advanced biomass to gasoline technology - us … · 2016-05-10 · key innovations in this...
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Grant # EE0002991 Exelus 1
Advanced Biomass to Gasoline
Technology
May 24th. 2013 Bio-Oil Technology Area Review
Mitrajit Mukherjee Exelus Inc.
This presentation does not contain any proprietary, confidential, or otherwise restricted information
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Grant # EE0002991 Exelus 2
Outline
Objectives Project Overview Technical Approach Summary of Results Relevance Critical Success Factors Future Work Summary
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Grant # EE0002991 Exelus 3
Goal Statement
Project seeks to develop a low-temperature chemical process to convert cellulosic biomass into a gasoline blend-stock
Key innovations in this technology are Novel biomass deconstruction scheme & Engineered catalysts that convert the de-polymerized
biomass into alcohols as high-octane gasoline additives
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Grant # EE0002991 Exelus 4
FOA Objectives
The objectives of this FOA are to develop: Technologies and processes necessary for abundant
commercial production of bio-fuels at prices competitive with fossil fuels;
High-value bio-based products: to enhance the economic viability of bio-fuels and power; to serve as substitutes for petroleum-based feedstocks and
products; and to enhance the value of co-products produced using the
technologies and processes; and A diversity of economically and environmentally sustainable
domestic sources of renewable biomass for conversion to bio-fuels, bio-energy and bio-based products.
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Grant # EE0002991 Exelus 5
Timeline
Start - September 1, 2010 End - August 31, 2013 Percent complete = 90%
Budget • Total project funding
– DOE share = $1.2 million – Contractor share = $0.4 million
• Funding received so far • DOE = $ 1.0 million • Project Partners = $0.5 million
• ARRA Funding = 0
Partners
Quad Chart
Barriers
1. Glucose Decomposition 2. High H2 Consumption 3. Dilute product concentration
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Exelus Grant # EE0002991 6
Project Overview
Biomass Structure Conventional Processes
Exelus Approach & Targets
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Grant # EE0002991 Exelus 7
Biomass has Complex Structure
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Grant # EE0002991 Exelus 8
Typical Approach
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Grant # EE0002991 Exelus 9
Exelus
Energy
Economics Environment
E3 Constraints
New process technologies must address all three aspects of modern fuel manufacturing:
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Grant # EE0002991 Exelus 10
Process Wish-list
Mild operating conditions Low Temperatures (< 250oC) Modest Pressures (< 40 bar)
Simple processing steps Fixed-bed reactors Conventional unit operations
Inexpensive catalysts Minimize use of precious metal catalysts No hazardous liquid acids
Modest utility requirements No biomass drying step Product concentrations > 20 wt% in water
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Grant # EE0002991 Exelus 11
Integrated Approach Catalyst Reactor
Process
<
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Grant # EE0002991 Exelus 12
Exelus Process Overview
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Exelus Grant # EE0002991 13
Technical Approach
Exelus Approach Technical Targets Major Mile-stones
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Grant # EE0002991 Exelus 14
Biomass-to-Gasoline Process
HOH
HOH
HH HH
OH
OH
Cellulose Crystal
Glucose Oligomers
De-crystalization & De-polymerization
Glucose
Hydrolysis
Deoxygenation & Cracking
Isopropanol
Ethanol
BioGasoline
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Grant # EE0002991 Exelus 15
Finding the Middle Ground
10
100
1000
0 1 10 100 1,000 10,000 100,000
Rea
ctio
n Te
mpe
ratu
re (o
C)
Reaction Time (Sec)
Enzymatic
Reactions
Exelus
Biomass-to-Gasoline (BTG)
Gasification
Pyrolysis
0.1
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Grant # EE0002991 Exelus 16
Innovations
0.00001
0.0001
0.001
0.01
0.1
1
10
100
0.0001 0.001 0.01 0.1 1 10 100 1000
Tim
e S
ca
le (s
ec
)
Length Scale (m)
10-10 10-8 10-6 10-4 10-2 100 102
104
102
100
10-2
10-4
10-6
10-8
Active Sites
Benign acid sites allow selective deconstruction of
cellulose to glucose
Pore Structure
Reactor Configuration
Process Design
Reduces glucose degradation to HMF, polymers, and other
undesired compounds
Uniform operating conditions reduce capital
and operating costs
Allows unrestricted diffusion of oligosaccharide molecules
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Grant # EE0002991 Exelus 17
