© 2006 UOP LLC. All rights reserved.
Challenges in the Exploration of Renewable Energy
Joseph KocalUOP LLC
July 15, 2008
© 2008 UOP LLC. All rights reserved.UOP 4926-01
Outline
• Background• 1ST Generation Renewable Fuels
- Natural oils and fats • 2nd Generation Renewable Fuels
- Lignocellulosics- Algae
• Summary
Inedible Oils: Camelina, Jatropha
Fuel Additives / Blends Fuels
Where is Biofuels Technology Headed?
JetDiesel
UOP’s Bio-Fuels Technology GoalsIdentify and utilize processing, composition, and infrastructure
synergies to lower capital investment, minimize value chain disruptions, and reduce investment risk.
BiodieselEthanol
• Lignocellulosic biomass to fuels
• Algal oils to fuels
Generation 1• Vegetable oils to
diesel, gasoline and jet fuel
Generation 2
Gasoline
UOP 4913C-09
Feed Process Product
Green OlefinsVegetable Oil Green GasolineCatalytic
Cracking
H2 Green DieselVegetable Oil
EcofiningTM
BiodieselGlycerol
BiodieselMethanol
Vegetable OilBiodiesel
Green Chemicals
Lignocellulosic Waste
Green FuelsUpgrading
H2 Green JetVegetable Oil
Refining
UOP 4856I-11
Biomass Processing Routes
Green Diesel vs. Biodiesel (FAME)Veg Oil/ Grease
+ Glycerol
Biodiesel (FAME) Green Diesel
+ Propane
HydrogenMethanol
Petroleum ULSD
Biodiesel (FAME) Green Diesel
Oxygen Content, % 0 11 0Specific Gravity 0.84 0.88 0.78Sulfur content, ppm <10 <1 <1Heating Value MJ/kg 43 38 44Cloud Point, °C -5 -5 to +15 -30 to -10Cetane 40 50-65 70-90Lubricity Baseline Good BaselineStability Baseline Poor Baseline
UOP/ENI EcofiningTM Process to Produce Green DieselUOP 4856I-12
Breakeven Analysis: Sensitivity to Feed Oil Prices
UOP 4856I-13
-$1,400
-$1,200
-$1,000
-$800
-$600
-$400
-$200
$0
$200
$400
Crude Price, $/bbl
$400/MT ($59/bbl)$600/MT ($88/bbl)$800/MT ($118/bbl)$1000/MT ($146/bbl)
Sensitivity to Vegetable Oil Price
NPV
, $M
$25 $35 $45 $55 $65 $85 $95 $105 $115 $125$75$30 $40 $50 $60 $70 $80 $90 $100 $110 $120
Economics Driven by Relative Cost of Feedstocks
DARPA-funded Project for Renewable JP-8 production
UOP 4788H-30DARPA, Project W911NF-07-C-0049
Dr. Douglas Kirkpatrick
Overall Program Objective
1. Demonstrate a process for conversion of natural oils and fats to on-spec JP-8 that is technically and economically feasible
2. Identify viable technology to increase volume and reduce cost of renewable-oil crops
Producing jet-range fuel from deoxygenated natural oils and fats
60 400 500 650 1000 1300Boiling Point, DegF
Gasoline Diesel No. 2 Lubricating Oils Asphalt
Jet
300
Heavy Fuel Oils
1 6 8 10 15 20 43 71Number of Carbon Atoms
5 18 75 4,000 366,000 >1000 TrillionNumber of Paraffin Isomers
Gases
Crude Oil
Deoxygenated Soybean Oil
Deoxygenated Coconut Oil
to JP-8
5-10 11 12 13 14 15 16 17 18 19+Coconut Oil 15 49 18 8 11 0Soybean Oil 0 0 0 11 88 0Deoxygenated Coconut oil 15 19 29 7 11 3 5 4 6 0Deoxygenated Soybean oil 0 0 0 0 0 4 7 35 53 0
Carbon Chain Length
EcofiningTM
Oil Isomerization
Production of Jet Fuel
New Bio-Oil to JP-8 Process Based on Existing UOP Technology
Deoxygenation Green Diesel
Oil Selective Cracking/IsomerizationDeoxygenation Green Jet
UOP 4788H-30
Selective cracking: Process and catalyst development to maximize economic production of
higher yields of jet-range paraffins
Maximizing jet fuel production: Identifying best catalyst through combinatorial chemistry
Combi Catalyst
Preparation
Combi testing
Lab Scale Preparation
Lab plant test/ confirmation
