Utilizing Biorenewable Materials for the
Production of Bio-Based Products in Sustainable
Ways: Learning Its Opportunities and Challenges
Justinus A. Satrio, Ph.D.
Biomass Resources & Conversion Technologies Laboratory and
Department of Chemical Engineering
Presented at
Faculty of Agricultural Technologies Brawijaya University
Lecture Outline
1. Introduction
–
About Villanova University
2. Technical presentation
–
Background: Why Biomass?
• Issues: Sustainability and climate change
–
Biomass:
• What is biomass and how is its potential?
–
Biomass Conversion Technologies
Why Biomass?
Issues:
“We cannot solve our problems with the
same thinking that we used when we
What is Sustainability or
Sustainable Development?
Natural Sinks
Eliminate tropical deforestation AND double the rate of new forest planting OR
Use conservation tillage on all cropland (1600 Mha
One wedge would require of new forests over an area the size of the continental U.S.
n.a. / $ / !*
How to meet the needs
of the present generation…
…without compromising
the ability of future
generations to meet theirs
Sustainability:
The triple bottom line
•
Society depends on the
economy
•
The economy depends
on the global
ecosystem
, whose
health represents the
ultimate bottom line
.
Big Picture: The “Master”
Equation
I = P x A x T
I = total environmental impact from human
activities
P = population
A = affluence or per capita consumption
I=PxAxT---Unique Role for the
Scientific Profession!!!
•
In the “Master” Equation,
T
, is the home
domain of the scientific profession
•
Our critical professional challenge is to reduce
T
in terms of “environmental impact” per unit
of GDP
•
For
I
to stay constant, the inevitable increases
Sustainability: Current Issues of
Concern
•
Climate Change or Disruption
•
Water
•
Ozone Depletion
•
Soil Degradation and Food Supply
•
Species Extinction
•
Oceans and Fishery Resources
•
Concentration of Toxics
•
Depletion and Degradation of Natural Resources
What changes climate?
•
Changes in:
–
Sun’s output
–
Earth’s orbit
–
Drifting continents
–
Volcanic eruptions
“Greenhouse effect”
Greenhouse Gases
Nitrous oxide
Water
Carbon dioxide Methane
Winter 2014 in PA – Snowiest Winter in Recent History
Climate Change Effect?
2
2
=4
billion tons go outOcean Land Biosphere (net)
Fossil Fuel Burning
+
8
800
billion tons carbon
4
billion tons go in
Billions of tons of carbon
“Doubled” CO2
Today Pre-Industrial Glacial 800 1200 600 400
billions of tons carbon (
ppm )
(570)
(380)
(285)
(190)
Princeton Institute:
15 Approaches for reducing CO
2emissions
1. Auto Fuel Efficiency
2. Transport Conservation
3. Buildings Efficiency
4. Electric Power Efficiency
5. CCS
—
Electricity
6. CCS
—
Hydrogen
7. CCS
—
Synfuels
8. Fuel Switching
—
Natural
Gas Power Plants
9. Nuclear Energy
10. Wind Electricity
11. Solar Electricity
12. Wind Hydrogen
13.Biomass Fuels
Biofuels
Photo courtesy of NREL
Using current practices, reducing CO2
emissions by 1 Gtons/year requires planting an area the size of India with biofuels crops Reducing CO2 emissions
by 1 Gtons/year requires scaling up current global ethanol production by 30 times
Take Home Messages
In order to avoid a doubling of atmospheric CO2, we need to
rapidly deploy low-carbon energy technologies and/or enhance natural sinks
We already have an adequate portfolio of technologies to make large cuts in emissions
No one technology can do the whole job – a variety of
strategies will need to be used to stay on a path that avoids a CO2 doubling
Wind Energy Nuclear Energy
Biomass Energy
Solar Energy Geothermal Energy
Ocean/Waves Energy
Alternative Energy Sources
•How much do you think the total contribution of these alternative energy sources to the total
Biomass Electricity Sunlight Wind Ocean/ Hydro Nuclear Organic Fuels Transportation Hydrogen Batteries Geothermal Sustainable Resources Primary Intermediates Secondary Intermediates End Utilization
Among sustainable resources, biomass is the only resource that produces carbon, which is the primary chemical element in
transportation (liquid) fuels.
