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Upgrading of pyrolysis oil for application in standardUpgrading of pyrolysis oil for application in standard refineries
Tcbiomass 2009, September 18, Chicago Kees HogendoornGroup of ThermoChemical Conversion of Biomass (TCCB)University of Twente, The Netherlands
BIOCOUP
Conventional fuels and chemicals
ResidualBiomass
SP1 Primary liquefaction
SP 2 De-oxygenationUT
SP 3 Co-processing in petroleum refinery
Oxygenated products
liquefactionVTT UT
SP 4 Recovery of Chemicals(Phenols Aldehydes Acids) TuE
refinery Shell
p(Phenols, Aldehydes, Acids) TuE
www.biocoup.eu for more info on scope and other SP’s
Goal SP2:Goal SP2:
Development of de-oxygenation technology for pyrolysis oil (derived) liquids
● Catalyst development (BIC), screening (RUG, TKK), support testing (Albemarle)
● Product research (RUG, UT)● Reactor development (UT, BTG)● Process development (BTG, UT)● Analysis feed stock and products (VTT, vTI, RUG)● Oil production and demonstration at PDU scale (BTG, UT)
Upgrading and Technologies
Advantages of pyrolysis oil: low ash content
Left wood; Right pyrolysis oillow ash content
‘high’ energy density (biomass)
Why upgrading: negative sides of pyrolysis oil
Right pyrolysis oilBoth 1 MJ
(Photo BTG)
high acidity/reactivity pyrolysis oiltendency of considerable char formation (blocking, catalyst poisoning)high oxygen and water contentmiscibility problems conventional feedssc b y p ob e s co e o a eeds
Technologies studied in SP2- BIOCOUP
HPTT: High Pressure Thermal Treatment 200-400 oC; 1-20 minutes; 50-200 bar
DCO: Catalytic Decarboxylation = HPTT + catalyst
HDO: Hydrodeoxygenation = DCO + Hydrogen 15 min-4 hours !
HPTT and DCO+ Phase separation: oil, aqueous, gas+ Deoxygenation to ~ 25wt% O (dry oil basis) possible+ Substantial energy densification (up to a factor of 2)
rapid! Increase MwHigh Molecular Mass formed during HPTT
Likely cause: Polymerization of ‘sugars’ in pyrolysis oil
This will complicate hydrodeoxygenation/co-processing
Increase of molecular weight: more so with severity
(minimum)
100 1000 10000
DCO similar to HPTT with respect to decarboxylation and polymerization
HDO results
Increasing severity (T, τ):
• Higher H2 consumption (150-Higher H2 consumption (150800 NL/kg feed)
• Higher deoxygenation (<10-40wt% O in dry remaining)75.0
100.0
ry, w
t.%)
100%
120%
C H O Yield organics
• HDO oil yield ~ 40wt%, decreases with severity
• No (substantial) increase in Mw
50.0
com
posi
tion
(dr
60%
80%
ld (w
t.% o
f oil)
Mw
25.0
Elem
enta
l c
20%
40% Yie
Remaining aqueous0.0
0 100 200 300
Hydrogen consumption (Nm3/t)
0%
Data BTG/RUG (packed bed)
Remaining aqueous phase can be used for chemicals extraction (acids: SP4) or hydrogen production
Data BTG/RUG (packed bed)
HDO process insight
Parallel HDO vs Repolymerization reactions
High Molecular Weight Fragments Char
No catalyst - hydrogen
CharringRe-polymerization
No catalyst and/or hydrogen
Pyrolysis oil
y y g≈ min
H2, catalyst HPTT
Hydrotreating
y y g≈ min (150<T<350oC)
Stable FragmentsHDO oil
and aqueous phase
H2, catalyst≈ min
H2, catalyst≈ min .. hours
HydrodeoxygenationStabilization
Adapted figure from BTG/RUG
≈ min at higher severity
Tested in lab scale refinery units (SP3)Feed back to SP2
Bio Fuels By Bio Fuels By Biomass Catalytic Cracking
by Paul O’Connor – KiOR
Biomass BCC Bio-FuelsCCMaking it all happen:
A Creative Network 2006-2009
ITQValencia
RFS targets requires strong RFS targets requires strong technologies
EISA renewable fuel(2007) mandatesBilli llBillion gallons per year
1 17 1821 22
9 11 14 167
2630
Biomass diesel
2824 Advanced biofuel
3336
913 14 15 17
3 4 61 1 2
9 11711 Cellulosic biofuel
Renewable biofuel
2009 2010 2011 2012 2013 2014 20152008 20172016 20192018 2020 2021 2022