Overall Chemistry
C6H10O5 + 6 H2 2 C3H8O + 3 H2O
C6H10O5 + 6 H2 3 C2H6O + 2 H2O
Cellulose Monomer
Hydrogen Propanol Water
Cellulose Monomer
Hydrogen Ethanol Water
ΔHf° = -186.5 kJ/mol propanol
ΔHf° = -103.4 kJ/mol ethanol
Propanol
Ethanol
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Grant # EE0002991 Exelus 18
Technical Targets & Barriers
Key Variables Technical Target Associated Barriers
Overall Process Performance (All Reactions Combined) Productivity >150 g biomass converted /
m3 catalyst /sec per reaction Reduced activity in low-cost catalysts Rate of cellulose decomposition
Selectivity >70% Selectivity to alcohols Methanation, reforming & etherification rxns Stability < 1 kg catalyst consumed /
ton alcohols produced Catalyst coking, corrosion under hydrothermal conditions
Catalyst Cost < $100 /kg Precious metal content Capital Requirements
Less than $8000 per barrel-per-day capacity
Separation requirements, reactor volume and configuration, process severity
Total Cost of Production
Less than $2.00 /gal alcohol product
Distillation costs, hydrogen requirement, energy inputs, process selectivity
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Grant # EE0002991 Exelus 19
Experimental Results
Cellulose Deconstruction Oligosaccharide Hydrolysis
Glucose Cracking/De-oxygenation Stability Test
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Grant # EE0002991 Exelus 20
Step 1: Cellulose Deconstruction
Breaking the hydrogen bonds
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Grant # EE0002991 Exelus 21
Types of Biomass Tested
Pine
Sawdust
Paulownia
Plant
Generic
Switchgrass
Switchgrass
EG1101 Switchgrass
EG1102
Exelus
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Grant # EE0002991 Exelus 22
Feedstock Flexibility
90%
92%
94%
96%
98%
100%
0 0.05 0.1 0.15 0.2Biomass Deconstruction Rate (1/hr)
Olig
osac
char
ide
Sel
ectiv
ity (%
) Micro-crystalline CelluloseGenetically Modified
Switch-Grass (EG-1102)
Birchwood
Pine
Genetically Modified Switch-Grass (EG-
1101)
Typical rates for industrial reactions
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Grant # EE0002991 Exelus 23
Step 2: Oligosaccharide Hydrolysis
Breaking the b-bonds
Oligosaccharide
Glucose
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Grant # EE0002991 Exelus 24
Step 2: Catalyst Screening Results
0
20
40
60
80
100
A B C D E F G
Olig
osac
char
ide
Conv
ersio
n to
Glu
cose
(%)
ConversionSelectivity
Catalyst Number
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Grant # EE0002991 Exelus 25
Step 3: Cracking and De-oxygenation
Breaking C-C and C-O bonds
Ethanol Iso-Propanol
Glucose
H2 H2
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Grant # EE0002991 Exelus 26
Step 3: Catalyst Screening Results
0
20
40
60
80
100
A B C D E
Glu
cose
to A
lcoh
ols
(%)
ConversionSelectivity
Catalyst Number
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Grant # EE0002991 Exelus 27
Integrated Test Unit
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Grant # EE0002991 Exelus 28
Integrated Stability Test Results
0
20
40
60
80
100
0 40 80 120 160 200 240 280 320
time on stream (hrs)
Con
vers
ion
/ Sel
ectiv
ity (%
)
Conversion of biomass
Selectivity to bio-gasoline
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Grant # EE0002991 Exelus 29
Bio-Gasoline Composition
Ethanol35%
Iso & n-Propanol60%
Methanol2%Butanol
3%
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Exelus Grant # EE0002991 30
Project Relevance
MYPP Mission & Goals Project Relevance
Approach to meeting targets
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Grant # EE0002991 Exelus 31
MYPP Mission & Goals
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Grant # EE0002991 Exelus 32
Project Relevance
BTG
Process80% Yield
1.3 Billion Tons of Biomass per
year
70% Usable for Biofuel
Lignin (burned for fuel), Inorganics, & Water
8.5 Million Barrels of
Gasoline Equivalent
per Day
450 Million Gallons per Year
of Alcohols
BTG
Process80% Yield
1.3 Billion Tons of Biomass per
year
70% Usable for Biofuel
Lignin (burned for fuel), Inorganics, & Water
8.5 Million Barrels of
Gasoline Equivalent
per Day
450 Million Gallons per Year
of Alcohols
Estimated Bio-Gasoline Cost = $2.00/gal
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Grant # EE0002991 Exelus 33
Approach to meeting project targets
Exelus Approach
Advantages Benefits
Liquid Phase Processing
No expensive solvents required “Green” process Ability to use wet biomass
Reduced energy consumption
Feedstock flexibility Heterogeneous
Catalysts No neutralization required No acid migration through process Simple separation of catalyst and process
streams
Low operating costs Low equipment costs
Engineered Catalyst Functionality
Intensifies and simplifies process by eliminating multiple separation steps.