The goal is not ethanol or biodiesel!
Ethanol and Biodiesel are 1st Generation Biofuels
Fuels Produced from Biomass
Not only Ethanol and Biodiesel!
Fuel Specific Gravity LHV (MJ/kg) Octane Number Cetane Number
Ethanol 0.794 27 109 -
Biodiesel 0.886 37 - 55
•
Developed to overcome the
limitations of 1
stgeneration
biofuels (fuel vs. food)
•
Feedstock: non-food crops, e.g
woods, organic waste,
agricultural waste & specific
biomass crops
Lignocellulosic Biomass
35
Cellulose 40-60%
Hemicellulose 20-40% Lignin
10-25%
Polymer of glucose
Complex aromatic structure p-hydroxyphenylpropene building blocks
Polymer of 5- and
Components of Biomass
Any type of plants may contain some or all of the
following components:
•
Cellulose
•
Hemicellulose
•
Lignin
•
Starch
•
Pectins
• Currently the U.S. consumes 190 million dry tons of biomass for energy consumption, which is approximately 3% of total energy consumption.
• Total potential in U.S. is in excess of 1.3 billion tons (about 21 EJ = 20 quadrillion BTU)
96 47 132 43 58 55 389 343 79
-50 50 150 250 350 450
Ag.process residues &manure Fuel wood Milling residues Urban Wood Lodging Residues Forest thinning Crop residues Dedicated crops Grains for biofuels
Million Dry Tons per Year
Herbaceous Crops
Energy Crops
Willow
Poplar
Other Energy Crops
Camelina
Mesquite
(Considered weeds, not energy crops)
Routes to Make a Biofuels
Lignocellulosic Biomass
(woody plants, fibrous plants)
Gasification
Syn-gas
CO2 + H2
Fast Pyrolysis Bio-oils Liquefaction Catalytic/ Non-catalytic Gasification Water-gas shift MeOH Synthesis Fischer-Tropsch Synthesis Hydrogen Methanol Gasoline Olefins Alkanes Hydrodeoxygenation Zeolite upgrading Emulsions Aromatics, hydrocarbons Aromatics, light alkanes, coke
Direct Use
Hydrodeoxygenation Zeolite upgrading
Alkyl benzenes, parrafins Aromatics, coke Dehydration Dehydration Furfural Levulinic Acid
Hydrogenation MTHF tetrahydrofuran) (methyl-Esterification
Hydrogenation MTHF (methyl-tetrahydrofuran) Levulinic Esters Lipids/ Triglycerides (Vegetable Transesterification Zeolite/Pyrolysis Hydrodeoxygenation
Alkyl esters (Bio-diesel)
C1-C14 Alkanes/Alkenes C12-C18 n-Alkanes
Lignin Pretreatment & Hydrolysis All Sugars Fermentation Ethanol, Butanol C6 Sugars (Glucose, Fructose)
Corn Corn
Grain Hydrolysis
C5 Sugars
(Xylose)
Sucrose (90%)
Glucose (10)
Sugarcane Bagasse
Bio-Refinery
“A processing and conversion facility that (1) efficiently
separates its biomass raw material into individual components
and (2) converts these components into marketplace products, including biofuels, biopower, and conventional and new
bioproducts.” The Biomass Research and Development
Technical Advisory Committee (2002) U.S. Departments of Energy and
Approaches
to Biorefineries
•
Chemical (lipid platform)
•
Biochemical (sugar platform)
•
Thermochemical
o
Gasification
o
Pyrolysis
Lipid-based Biorefinery
Lipid-based Biorefinery
• Extract lipids from plants like soybean, palm oil, jatropha or microalgae or from animal fats, then convert the lipids to fuel, called biodiesel, by reaction called transesterification.
