Biomass Basics:

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• Biomass Basics
• Renewable Energy and Chemicals
• Dennis J. Miller
• Department of Chemical Engineering and Materials
  Science
• Michigan State University
• East Lansing, Michigan 48824
• [phone]
• millerd_at_egr.msu.edu

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Benefits of the Chemical IndustryTell Our
Students About It!!
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The Emerging Paradigm Sustainability and Green
Chemistry
"Sustainable development is development that
meets the needs of the present without
compromising the ability of future generations to
meet their own needs. The Brundtland Commission
Report, The United Nations, 1987.

• Environmentally Sustainable
• Economically Sustainable
• Socially Sustainable

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Petroleum
www.bp.com
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Distribution of proven (oil) reserves 1984,1994,
2004
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Oil reserves-to-production (R/P) ratios
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Oil consumption by region
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Major oil trade movements
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Energy Consumption Concepts(A great web site
www.bp.com)

• Material and Energy Balances
• How much fossil energy in MJ (oil, coal, gas)
  does the world use annually?
• How much oil does the U.S. use annually? (A
  about 1.5 cubic miles)
• How many watts per person does that equate to in
  the U.S.?

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Biorenewable Fuels and Chemicals
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Corn The Near-term Biofuels Feedstock

• 2005 Statistics
• Production 11.8 billion Bushels
• Acres planted 80.9 million acres
• Average yield 160 bushels/acre
• (vs. 137 bu/a in 2000!)
• The corn plant
• ?3.8 tons corn stover / acre (lignocellulosic)
• 3.8 tons corn grain / acre
• Societal/Global perspective questions
• How much of our fuel needs can corn provide?
• What are the costs associated with using corn
  for fuel?
• How does politics enter into corn ethanol?

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Corn to ethanol energetics

• C6H12O6 2 C2H5OH 2 CO2
• glucose ethanol carbon
  dioxide
• 1.0 kg 0.51 kg 0.49
  kg
• 17 MJ 15.8 MJ 0 MJ
• Theoretical yield 2.7 gal/bu
• EtOH yield (grain only) 450 gal/acre
• EtOH yield w/ 50 stover 670 gal/acre
• Ethanol energy content 80,000 Btu/gal
• Gasoline energy content 130,000 Btu/gal

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Ethanol fuel supply

• U.S. gasoline consumption (2006) 150 billion
  gal
• U.S. fuel ethanol consumption (2006) 6
  billion gal
• 4 of total gasoline demand
• Blended 10 with gasoline (40 of U.S. gasoline
  contains ethanol)
• 14 million of 80 million acres of corn harvested
• Ethanol energy exercises
• How much corn would be required to provide E10
  for the entire U.S.?
• A About 5 billion bushels (40 of 2006 U.S.
  crop)
• What land mass would be required to replace all
  U.S. gasoline with ethanol?
• A 200 billion gal EtOH equates to 75 billion
  bushels corn / yr or
• 300 million acres (22 of U.S. landmass)!

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Cellulosic Biomass long-term renewable biofuel
feedstock

• Composition (wt) Wood Switchgrass
• Cellulose 55 55
• Hemicellulose 20 30
• Lignin 25 15
• Yield (ton/acre) 3 - 8 3 - 10
• Ethanol yield (gal/ton) 90 - 100 90 - 100
• Challenges
• Switchgrass is low-density compared to corn, more
  costly to collect and transport.
• Cellulose difficult to hydrolyze (structural
  polymer) starch is amorphous and easy to
  hydrolyze.
• Can burn lignin to provide energy for plant
  operation

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Senior Design Problem Bioenergy plantation
design

• Fundamental concept there exists an optimum
  biorefinery capacity (M) for biofuel production.
  (Tradeoff between capital cost (M0.6) and cost
  of transporting biomass (M1.5)).
• Process energy provided by lignin combustion
• Can choose parameters arbitrarily or use standard
  values (NREL website).
• Possibilities for open-ended design, multiple
  smaller feeder process units in remote
  locations.

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Biomass Plantation Economics (NREL)
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Biodiesel from plant oils

• Plant oils include soy, rapeseed, canola, etc..
  
• Waste cooking oils are minor potential source,
  are inexpensive,
• but contain water and free fatty acids that
  must be cleaned up.
• Other sources include algae, sewage, etc..
• Reversible reaction system
• Typical methanoloil feed ratio of 61 gives two
  product phases,
• gt98 methyl ester yield

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Current biodiesel production(Batch production,
labor and energy intensive)
Biodiesel Product (100 kg) (30 gal)
purification
Plant oil (100 kg) (30 gal)
Methanol (22 kg) (61 ratio)
Neutralize purify
60oC, 2 hr
Glycerol byproduct (10.4 kg) (0.7 lb/gallon)
Glycerol NaOCH3
NaOCH3 (0.5 kg)
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Biodiesel in the classroom

• Material and energy balances
• a) Calculate stoichiometric reaction masses,
  byproduct glycerine yields
• b) Calculate biodiesel energy density relative
  to diesel fuel
• c) Optimizing energy yields from land - Which
  fuel type gives higher energy yield per acre,
  biodiesel or ethanol?
• Canola 1000 kg/acre0.44 kg oil/kg canola39
  mJ/kg 17160 MJ/acre
• Ethanol 160 bu/acre2.7 gal/bu3 kg/bu27 MJ/kg
  35000 MJ/acre
• Reaction engineering
• Make biodiesel as classroom demo (cooking oil
  methanol sodium hydroxide/methoxide)
• Good example of homogeneous catalysis (can see
  color change upon addition of sodium hydroxide in
  methanol)