of combi results
Candidates for
development
Variables screened:•Acid supports•Metal type/concentration•Process Variables
g scale 500g scaleModelfeed
DeOx natural oil feed
Pilot plant screening: Yield confirmations/
short term stability
referenceGood performers
Poor performers
Many catalysts
6-8 candidates
Jet r
ange
Cracking Severity
•>70 supports•>2000 final catalysts (with metals)
9 months
Distribution Statement "A" (Approved for Public Release, Distribution Unlimited)
Properties of UOP’s Bio-Based JP-8
SampleFreeze Point,
oC Flash Point, oC Density, g/ccJP8 Spec -47 38 0.775UOP JP-8 range paraffins -52.6 53 0.759†
†Aromatic additives required to make JP-8 specification; also true for synthetic jet fuel
2 samples from different biofeedstocks met JP-8 specifications
JP8 SpecSoybean oil derived JP-8
Coconut oil derived JP-8
Petroleum JP-8
% aromatic (*added) max 25 vol % 15%* 22%* 18.8Freeze Point, C -47 -50 -62 -50Flash Point C 38 54 56 51Specific Gravity @ 15 C .775-.84 0.779 0.780 0.804Heat of combustion (Btu/lb) 18400 min 18600 18655 18600IBP C (D86) 165 169 15910% (D86) 157-205 176 177 18220% (D86) 180 179 18950% (D86) 168-229 199 188 20890% (D86) 183-262 268 226 244FBP C (D86) 300 279 262 265
Distribution Statement "A" (Approved for Public Release, Distribution Unlimited)
Meeting JP-8 specifications: Aromatics to meet density specs
Oil Selective Cracking/IsomerizationDeoxygenation
Green Jet-range
paraffins
UOP 4788H-30
Renewable JP-8
Aromatics(<25%)
Sources of Aromatics• Refinery sources
- Aromatics complexes- Platforming
• Renewable sources- Deoxygenated pyrolysis
oil
BiofuelsSustainability
UncompromisedProduct Quality
Life Cycles
Emissions
Vehicle Fleet
Technology
LignocellulosicCost
Net EnergyProduction ≤Consumption
Efficiency
Supply Chain
Algal
Energy Content
Distributed
FeedstockAvailabilityWorld Trade
Standards
Reduction inClimate Active
CO2 Equivalents
Sustainability
Uses Sustainable Feedstock Source
Established Technology
Supply Chain Issues Addressed
Minimizes Infrastructure Investment
Fleet Compatibility
Cost Neutral or Profitable Within The Fuel Pool
Allows Bio-component Substitution
Sustainability Scorecard
Renewable Fuels: Unlocking the Potential
XX
UOP 4856I-22
Inedible Oils: Camelina, Jatropha
Fuel Additives / Blends Fuels
Where is Biofuels Technology Headed?
JetDiesel
UOP’s Bio-Fuels Technology GoalsIdentify and utilize processing, composition, and infrastructure
synergies to lower capital investment, minimize value chain disruptions, and reduce investment risk.
BiodieselEthanol
• Lignocellulosic biomass to fuels
• Algal oils to fuels
Generation 1• Vegetable oils to
diesel, gasoline and jet fuel
Generation 2
Gasoline
UOP 4913C-09
Relative Heat Content
Source: EIA
(Mill
ion
Btu
/Sho
rt to
n) 25
30
20
15
10
5
0Pet
CokeCoal Pulp &
PaperWaste
Wood/WoodWaste
Muni-cipalSolidWaste
Agri-cultural
by-products
SludgeWaste
Biological feedstocks have lower heat content than fossil feedstocks
UOP 4913C-15
Lignocellulosic Biomass to Fuels Via Pyrolysis
StabilizationPyrolysisBiomass
Mixed Woods
Corn Stover
Deoxygenate
GasolineDieselJetChemicals
Other Refinery
Processes
Biocrude
Refin
ery
P P
P P
P P
UOP 4913C-17Collaboration with DOE, NREL, PNNL
Typical Fast Pyrolysis Process
Biomass
Char
Heat for Drying
Heat for Pyrolysis
Gas
Gas RecycleFluidizingGas
PyrolysisOil
From “Fast Pyrolysis of Biomass: A Handbook.” A.V. Bridgwater et al.