• By 2022, at least 16 billion gallons of cellulosic capacity must be added to meet EISA goals
Key to meeting mandates:
• If plants are 50 MM gallons/yr capacity, need 320 plants, or average of about 25 plants/year
• If average development time for plant is 48 months*, need about 100 plants under development at any given time
•Robust technology• Infrastructure ready productproduct
•Scalable process with rapid rollout* Average total time for pioneer process plants, RAND 1984
Source: Energy Independence and Security Act of 2007, RAND, KiOR analysis
Evolution of Biofuels and Technologies
Vegetable Corn Lignocellulose
Evolution of Biofuels and Technologies
VegetableOil
Corn Lignocellulose
PyrolysisDelignification
Gasification
Fermentation
g
Hydrogenolysis Stabilization BCCF‐T Methanol
MTG Upgrading
RefiningEthanol
G pg g
Renewable (Biomass based) Fuels
Geo Thermo BCCMillions of Years Minutes Seconds
1methanol
Millions of Years Minutes Seconds
3/4
cellulose
lignocellulosicbiomass
l i ile
BCC:“One pot”
2/4 hemicellulosesethanol DMEmethyl
levulinate
pyrolysis oil
mol
e/m
ol
pLiquefaction
+De-oxygenation2/4
lignin butanol
ethyllevulinate
hydrothermalli f ti
O/C
, De-oxygenation
1/4
methane hydrogen
lignin
crude oildiesel (FT)gasoline
MTBE
antracitecoal
FAMEFAEE
MTHFliquefactionoil
5
0 1 2 3 4
0
H/C [mole/mole]
methane hydrogen
History repeatingHeavy Oil Conversion (WWII) Biomass?y ( )
Fluid Catalytic Cracking:ll d f l l f
Biomass Catalytic Cracking:F ll i f l i li i f• Followed successful commercialization of
“topping” refineries•Objective: catalytically convert heavy product to gasoline
l d l ’ l
• Following successful commercialization of ethanol and biodiesel
•Objective: catalytically convert cellulosic biomass to crude substituteD l d 2005 2007 l i• Developed in early 1940’s to solve
pressing national problem (aviation gasoline for WWII)
• Rapidly scaled up (<4yrs from idea to d i ) d hi hl f l
• Developed 2005‐2007 to solve pressing problem (domestic, green source of fuel)
•…In process of scaling up from pilot to demonstration and first
production) and highly successful• Platform for continuous improvement for next 50 years
p fcommercial unit
•…Growing world class R&D for continued improvements
leveraging existing technology and leveraging existing technology and infrastructure
BCC reduces technical and scale up risk while reducing market risk and roll outBCC reduces technical and scale up riskby leveraging existing refining and solids handling equipment….
… while reducing market risk and roll out costs by using existing infrastructure to make existing products
Bio Crude
Core equipment based on FCC technology• Robust conversion technology, over 60 years
Biomass feed
High quality oil processed in existing refineries:• Non corrosive miscible withoperating history
• Well known scale up and cost• Solid catalyst handling – minimal retrofit for
biomass feed
• Non-corrosive, miscible with refining process streams
• Easily refined into on-spec gasoline diesel and jet fuel with low sulfur, no heavy metals
SummarySummary
• BCC produces low oxygen content stable oils suitable for refinery processing into liquid transportation fuelsrefinery processing into liquid transportation fuels.
• BCC can convert solid biomass (500-2000tpd) in distributedBCC can convert solid biomass (500 2000tpd) in distributed local units, while the stable oil produced can be upgraded in existing large scale refineries (economy of scale).
• BCC can be scaled and commercialized fast based on existing extensive FCC technology experienceextensive FCC technology experience
• BCC can compete economically with fossil fuels.
• BCC can handle all types of feed stocks (Straws, Algae,…).
