The Biorefinery Concept: Its emergence and application on Long Island

1
The Biorefinery Concept Its emergence and
application on Long Island

• Devinder Mahajan
• Advanced Energy Research and Technology Center
  (AERTC)/
• Chemical Molecular Engineering (CME)
• Stony Brook University
• Energy Sciences and Technology Department (ESTD)
• Brookhaven National Laboratory
• Presented at
• Energy Long Island Conference 2007- Challenges
  of Today and Tomorrow
• Farmingdale State College
• Farmingdale, NY

2
The Future Fuels Group (BNL/SBU)

• Collaborators
• CR Krishna (BNL)
• T. Butcher (BNL)
• N. van der Lelie (BNL)
• K. Ro (USDA)
• P. Hunt (USDA)
• M. Rafailovich (SBU)
• H. Zhang (SBU)
• M. Castaldi (Columbia U.)
• Farmingdale
• H. Tawfik
• 10 Students

• Students
• Graduate
• - M. Eaton
• M. Anjom
• P. Kerkar
• Y. Hung
• CME Undergrads
• SULI/Battelle Fellowship program
• 9 students

• FUNDING
• U.S. Department of Energy (US DOE)
• BNL Laboratory Directed R D (LDRD)
• U.S. Department of Agriculture (USDA)
• USB Research Foundation
• Industry

3
Alternate Energy Options

• Non-petroleum options
• ? Biomass
• ? Geothermal
• ? Solar
• ? Wind
• ? Tidal
• Impact Sectors
• ? Transportation
• ? Utilities (electric, gas)
• ? Manufacturing
• Focus of RD in our group

4
Presentation Focus

• ? Biorefinery concept and Distributive fuel
  production concept
• ? Biofuels
• ? Our Research in biofuels
• ? Relevance to Long Island

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Possible Routes from Biomass to Energy Fuels

• Source 1 billion tons of biomass available
  (USDA estimate).
• Biomass Processing-
• Sugar Platform Biochemical Route
• Syngas Platform- Thermochemical Route

gy
Resources
Conversion
Product
Market
Solid Biomass (Wood, straw)
Combustion
Heat
Heat/CHP
Gasification
Fuel Gas
Electricity
Wet Biomass (organic waste, manure)
Pyrolysis
Bio oil
Transportation Fuels
Sugar, Starch plants (sugar beet, cereals)
Digestion
Biogas
Hydrolysis Fermentation
Bioethanol
Chemicals
Oil Crops (rapeseed, other oils)
Extraction Esterification
Biodiesel
Source Chemical Engineering, October 2006
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Biorefinery Concept

Esterification
Biodiesel
Fermentation
Biomass
Bioethanol
Gasification
BioFuels
Syngas
Biofuels includes any liquid fuel
? Biorefinery concept is appealing because it
will use the existing infrastructure. ? Biomass
to BioFuels- Next-generation technologies are
needed. Fischer-Tropsch technologies will play
a role.
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Biofuels

• Definition Fuels derived from CO2-net neutral
  feedstocks.
• Gasoline Consumption (2005) 140 billion gallons
• Biofuels Market Share (2005) 4 gasoline
  consumption
• Target Fuel 2005 2012 2025 (gallons/year)
• Bioethanol U.S. 5x109 7.5x109 60x109
• Biodiesel U.S. 0.6x109 1.3x109 (2008) ---
  
• Bioethanol Brazil 4.5x109
• Corn based Data from NBB Sugarcane based
  (45 of the world total).
• Goal Replace 75 oil imports by 2025.

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Biofuel 1 Biomass to Biodiesel

Esterification
Biomass
Biodiesel

• Biodiesel Production Methods
• Base catalyzed transesterification of oil
• Direct acid catalyzed transesterification of oil
• Convert oils into fatty acids and then to
  biodiesel

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Biomass to Biodiesel- Production

Base catalyzed esterification reaction CH2OCOR''
CH2OH R'''COOR CHOCOR''
3 ROH Catalyst CHOH R''COOR
CH2OCOR CH2OH R'COOR (100 lbs)
(10 lbs) (10 lbs) (100
lbs)
Oil or Fat Alcohol (excess)
Glycerin Biodiesel
(Triglyceride) Mono-alkyl ester
Oil or Fat Soybean, Palmitic, oleic, stearic,
linoleic acids Catalyst KOH, NaOH ROH MeOH,
EtOH

• The process needs MeOH or EtOH
• Glycerin as a byproduct is a major issue.