Starch-based Biochemical Biorefinery
CO2 Starch
Enzymes
Fermenter
Grain Pretreatment
Distillation EtOH
Whole Stillage
Drying Cooking
DDGS (byproduct)
Cellulose-based Biochemical Biorefinery
•
Similarities with conventional corn ethanol plant:
– Pretreatment
– Saccharification (release C5 and C6 sugars)
– Fermentation (both C5 and C6 sugars)
CO2 Cellulose Enzymes Fermenter Saccharification Cellulosic Pretreatment Distillation water
Lignin (byproduct) Ethanol &
other
Thermo-Chemical Conversion Modes
Process Parameters
5% 10% 85% Gasification: 750-900C 75% 12% 13%Fast: 500C, 1sec
Gasification Approach: Challenge
Syngas needs to be cleaned and pressurized to be used as
feedstock for power, fuels and chemical production COSTLY!!
Organic acids Alcohols Esters
Hydrocarbons
Biomass
CO + H2
CO2 + H2O
HEAT GASI FI CA TI ON REFORMING +
WGS H2 + CO2
THERMAL POWER FUEL CELLS FUELS & CHEMICALS Air Steam COMBUSTION CATALYSIS/ FERMENTATION Gas Cleaning Char
Why Liquefying Biomass?
•
Biomass is bulky with low energy density,
which makes transporting them costly
• Liquefying biomass increases the energy density by 10 folds,
Fast Pyrolysis
•
Rapid thermal decomposition of
organic compounds in the
absence of oxygen to produce
liquids, char, and gas
– Small particles: 1 - 3 mm
– Short residence times: 0.5 - 2s
– Moderate temperatures (400-500 oC)
– Rapid quenching at the end of the process
Py rol yz er Bio-Oil Recovery Biomass Bio-oil vapor Cyclone Char Combustor Combustion Gases Syngas Air Bio-Oil High Water-Content Phase Steam Reformer H ydr oc rack er Hydrogen Green diesel Low Water-Content Phase Phase Separation Transport Distributed (Small-scale) Facilities Centralized (Large-scale) Facility
Applications of Bio-Oil
Liquid Extraction Steam Distillation Alcohol treatment Steam Reforming Hydrogen Hydrodeoxy- genation Hydro- crackingBio-Oil from Fast Pyrolysis of Biomass
Biomass
Wt%
Water 20-30
Lignin fragments: insoluble pyrolytic lignin 15-30 Aldehydes: formaldehyde, acetaldehyde, hydroxyacetaldehyde, glyoxal 15-20 Carboxylic acids: formic, acetic, propionic, butyric, pentanoic, hexanoic 10-15 Carbohydrates: cellobiosan, levoglucosan, oligosaccharides 5-10 Phenols: phenol, cresol, guaiacols, syringols 2-5 Furfurals 1-4 Alcohols: methanol, ethanol 2-5 Ketones: acetol (1-hydroxy-2-propanone), cyclopentanone 1-5
Composition of Bio-Crude Oil
Properties of Bio-oil vs. of Diesel Fuel Oil
Physical Property Bio oil (from wood) Diesel Fuel
Moisture Content, wt % 15-30 0.1
pH 2.5 -
Specific gravity 1.2 0.94
Elemental composition, wt %
C 54-58 85
H 5.5-7.0 11
O 35-40 1.0
N 0-0.2 0.1
HHV, MJ/kg 16-19 40
Viscosity (at 50% C), cP 40-100 180
Direct use of bio-oil present difficulties due to high viscosity, poor heating value, incomplete volatility corrosiveness, and chemical instability.
Presence of water in bio-oil (15-30%) lowers the heating value. It reduces the viscosity and enhances fluidity.
High levels of oxygen (35-40%) is the major factor responsible for instability and corrosiveness. It also leads to the lower
energy density and immiscibility with hydrocarbon fuels.
