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
BioBio--Oil Analysis (2DGC/TOFMS)Oil Analysis (2DGC/TOFMS)
Thermal Biooil Catalytic Biooil
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
Upgrading the Biomass Fast Pyrolysis Liquids (BFPL)
CPERI/CERTHCPERI/CERTH
BioBio--oil UPGARDING PROCESSES oil UPGARDING PROCESSES
Hydroprocessing (HP) of BFPL– Catalytic Hydroprocessing (CHP) – Thermal Hydroprocessing (THP)
Catalytic Cracking of BFPL
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
Co-Processing Upgraded Biomass Fast Pyrolysis Liquids-
BFPL
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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
CPERI/CERTHCPERI/CERTH
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