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Biomass to Biodiesel- Process
Base Catalyzed Esterification of Oils
Source Lurgi Process

• Advantages
• Low T
• Low P
• Direct high conversion ( 98)

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Biodiesel Properties

• ASTM Standard- D6751
• Reaction completion
• Glycerin removal
• Catalyst removal
• Free fatty acids removal
• Fuel properties of biodiesel from Soybean oil

Ester Viscosity mm²/s Cetane No. ?Hg kJ/kg Tflash C CP C PP C
Methyl 4.08 46.2 39,800 191 2 -1
Ethyl 4.41 48.2 40,000 174 1 -4
Isopropyl 52.6 -9 -12
N-Butyl 5.24 51.7 40,700 185 -3 -7

No. 2 Diesel 2.39 45.8 45,200 78 -19 -23
?Hg gross heat of combustion Tflash flash
point (Penske Martins closed cup) CP cloud
point PP pour point
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Biodiesel Fuel Quality for Diesel Engines

• ASTM Specification for B100 for Blending has
  been developed (D6751)
• Changes being considered to improve quality
• Attempts are being made to address stability and
  compatibility
• with newer diesel technology concerns of
  engine manufacturers
• Additional research required to define and test
  for stability
• Lack of data relating stability and deposit
  formation in engine

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Biodiesel Production- Economics

• Improve Esterification
• - Processing steps
• Fuel to diesel engine specifications
• - Minimize impurities
• Glycerin Utilization
• - Catalytic conversion to fuels
• CH2OH
• CHOH CO H2
• CH2OH

Pt
Fuels
250- 3000C
? Work is ongoing at BNL/SBU to find a catalyst
for conversion of this byproduct to fuels.

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Biofuel 2 Biomass to Bioethanol
Biomass
Fermentation
Bioethanol

• C6H12O6 (aq) 2 C2H5OH (aq) 2 CO2 (g)
  
• Glucose
• Theoretical C Utilization 67
• CO2 product of fermentation process
• Typical processing time 48 hrs

Yeast
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Bioethanol Production- Schematics
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Bioethanol Production- Plant
Source Waste Conversion Technologies, UCLA
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Our Research on Biofuels- Next-generation
Technologies

(DOE Report)
Goal Maximize C conversion
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Distributive Fuel Generation Concept- BioFuels
on a Farm

• Goal
• Skid-mounted fuel production plants- Economy of
  scale!
• Approach
• Biomass contains both C and H atoms- Total
  carbon utility is
• the key.
• - driven by highly active catalysts
• - driven by process modifications

The approach combines process requirements
with process chemistry to design
next-generation atom economical fuel
production technology.
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Atom Economical Synthesis of Liquid Fuels
CO2
Ultra-Clean Fuels
Biomass
By-products
Process Waste
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Biomass Structural Units
Source US DOE
Cellulose Polymer and cross-linkages among
glucose units.
Hemicellulose 5, 6 carbon sugars, sugar acids,
acetyl esters- more complicated than cellulose.

Typical composition Carbohydrates/Sugars 75
Lignin 25
Lignin Phenolic polymers- impart strength to
plants.
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Biofuels via Catalytic Thermal Processing-An
Alternative to the Bio Route

Biomass
Gasification
BioFuels
Syngas

• Technical Barriers (U.S. DOE)
• Handling varying feed composition
• Syngas clean-up steps needed
• Develop utilization of produced gas
• Quote from T. Patzek, UC Berkeley- Presented at
  the National Press Club Conference, Washington,
  DC, August 2005
• Thermodynamically and kinetically,
  lignocellulosic ethanol is the poorest choice in
  comparison with 1) direct Biomass burning for
  Electricity or 2) Biomass Gasification.

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Biofuels from Biomass- The Gasification Route
Methanol
B I O M A S S
(Feedstock)
Hydrogen
SYNGAS CO,CO2,H2
(direct Indirect)
F-T Liquids
(Biorefinery Concept)
Alcohols (C2)
CO 2 H2 CH3OH CO 2 H2 -(CH2-)n
H2O
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Syngas Catalysis Reaction Characteristics
CO H2 Fuels ?H (-)
(Oxygenates, Hydrocarbons)

• Reaction Characteristics
• Exothermic
• Require a Catalyst
• Commercial catalyst micron-sized
• Gas/solid reaction in packed-bed reactor
• - Poor heat management
• Poor product selectivity
• Fuels are Ultra-Clean

