Justinus A. Satrio, Ph.D. Biomass Resources & Conversion - - PowerPoint PPT Presentation

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 Malang, Indonesia, April 24th 2014

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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 – Sustainability issues with biomass utilization

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Why Biomass? Issues: Thinking about Sustainability and Climate Change (?)

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“We cannot solve our problems with the same thinking that we used when we created them.” – Albert Einstein

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What is Sustainability or Sustainable Development?

Terms Now Used Interchangeably

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Natural Sinks

Photo courtesy of NREL, SUNY Stonybrook, United Nations, FAO

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. / $ / !*

Conservation tillage is currently practiced on less than 10% of global cropland 6

How to meet the needs

• f the present generation…

…without compromising the ability of future generations to meet theirs

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Sustainable Development (United Nations)

Sustainability: The triple bottom line

• Society depends on the

economy

• The economy depends
• n the global

ecosystem, whose health represents the ultimate bottom line.

Coined by John Elkington, SustainAbility

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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 T = environmental damage from technology per unit of consumption

Source: Ehrlich and Holdren (1971)

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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

• f GDP
• For I to stay constant, the inevitable increases

in P x A must be offset by corresponding reductions in T

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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
• Etc

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Climate Change

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What changes climate?

• Changes in:

– Sun’s output – Earth’s orbit – Drifting continents – Volcanic eruptions – Greenhouse gases

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“Greenhouse effect”

Increasing greenhouse gases trap more heat

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Greenhouse Gases

Nitrous oxide Water Carbon dioxide Methane Sulfur hexafluoride

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Could the warming be natural?

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Winter 2014 in PA – Snowiest Winter in Recent History

Climate Change Effect?

2 2

= 4 billion tons go out Ocean Land Biosphere (net) Fossil Fuel Burning +

8 800

billion tons carbon

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billion tons go in billion tons added every year

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Billions of tons of carbon

“Doubled” CO2 Today Pre-Industrial Glacial 800 1200 600 400

billions of tons carbon

( ppm )

(570) (380) (285) (190)

Past, Present, and Potential Future Carbon Levels in the Atmosphere

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Princeton Institute: 15 Approaches for reducing CO2 emissions

• 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

• 14. Forest Storage
• 15. Soil Storage

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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

T, H / $$

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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

• Every “wedge” has associated impacts and costs

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Biomass, Biofuels and Sustainability

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Wind Energy Nuclear Energy Biomass Energy Solar Energy Geothermal Energy Ocean/Waves Energy Hydro Energy

Alternative Energy Sources

• How much do you think the total contribution of

these alternative energy sources to the total production of energy in the World?

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What separates biomass from other sustainable resources?

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Biomass Electricity Sunlight Wind Ocean/ Hydro Nuclear Organic Fuels Transportation Hydrogen Batteries Geothermal Sustainable Resources Primary Intermediates Secondary Intermediates End Utilization

Sustainable Alternative Resources for Transportation Fuels

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Among sustainable resources, biomass is the only resource that produces carbon, which is the primary chemical element in transportation (liquid) fuels. Until our transportation systems are no longer energized by liquid fuels, we will continue rely on carbon-based resources.

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The goal is not ethanol or biodiesel!

Ethanol and Biodiesel are 1st Generation Biofuels 1st Generation biofuels have issues

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1st Generation Biofuels: Main Issue

http://www.naturalnews.com/023092_corn_ethanol_biofuels.html 32

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

Methanol 0.796 20.1 109

• Butanol

0.81 36 96 - 105

• Mixed Alcohols

~0.80 27-36 96-109

• Fischer-Tropsch Diesel

0.770 43.9

• 74.6

Hydrogen 0.07 (liq) 120 >130

• Methane

0.42 (liq) 49.5 >120

• Dimethyl Ether

0.66 (liq) 28.9

• >55

Gasoline 0.72-0.78 43.5 91-100

• Diesel

0.85 45

• 37-56

• Developed to overcome the

limitations of 1st generation biofuels (fuel vs. food)

• Feedstock: non-food crops, e.g

woods, organic waste, agricultural waste & specific biomass crops

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2nd Generation Biofuels

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 6-carbon sugars

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Components of Biomass

Any type of plants may contain some or all of the following components:

• Cellulose
• Hemicellulose
• Lignin
• Starch
• Pectins
• Vegetable Oil/Fats

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• 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)

Our Biomass Resources

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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

Our Biomass Resources

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Herbaceous Crops

Switchgrass Mischantus Coastal Bermuda Grass

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Energy Crops

Willow Poplar Eucalyptus Pine Sugarcane Jatropha Curcas

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Other Energy Crops

Camelina Mesquite (Considered weeds, not energy crops) Hemp Algae

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How about biomass potential in Indonesia?

