Utilizing Biorenewable Materials for the Production of Bio-Based Products in Sustainable Ways: Learning Its Opportunities and Challenges

  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 24 th

  2014 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

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

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

  What is Sustainability or Sustainable Development? Terms Now Used Interchangeably

  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. Conservation tillage is currently practiced on less than 10% of global cropland n.a. / $ / !*

  How to meet the needs of the present generation… …without compromising the ability of future generations to meet theirs

  Sustainable Development (United Nations)

  Sustainability:

The triple bottom line

• Society depends on the economy
• The economy depends on the global

  ecosystem , whose health represents the ultimate bottom line .

  Coined by John Elkington, SustainAbility

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

  

I=PxAxT---Unique Role for the

Scientific Profession!!!

T , is the home

• In the “Master” Equation, domain of the scientific profession

• • Our critical professional challenge is to reduce

  T in terms of “environmental impact” per unit of GDP

  I to stay constant, the inevitable increases

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

  

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

  Climate Change

  

What changes climate?

• Changes in:
• – Sun’s output
• – Earth’s orbit
• – Drifting continents
• – Volcanic eruptions
• – Greenhouse gases

  “Greenhouse effect” Increasing greenhouse gases trap more heat

Greenhouse Gases

  Nitrous oxide Water Carbon dioxide

  Methane Sulfur hexafluoride

  Could the warming be natural?

  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

  4 billion tons go in billion tons added every year

  

Past, Present, and Potential Future

Carbon Levels in the Atmosphere

1200 (570) “Doubled” CO ₂

  (380) 800 Today Pre-Industrial (285) 600 400 (190) Glacial Billions of tons of carbon billions of tons ppm

  ( ) carbon Princeton Institute:

  2 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

  Biofuels

Reducing CO2 emissions by 1 Gtons/year requires scaling up current global ethanol production by 30 times

  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

  T, H / $$

  Take Home Messages , we need to

   In order to avoid a doubling of atmospheric CO

  2 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 CO doubling

   Biomass, Biofuels and Sustainability

  

Alternative Energy Sources

  Wind Energy Nuclear Energy Biomass Energy

  Solar Energy Geothermal Energy Ocean/Waves Energy

• How much do you think the total contribution of these alternative energy sources to the total production of energy in the World?

  Hydro Energy

  What separates biomass from other sustainable resources?

Sustainable Alternative Resources for Transportation Fuels End Sustainable Primary Secondary Utilization Resources Intermediates Intermediates

  Sunlight Wind

  Organic Biomass

  Fuels Ocean/ Hydro

  Transportation Electricity Hydrogen

  Geothermal Batteries

  Nuclear 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.

The goal is not ethanol or biodiesel!

  

st

Generation Biofuels

  1 st Generation biofuels have issues

  1 st Generation Biofuels: Main Issue http://www.naturalnews.com/023092_corn_ethanol_biofuels.html

  Fuels Produced from Biomass

Not only Ethanol and Biodiesel!

  

Fuel Specific LHV Octane Cetane

Gravity (MJ/kg) Number Number 27 109

• Ethanol 0.794

  Biodiesel 37 - 0.886

  55

  20.1 109 - Methanol 0.796

  0.81 36 96 - 105 - Butanol Mixed Alcohols ~0.80 27-36 - 96-109

  43.9 - Fischer-Tropsch Diesel 0.770

  74.6

• Hydrogen 0.07 (liq) 120 >130 Methane 0.42 (liq)

  49.5 >120 - 28.9 >55 - Dimethyl Ether 0.66 (liq) 43.5 91-100 - Gasoline 0.72-0.78

  0.85 45 37-56 - Diesel

  nd

• Developed to overcome the

  st

  limitations of 1 generation biofuels (fuel vs. food)

• Feedstock: non-food crops, e.g woods, organic waste, agricultural waste & specific biomass crops

Lignocellulosic Biomass

  Polymer of 5- and Complex aromatic structure p-hydroxyphenylpropene

  6-carbon sugars building blocks

  Lignin Hemicellulose 10-25% 20-40% Cellulose 40-60% Polymer of glucose

  35

Components of Biomass

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

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

Our Biomass Resources

• 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

  Ag.process residues &manure Fuel wood

  Milling residues Urban Wood

  Lodging Residues Forest thinning

  Crop residues Dedicated crops

  Grains for biofuels

• 50 50 150 250 350 450

  Million Dry Tons per Year

Our Biomass Resources

Herbaceous Crops

  Switchgrass Mischantus

Energy Crops

  Willow Poplar

  Eucalyptus Pine

  Sugarcane Jatropha Curcas

Other Energy Crops

  Camelina Algae

  Mesquite (Considered weeds, not energy crops)

  Hemp How about biomass potential in Indonesia?

Routes to Make a Biofuels Hydrogen Gasoline

  Water-gas shift Syn-gas Methanol

  Gasification CO + H MeOH Synthesis _{2 2} Olefins Alkanes

  Lignocellulosic Biomass Fischer-Tropsch Synthesis Catalytic/

  (woody plants, fibrous Non-catalytic plants)

   Aromatics, hydrocarbons Gasification Hydrodeoxygenation

  Aromatics, light alkanes, Fast Pyrolysis Zeolite upgrading coke Bio-oils Direct Use

  Liquefaction Emulsions Alkyl benzenes, parrafins

  Hydrodeoxygenation Lignin

  Pretreatment & Aromatics, coke Corn

  Hydrolysis Zeolite upgrading Stover

  MTHF (methyl- Furfural Bagasse

  C5 Sugars Hydrogenation Dehydration tetrahydrofuran)

  (Xylose) Corn

  Levulinic Levulinic Corn C6 Sugars Dehydration Esterification

  Hydrolysis Grain

  Esters Acid (Glucose, Fructose)

  MTHF (methyl- Hydrogenation

  Sucrose (90%) tetrahydrofuran)

  Sugarcane Glucose (10) Alkyl esters (Bio-diesel) Transesterification

  Lipids/ Ethanol, C -C Alkanes/Alkenes _{1 14} All Sugars

  Fermentation Butanol Triglycerides Zeolite/Pyrolysis C -C n-Alkanes (Vegetable _{12 18} Hydrodeoxygenation Oils, Algae)

  Direct Use Blending/Direct Use 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

   to Biorefineries Approaches

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

  Lipid-based Approach

  

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.