Progress in Bio‐oil Upgrading atMi i i i St t U i itMississippi State University
Philip SteelePhilip Steele
Professor and SERC
Bio‐oil Thrust LeaderBio‐oil Thrust Leader
Sustainable Energy Research Center
Mississippi State UniversityMississippi State University
MSU proprietary HDO catalyst produces a high‐quality hydrocarbon mix:quality hydrocarbon mix:
Hydrogen
Removal of oxygen
Hydro‐CO H OHydrogen +HT catalyst
Water
Hydro‐carbons
‐ CO2 + H2O
HDO bio‐oil
Water
Bio‐oil
Current HDO bio‐oil quality:
Paraffins&
PNA's11%
iso-paraffins
36%
Aromatics17%
Napthenes 100 % U d d
p36% Upgraded
HDO
Properties of HDO bio‐oil vs diesel:
P t HDO bi ilProperty HDO bio-oil
Water content (wt%) 0
Acid value (mg KOH/g) ~0 13Acid value (mg KOH/g) ~0.13
HHV (MJ/kg) 45.5
Oxygen (%) <0.1
FTIR spectra comparison of jet fuel, gasoline and HDO bio‐oil:
180Raw Bio oil HDO Diesel Gasoline
120
140
160
ce
80
100
120
nsm
itta
nc
40
60
% t
ran
0
20
1000125015001750200022502500275030003250350037504000
5
1000125015001750200022502500275030003250350037504000
wavenumber cm-1
Simulated distillation of jet fuel, gasoline and HDO bio oil:and HDO bio‐oil:
700
500
600
e (F
)
Jet fuel Gasoline HDO bio-oil
200
300
400
Tem
pera
tur
0
100
200T
00 10 20 30 40 50 60 70 80 90 100
Distilled (%)
6
Mild Hydrotreating of Pyrolysis OilMild Hydrotreating of Pyrolysis Oil
Robert M. BaldwinPrincipal Scientist and Group
ManagerThermochemical Process R&D and
Bi fi A l iBiorefinery Analysis
tctcbiomassbiomass20092009
NREL is a national laboratory of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy operated by Midwest Research Institute • Battelle
Yesterday’s Panel Discussions
Q: Role of R&D community in developing andQ: Role of R&D community in developing and accelerating commercial deployment of pyrolysis oil?
p oil as a commodit• py-oil as a commodity• quickest path to commercial acceptance: take
advantage of existing fossil fuel infrastructure• engage refining industry in R&D activities
National Renewable Energy Laboratory Innovation for Our Energy Future
Integration with Refining Infrastructure
Bio-Crude from Biomass PyrolysisIntegration with Existing Refining Infrastructure
P l iBio-Crude Fuels
andBiRefining
Pyrolysis andChemicalsBiomass Infrastructure
Improve oil quality-Stabilize oil by partial
di- Improve oil qualityby catalysis- Produce bio-oils with lowash (hot-gas filtration)
upgrading- Reduce oxygen content and acidity-Build molecular structure
National Renewable Energy Laboratory Innovation for Our Energy Future
Effect of Economies of Scale
40
45
25
30
35
Cos
t ($/
bbl)
0 2% O
10
15
20
Upg
radi
ng C 0.2% O
7% O
0
5
1000 10000 100000 1000000
U
C it (bbl/D)
7% O
Capacity (bbl/D)2000 MTDDry Wood
$4-6/bbl total upgrading costs for conventional refining
Source: Global Energy Management Inst. (GEMI), U Houston, 2009
Biofuels: Refinery Integration Strategies
National Renewable Energy Laboratory Innovation for Our Energy Future
Global Energy Management Institute Study
NREL/GEMI Study
“Alternate Value Chains for the Manufacture, Upgrading and Transport of Pyrolysis Oil to
Conventional Petroleum Refineries”Conventional Petroleum Refineries
National Renewable Energy Laboratory Innovation for Our Energy Future
Primary Conclusions: Cost Drivers
• Improved oxygen removal during pyrolysis (CFP)p yg g py y ( )• Partial upgrading• Improved HDO catalysts (selective oxygen
removal)• Multi-stage HT with interstage aromatics removal
Use of aqueous phase reforming for manufacture• Use of aqueous phase reforming for manufacture of H2
Combined effect on upgrading costs:$47/bbl → $14/bbl
Value Chains: GEMI
Lowest cost case:1) Centralized pyrolysis facility located near
refinery with XS H22) Upgrading to ~7 % oxygen3) Blend 7/1 (v/v) with low-TAN crude (<0.2)
• Gives feed of TAN = 2 oxygen = 0 9 wt%• Gives feed of TAN = 2, oxygen = 0.9 wt%4) Co-process with crude oil in refinery
• Requires “armored” metallurgy in refinery• Cost may be partially offset by low sulfur content of
pyrolysis oil
National Renewable Energy Laboratory Innovation for Our Energy Future