H2O= 10-40%
H2O= 5%
H2O= 15-40%
Reactor
Cyclone
Grind
Dry Cooland
Collect
UOP 4913C-18
Hydrocarbon product rich in cyclic hydrocarbons:product can produce gasoline, jet fuel, diesel, and
chemicals
Deoxygenated Product PropertiesBiofuel
(from mixed wood)
Conventional(from petroleum)
Min Max Gasoline Typical
ULS Diesel Typical
Paraffin, wt% 5 1044 10-60
Limited by cold flowIso-Paraffin, wt%
17 25
Olefin, wt% 0.6 0.9 4 Nil
Naphthene, wt%
40 55 7 10-80
Aromatic, wt% 10 35 38 35 maxLimited by emissions
Oxygenate, wt%
0.1 0.8 Nil Nil
UOP 4913C-19
Deoxygenated Pyrolysis Oil to Jet Fuel
Range of jet range hydrocarbons: 45 – 65% depending on feed source and process conditions
Boiling Point Distribution
0.0
2.0
4.0
6.0
8.0
10.0
0 50 100 150 200 250 300 350 400 450 500 550 600Temperature, °C
wt%
in 1
0° D
elta
T
Mixed Wood Derived (Cond. 1) Mixed Wood Derived (Cond. 2)Corn Stover Derived (Cond. 1) Corn Stover Derived (Cond. 2)
2nd generation Renewable Jet Fuel from oils and biomass
Green Jet-range paraffins
Selective Cracking/
Isomerization
Natural Oils and
FatsDeoxygenation
UOP 4788H-30
Renewable Jet Fuel
Biomass contribution can be >50%
Solid Biomass
Catalytic Stabilization/
DeoxygenationPyrolysis
Jet Range cyclic
hydrocarbons
Renewable Aromatics
JP-8 Spec
StartingParaffin
Deoxygenated Pyrolysis Oil (Corn Stover derived)
Deoxygenated Pyrolysis Oil (Mixed wood derived)
Freeze Point (oC) -47 -53 -56 -54
Flash Point (oC) 39 53 49 54
Density (g/mL) 0.775 0.759 0.790 0.782
100% Bio-derived JP-8 product is possible
Distribution Statement "A" (Approved for Public Release, Distribution Unlimited)
2nd generation Renewable Jet Fuel from algae
Source: Q. Hu,
• High cellular oil content (~50% of dry weight) • High photosynthetic efficiency (10~20%)• Excellent CO2 capture and sequestration capability• Water requirement: less than 1/40 of land plants and thrive
in saline/brackish/waste water• Land requirement: desert and arid lands
Integrated Algal Processing for jet fuel production
CO2
Green Jet (paraffin-rich)Other Products: Green diesel and chemicals
Green Jet (rich in cyclic hydrocarbons)Other products: Green gasoline; diesel; chemicals
2nd Generation On-spec
Renewable Jet Fuel
BiofuelsSustainability
UncompromisedProduct Quality
Life Cycles
Emissions
Vehicle Fleet
Technology
LignocellulosicCost
Net EnergyProduction ≤Consumption
Efficiency
Supply Chain
Algal
Energy Content
Distributed
FeedstockAvailabilityWorld Trade
Standards
Reduction inClimate Active
CO2 Equivalents
Sustainability
Uses Sustainable Feedstock Source
Established Technology
Supply Chain Issues Addressed
Minimizes Infrastructure Investment
Fleet Compatibility
Cost Neutral or Profitable Within The Fuel Pool
Allows Bio-component Substitution
Sustainability Scorecard
Renewable Fuels: Unlocking the Potential
X
X
UOP 4856I-29
Summary
• 1st generation renewable processes commercialized or in development: Natural oils and fats to diesel and jet fuel
• 2nd generation renewable fuel: Biomass and algae to fuels- Proof of principle work completed in NREL-PNNL-UOP
CRADA: Biomass to fuel via pyrolysis oil hydrodeoxygenation
- Algae offers great potential to produce large quantities of oils and biomass for sustainable jet fuel production
Acknowledgements
• NREL - Richard Bain- David Hsu
• PNNL - Doug Elliott - Don Stevens
• UOP - Mike McCall- Tim Brandvold- Graham Ellis- Zhihao Fei- Chris Gosling - Tom Kalnes - Peter Kokayeff- Rich Marinangeli- Terry Marker - Prabhakar Nair
DOE, Project DE-FG36-05GO15085Paul Grabowski
UOP 4913C-28
DARPA, Project W911NF-07-C-0049Dr. Douglas Kirkpatrick
UOP 4926-28
Top Related