Minimize coke, acid and polymer formation High overall selectivity
Low capital cost High catalyst stability Efficient conversion of
feedstock Novel Process
Chemistry High carbon efficiency and retention of 94%
of input chemical energy Highly efficient
process
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Exelus Grant # EE0002991 34
Critical Success Factors
RFS Mandates Biomass Logistics
Capital Cost Variable Cost of Production
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Grant # EE0002991 Exelus 35
RFS Mandate
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Grant # EE0002991 Exelus 36
Biomass Logistics
Biomass is a diffuse energy source
Has low energy content per unit mass and unit volume
Is limited in the amount that can be produced per unit land area.
Transporting biomass over large distances is energy-inefficient and economically prohibitive
Feeding solid bio-mass to reactors under pressure is a challenge
0
2000
4000
6000
8000
10000
5 10 15 20
Maximum Transport Distance (miles)
Max
imum
Bio
fuel
Pro
duct
ion
(bar
rels
per
day
)
Operating Window
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Grant # EE0002991 Exelus 37
High Capital Costs
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Grant # EE0002991 Exelus 38
Variable Costs
Biomass34%
Hydrogen38%
Utilities14%
Fixed Costs14%
Total Cost of Production = $530 /MT
Assumes 75% biomass and hydrogen selectivityEstimated Bio-Gasoline Cost = $2.00/gal
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Exelus Grant # EE0002991 39
Future Work
Techno Economic Evaluation Technology Validation
Developing Consortium Team
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Grant # EE0002991 Exelus 40
Mass Balance
Biomass to Fuels
Process
Biomass 1000 kg/hr
Hydrogen 50 kg/hr
Hydrocarbons 400 kg/hr
Water 400 kg/hr
By-products 250 kg/hr
Carbon Efficiency = 75%
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Grant # EE0002991 Exelus 41
Exelus
Bio-Gasoline Cost of Production
0
1
2
3
50 60 70 80 90 100Biomass Selectivity to Alcohols (%)*
Cos
t of P
rodu
ctio
n ($
/gal
)
$0.45/gal Utility Costs
Hydrogen Selectivity = 100%
50%
$0.45/gal Fixed Costs
*Lignin-free
Cost of Biomass $100/tonCost of Hydrogen $1500/ton
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Grant # EE0002991 Exelus 42
Technology Validation
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Grant # EE0002991 Exelus 43
Develop Consortium
Exelus
Launch
Customer
Catalyst
Manufacturer
Engineering Company
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Grant # EE0002991 Exelus 44
Summary
This project seeks to develop a break-through thermo-chemical process to convert cellulosic biomass into a high-octane gasoline blend-stock
Exelus process replaces conventional high-temperature processes like gasification and pyrolysis with a series of mild, low-temperature reactions achieved using novel catalytic methods
Selective conversion (>90%) of bio-mass to mixed alcohols has been demonstrated at mild conditions using “green” catalysts
Future work will focus on techno-economic evaluation of this new B2G process
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Grant # EE0002991 Exelus 45
Questions