Challenges in Utilizing Bio-Oil
Upgrading is needed top make bio-oil more useful and
Reactivity Scale of Oxygenates under Hydrotreatment
Olefins Aldehydes Ketones Phenols Dibenzofuran Alcohols Olefins150oC
200oC
250oC
300oC
350oC
400oC
Primary Challenge in Upgrading Bio-Oil
Chemical components in bio-oil come from various classes. Many
components are “stable”; some are “un-stable” due to active functional groups.
“Bad” components in bio-oil to be removed/modified typically are
highly oxygenated with functionalities that make them ‘unstable’.
A ONE for ALL treatment may be difficult to be applied.
Research Explorations
Explore strategies in fast pyrolysis to produce bio-oil with
more stable components
•
Can we control the mechanistic of reactions during fast
pyrolysis in order to produce the desirable components
based on the end of use of the bio-oil?
Explore ways to make certain bio-oil components more
stable during upgrading reactions
Fast Pyrolysis Reaction Mechanisms
Biomass
Monomers/ Isomers
Low Mol.Wt Species Ring-opened Chains
H+
H+
M+ M+
Aerosols High MW Species Gases/Vapors Thermo- mechanical Ejection Vaporization Molten Biomass T ~ 430oC
(dT/dt)→∞
CO + H2
Synthesis Gas Reforming
TM+
Volatile Products
M+ : Catalyzed by Alkaline Cations
H+ : Catalyzed by Acids
TM+ : Catalyzed by Zero Valent Transition Metals
(Observed at very high heating rates)
Oligomers
• Fast pyrolysis reactions are very complex
Research Exploration
Bio-Oil Upgrading
Understand the mechanism and relative rates of reactions
involved for certain key components of bio-oil
•
Understand effects of levels of catalyst functionalities
(metals and acids)
Synthesize upgrading reaction catalysts specifically
Biomass Utilization for Bioenergy and
chemicals is not only about technology
A system for utilizing biomass to energy, chemical and fuels. Biomass Conversion Processes Products Utilization Biomass Pretreatment/ Preconditioning Biomass Production CO2, H2O, Plant Nutrients CO2, H2O,
Plant Nutrients CO2, H2O CO2, H2O
Thermal energy for processes Sunlight Energy for
fertilizer
Liquid fuels for production and transportation
Electricity Water
Recycle
Various aspects to make the system successful, economically and
Research in Biomass Resources and Conversion Technologies
“If one step of the value chain does not work, the entire value
chain does not work”
Germplasm Cultivation Harvest Transport Storage Processing
Lack of focus on economic drivers
Overly simplistic assumptions by bio-fuel industries
Agricultural companies
Energy companies
Applications and Technology to Choose
•
What are potential final products that can be
produced from each biomass?
•
What are the technologies that can be utilized
for each feedstock?
Life Cycle Assessment of Biofuels
Where is the energy put in to this cycle?
In what form?
How is energy used in the cycle?
How much are the green house gases emitted from the cycle?)
Plants Farming Practices
Feedstock Transport
Take Home Messages
Biomass is the only renewable resources that can be used directly to substitute fossil fuels for the production liquid transport fuels
Lignocellulosic biomass is the largest source of biomass that are potential to be used for the production of liquid fuels. The chemical nature of
lignocellulosic biomass makes it difficult to process.
There are many potential conversion technologies that can be used for
utilizing lignocellulosic biomass. Thermochemical process, particularly fast pyrolysis, is very promising technology to do the job.
Whether or not biomass as a right solution for our energy issues is
dependent on how ‘sustainable and environmentally friendly’ is the
Questions/Comments?
Biomass Resources and Conversion Technologies BRCT Laboratory
Questions/Comments?
Contact:
Dr. Justinus A. Satrio, Ph.D. Villanova University
Dept of Chemical Engineering 800 E. Lancaster Avenue
Villanova, PA 19085
E-mail: [email protected]