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Chemical Building Blocks from Biomass

• Carbon number Biomass Blocks
  Petroleum Blocks
• C1 methanol, CO methane
• C2 acetic acid, ethanol ethylene
• C3 lactic acid, acetone, propylene
  propionic acid, glycerol
• C4 succinic acid, n-butanol isobutylene
• 3-hydroxybutyrate butadiene
• C5 xylose, glutamic acid
• 3-hydroxyvalerate
• C6 glucose, lysine benzene
• C7, C8 toluene xylene

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Chemicals from Carbohydrates
STARCH CELLULOSE
BIOMASS (CORN, WOOD..)
Industrial starches, cellulose derivatives
CORN
GLUCOSE
Syrups, sweeteners
Fermentation
Chemical conversion
H2
O2
Organic acids
Others
Gluconic acid
Sorbitol
Polymers
Ethanol
Lactic acid Succinic acid Citric acid Acetic
acid Propionic acid Itaconic acid Lysine D,L-Methi
onine Other amino acids Aromatics
1,3-propanediol 2,3-butanediol ABE
Starch copolymers Xanthan gum Alginates Hydroxyalk
anoate
PG, EG Glycerol Sorbitan Ascorbic acid
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Lactic Acid
Fermentation C6H12O6 ? 2 C3H6O3
(glucose) (lactic acid) - Yields exceed
0.95 lb/lb glucose - Product concentrations
gt 90 g/L - Production rates gt 3 g / L hr
- Ca(OH)2 to neutralize, acidulation w/ H2SO4
(CaSO4 waste) Production cost lt
0.25 / lb Production capacity 350 MM lb/yr
(Cargill) 100 MM lb/yr (all others)
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Equilibrium Lactate Ester Reactions
- Lactic acid oligomerization reactions
characterized by Ke 0.23
Nominal lactic acid concentration (wt) L1 L2 L3 L4
20 20 - - -
50 42 8 - -
88 58 22 6 2
Equilibrium oligomer distribution
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Lactate esters via reactive distillation
Lactic Acid Ethanol Ethyl
lactate Water
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Reactive distillation for lactate ester production
Stream 3 Flow 65.98 kmol/hr
Wt EtOH
82.93 EtLA 0.13 Water
16.94
FEED (88 LA feed) LA 9.519
kmol/hr L2 Acid 2.005 kmol/hr L3 Acid
0.505 kmol/hr Water 9.847
kmol/hr EtOH 54.000 kmol/hr
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Stream 4 Flow 9.90 kmol/hr
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Wt LA
0.00 EtOH 0.30 EtLA
72.64 Water 0.13 L2ES 19.44
L3ES 6.11 L2 Acid 0.66
L3Acid 0.63
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Stages 35 Reflux ratio 0.1 Lactic acid
conversion () gt99
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Chemicals from Renewables

• Material balances/reaction engineering Determine
  theoretical yields - renewables generally undergo
  weight loss in conversion, whereas petroleum
  generally undergoes weight gain in conversion.
• Separations schemes for purifying low volatility
  organic/renewable products (evaporation, reactive
  distillation, chromatography, other novel
  separations)
• Thermodynamics Many biobased reactions are
  reversible, involve nonideal solutions, physical
  properties estimation required

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Summary

• Renewable fuels and chemicals can be incorporated
  across the core ChE curriculum
• Energy and mass balance calculations
• Thermodynamics physical properties, phase
  equilibria, reaction equilibria
• Reaction engineering kinetics, reactor design,
  catalysis
• Separations design separations schemes for
  non-volatile, thermally fragile compounds
• Process design core chemical engineering
  principles and unit operations are key to
  designing biorefineries

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GREEN CHEMISTRY

• DEFINITION
• Green Chemistry is the utilisation of a set of
  principles that reduces or eliminates the use or
  generation of hazardous substances in the design,
  manufacture and application of chemical products
  .
• GREEN CHEMISTRY IS ABOUT (12 principles)
• Waste Minimisation at Source
• Use of Catalysts in place of Reagents
• Using Non-Toxic Reagents
• Use of Renewable Resources
• Improved Atom Efficiency
• Use of Solvent Free or Recyclable Environmentally
  Benign Solvent systems
  
  

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Traditional Synthesis of Ibuprofen
O
O CHCO2C2H5
ClCH2CO2C 2H5
(CH3CO)2O
NaOC2H5
AlCl3
IBu
IBu
CH NOH
CHO
H2NOH
H
H20
IBu
IBu
CO2H
60 Waste
C
N
Ibuprofen
IBu
(BASF and Celanese Corporation)
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Green Chemistry Alternative Synthesis of
Ibuprofen PGCC Winner 1997
(CH3CO)2O
CH3COOH
HF
CO2H
OH
CO, Pd
1 Waste
Ibuprofen
(BASF and Celanese Corporation)
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Green chemistry in the curriculum

• Material and Energy Balances
• Define and implement atom economy and waste
  generation into stoichiometry problems
• Yield calculations for multiple step syntheses
• Reaction Engineering and Design courses
• Carry out reactor design for green process and
  compare with traditional process
• Resource ACS Green Chemistry Institute