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Syngas Catalysis Process Engineering Materials
Science/Chemistry/Chemical Engineering
Goal Atom Economy
Approach Liquid Phase Low Temperature (LPLT)
Approach
Controlled-site Catalyst
Liquid Phase Operation
Low Temperature
M
M
Use Single site or Clusters
M
M
? Center for Functional Nanomaterials (CFN) and
Process Engineering Laboratories in the new AERTC
building will be utilized for this work.
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BioMethanol Synthesis from Biomass

• Why Methanol?
• A liquid energy carrier- compatible with
  existing infrastructure.
• Excellent feedstock for fuels and chemicals
  (Replacement for
• petroleum feedstock).
• Contains 12.5 wt H2 - MeOH reacts with H2O to
  extract more H2
• (total H2 18.75 wt), highest H2 storage
  capacity.
• Methanol is a transition to HYDROGEN ECONOMY
• Methanol is converted to ethanol through
  Homologation (C-C Coupling)
• Challenge
• Develop an efficient Biomethanol synthesis
  process from Biomass.

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Flow Diagram Commercial Methanol Synthesis

• Catalyst is micron-sized Cu/ZnO
• Uses fixed bed or slurry-phase
• Problem identified
• lt 20 syngas (C) conversion per pass. Requires
  large gas recycle, expensive compressors.

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An Ideal Methanol Process
T and P Curves for Methanol Synthesis (Lit.)
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Evolution of Single-site MeOH Catalyst

• External activation of CO by Alkoxide base
• Hydrogenation of activated CO by Ni

Pt-Group Metals
AM-OR
Solvent
KOMe/NiCl2/Triglyme-MeOH
CO/H2
MeOH
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Methanol Synthesis Process Comparison
Parameter (Bio) LPLT Commercial Syngas
production Air O2
separation plant Reaction T, oC ..
110 265 Reaction P, MPa
1 5 Equilibrium CO Conversion,
94 61 Operating CO
Conversion, 90 20 Gas
recycle, No High
NRC Report (1992)- Catalysis Looks to the
Future
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End use Application of Biofuels- Low Temperature
Cascade for Fuel Cell
Biomethanol Synthesis
Biomethanol Decomposition
Water-Gas Shift
Fuel Cell
3H2 CO2
T lt 150ºC
CO 2H2 H2O
Biomass Methane

• CH3OH H2O ? CO2 3H2
• ? H2 Storage capacity 18.75 wt.

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The Future of BioFuels

• Interest from Major Commercial Companies
• Dupont
• Chevron
• BP
• VeraSun
• Broin
• Other Biofuels Biobutanol
• Advantages (compared to Ethanol)
• Higher energy content
• Easily blends with gasoline
• Higher blending ratio
• Oxidation products less volatile (???)
• Butanol yields butraldehyde/butyric acid
• Ethanol yields acetaldehyde/acetic acid
• Processing Cellulosic Materials
• Breakdown complex molecules to simple sugar for
  further processing to biofuels.
• Develop better bio or chem. Catalysts

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The Future of BioFuels

• Other biofuels portfolio
• Biobutanol, biomethanol, biohydrocarbons (F-T
  process)
• Tax Credits (Energy Policy Act of 2005)
• 10 / gallon (up to 15x106 gallons of
  agri-biodiesel.
• Net energy content (based on LCA)
• Energy input 1.00
• Biodiesel (1.93) gt bioethanol (1.25)
• Environmental Concerns
• Increased use of 1) fertilizers and 2)
  Pesticides.
• Fate of environmental oxidation products
• Proc. Natl. Acad. Sci. USA 103 11206 (2006).

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A Path to Sustainable Development

• Resource consideration
• - 1 billion ton biomass is available
• Distributive fuel production
• - Small is beautiful
• Process and related chemistry need to be
  integrated
• for Product flexibility
• Closely related process chemistry
• ? Alcohol Economy- A transition to Hydrogen
  Economy

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Relevance and Challenges to Long Island

• What are our resources?
• - MSW, trapped grease (Bergen Point), wood
• chips, pine cones
• Environmental Considerations
• - Protect Pine Barrens and Aquifers
• Small plants could be located on LI (work with
  towns, Counties)
• ? Nurture intellectual resource of New York
  State- Develop and license technologies globally

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Publications
Guest Editor D. Mahajan
Clean Fuels
Methane Hydrates 2007
Biomass to Fuels Scheduled
publication Dec. 2007
2005