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

  65 o

C, 30-60 min. Biochemical Approach (Fermentation)

Starch-based Biochemical Biorefinery

  CO

  2 Starch

  Enzymes Fermenter

  Grain Pretreatment

  Distillation EtOH

  Whole Stillage

  Drying Cooking

  DDGS (byproduct) Corn Oil

Cellulose-based Biochemical Biorefinery

• Similarities with conventional corn ethanol plant:
• – Pretreatment – Saccharification (release C5 and C6 sugars)
• – Fermentation (both C5 and C6 sugars)

  Distillation

  Lignin (byproduct)

  Fermenter

  Ethanol & other

  CO

  2 fermentation Cellulose Enzymes products

  Pretreatment Saccharification

  Cellulosic water C5 & C6 Sugars

  Biomass

  Thermochemical Biorefineries

  Thermo-Chemical Conversion Modes

[2] Bridgewater

  

Process Parameters

Fast: 500C, 1sec Gasification: 750-900C Torrefaction (slow): 290C, 10-60min

  5% 13% 10% Liquid

  12% Solid 20% Gas

  75% 85%

  80% Figures [2] Bridgewater

Gasification Approach: Challenge Air CO O + H

  _{2 2} THERMAL COMBUSTION HEAT POWER Steam

  ON Gas

  REFORMING + FUEL CELLS TI

  H + CO _{2 2} CO + H Cleaning ₂ WGS CA FI Biomass

  GASI Char

  Organic acids Alcohols CATALYSIS/

  Air/O /Steam ₂ FUELS & FERMENTATION Esters

  CHEMICALS Hydrocarbons Syngas needs to be cleaned and pressurized to be used as feedstock for power, fuels and chemical production COSTLY!!

   Fast Pyrolysis Approach

  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 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

  o Typical yields (400-500

  C) Oil: 60 - 70%

• – Rapid quenching at the end of the process

  Char: 12 -15% Gas: 13 - 25%

Fast Pyrolysis-based Biorefinery Green diesel Centralized Distributed (Large-scale) Facility (Small-scale) Facilities

  Bio-oil vapor Cyclone

  er Hydrogen

  Steam

  rack Char oc

  Reformer Bio-Oil

  ydr H

  Recovery

  High Water- Content Phase er

  Syngas yz rol

  Bio-Oil

  Combustor Phase

  Py

  Separation

Biomass

  Low Water- Content Phase Combustion

  Transport Gases

  Air

Applications of Bio-Oil

Biomass

  Liquid Extraction

  Steam Distillation

  Fuels for Turbine, Engine, Heat, Electricity and Transport Steam

  Reforming Hydrogen

  Hydrodeoxy- genation Chemicals

  Hydro- cracking

  

Bio-Oil from Fast

Pyrolysis of Biomass

  Hydropyrolysis Catalytic Pyrolysis

  Conventional

Alcohol treatment

Composition of Bio-Crude Oil

  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 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 15-30

  0.1 Moisture Content, wt %

  2.5

  pH

• Specific gravity

  1.2

  0.94 Elemental composition, wt % C

  54-58

  85 H 5.5-7.0

  11

  35-40

  1.0 O

  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

Challenges in Utilizing Bio-Oil

   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.

  Upgrading is needed top make bio-oil more useful and commercially feasible for final applications

Reactivity Scale of Oxygenates under Hydrotreatment

  o 150 C

  Olefins Aldehydes

  o

  Alcohols

  200 C

  Ketones

  o Aliphatic Ethers 250 C

  Thermal Olefins

  Aliphatic Alcohols dehydration

  o 300 C

  Carboxylic Groups Phenolic Ethers

  o 350 C

  Phenols Di-Phenyl Ether

  o 400 C

  Dibenzofuran

  Douglas C. Elliott (2007)

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?

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 ~ 430 ^o C (dT/dt)

  →∞ CO + H ₂ 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.

  

Biomass Utilization for Bioenergy and

chemicals is not only about technology

development !

  Biomass Conversion Processes Products

  Utilization Biomass Pretreatment/ Preconditioning

  Biomass Production CO2, H2O, Plant Nutrients

  CO2, H2O, Plant Nutrients

  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

A system for utilizing biomass to energy, chemical and fuels

Agricultural and Bioenergy Value Chain

  Germplasm Cultivation Harvest Transport Storage Processing

  Energy Agricultural companies companies

  

Lack of focus on economic drivers

Overly simplistic assumptions by

bio-fuel industries

  

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

chain does not work”

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 Plants Farming Practices

  Where is the energy put in to this cycle? In what form? How is energy used in the cycle?

  Feedstock Transport

  How much are the green house gases emitted from the cycle?)

  Automobiles Refining Product 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 utilization process chain. Evaluation of a process by using Life Cycle Analysis

(LCA) can be used to determine the sustainability of biomass utilization.

  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:

Phone: 610-519-6658