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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 (methyl-

tetrahydrofuran) Esterification Hydrogenation MTHF (methyl- tetrahydrofuran)

Levulinic Esters Lipids/ Triglycerides (Vegetable Oils, Algae)

Transesterification Zeolite/Pyrolysis Hydrodeoxygenation Blending/Direct Use

Alkyl esters (Bio-diesel) C1-C14 Alkanes/Alkenes C12-C18 n-Alkanes Direct Use 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 Corn Stover G.W. Huber, S. Iborra, A. Corma; Chemical Reviews 106, 4044 (2006).

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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 Agriculture

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Approaches to Biorefineries

• Chemical (lipid platform)
• Biochemical (sugar platform)
• Thermochemical
• Gasification
• Pyrolysis
• Hybrids (e.g. biochemical-

thermochemical)

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Lipid-based Approach

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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.

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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.

Methanol , Catalyst 65o C, 30-60 min.

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Biochemical Approach (Fermentation)

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Starch-based Biochemical Biorefinery

CO2 Starch Enzymes Fermenter Grain Pretreatment Distillation EtOH Whole Stillage Drying Cooking DDGS (byproduct) Corn Oil

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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 Biomass Pretreatment Distillation water Lignin (byproduct) C5 & C6 Sugars Ethanol &

• ther

fermentation products

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Thermochemical Biorefineries

Thermo-Chemical Conversion Modes

[2] Bridgewater

Process Parameters

5% 10% 85% Gasification: 750-900C 75% 12% 13% Fast: 500C, 1sec Liquid Solid Gas 80% 20% Torrefaction (slow): 290C, 10-60min

Figures [2] Bridgewater

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 GASIFICATION

REFORMING + WGS

H2 + CO2 THERMAL POWER FUEL CELLS FUELS & CHEMICALS Air Steam

COMBUSTION CATALYSIS/ FERMENTATION

Gas Cleaning Char Air/O2/Steam

Fast Pyrolysis Approach

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Why Liquefying Biomass?

• Biomass is bulky with low energy density,

which makes transporting them costly

• Liquefying biomass increases the

energy density by 10 folds, reducing the cost of transportation

Fast Pyrolysis

• Rapid thermal decomposition of
• rganic 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 Typical yields Oil: 60 - 70% Char: 12 -15% Gas: 13 - 25%

Pyrolyzer Bio-Oil Recovery

Biomass

Bio-oil vapor Cyclone Char

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Combustor

Combustion Gases

Syngas Air Bio-Oil

High Water- Content Phase

Steam Reformer Hydrocracker Hydrogen

Green diesel

Low Water- Content Phase

Phase Separation Transport Distributed (Small-scale) Facilities Centralized (Large-scale) Facility

Fast Pyrolysis-based Biorefinery

Applications of Bio-Oil

Liquid Extraction Steam Distillation

Alcohol treatment

Fuels for Turbine, Engine, Heat, Electricity and Transport Steam Reforming Hydrogen Hydrodeoxy- genation Chemicals Hydro- cracking

Bio-Oil from Fast Pyrolysis of Biomass Biomass

Hydropyrolysis Catalytic Pyrolysis Conventional

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

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Direct use of bio-crude oil presents difficulties due to high viscosity, poor heating value, incomplete volatility, corrosiveness, and chemical instability.

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 Solids, wt% 0.2-1 1 Distillation residue, wt % Up to 50% 1

 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 commercially feasible for final applications

Reactivity Scale of Oxygenates under Hydrotreatment

Douglas C. Elliott (2007)

Olefins Aldehydes Ketones Phenols Dibenzofuran Alcohols Olefins

150oC 200oC 250oC 300oC 350oC 400oC

Aliphatic Ethers Aliphatic Alcohols Phenolic Ethers Carboxylic Groups Di-Phenyl Ether Thermal dehydration

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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.

Individual treatments needed to serve individual needs.

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

• Can we modify/transform certain components into new

forms that lead to desirable pathways instead of to non- desirable ones?

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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
• Bi-oil is formed as vapors and aerosols

Source: Raedlin, 1999

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

designed to handle multiple functionalities in bio-oils.

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Biomass Utilization for Bioenergy and chemicals is not only about technology development !

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 environmentally, need to be researched in concerted manners.

Research in Biomass Resources and Conversion Technologies

(BRCT) Laboratory

“If one step of the value chain does not work, the entire value chain does not work”

Germplasm Processing Cultivation Harvest Transport Storage Lack of focus on economic drivers Overly simplistic assumptions by bio-fuel industries Agricultural companies Energy companies

Agricultural and Bioenergy Value Chain

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?

• What are the processes?

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 Product Transport Refining Automobiles

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 utilization process chain. Evaluation of a process by using Life Cycle Analysis (LCA) can be used to determine the sustainability of biomass utilization.

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Questions/Comments?

http://www3.villanova.edu/biomass/

Biomass Resources and Conversion Technologies BRCT Laboratory

Thank you for Listening!

Questions/Comments?

Contact:

• Dr. Justinus A. Satrio, Ph.D.

Villanova University Dept of Chemical Engineering 800 E. Lancaster Avenue Villanova, PA 19085 E-mail: justinus.satrio@villanova.edu Phone: 610-519-6658