Biofuel and Energy

Conversion from Bioresources

By Dr Leong Yoong Kit
Three categories of biomass  
• Forest Products: Wood, logging residues, trees, shrubs and wood
residues, sawdust, bark, etc., from forest clearings
• Energy crops: Short rotation woody crops, herbaceous woody crops,
grasses, starch crops (corn, wheat and barley), sugar crops (cane and
beet), oilseed crops (soyabean, sunflower, safflower)
• Wastes: Agricultural production wastes, agricultural processing
wastes, crop residues, mill wood wastes, urban wood-wastes, urban
organic wastes.
 Advantages Disadvantages
• Abundancy • Generally low energy content
• Energy security • Competition for the resource
• Generally lower cost compared with with food, feed, and
fossil fuels applications like particle
board or paper
• Can be stored in large amounts and
produced on demand • Generally higher investment
costs for conversion into final
• Creation of stable jobs, especially in energy in comparison with
rural areas fossil alternatives
• Mitigation of GHG emission
Government Policies
• US – Energy Independence and Security Act (EISA) aims to reach 36
billion gallons of bioethanol by 2022
Bioenergy Types
Biofuels
Liquids
Methanol, Ethanol, Butanol, Biodiesel
Gases
Methane, Hydrogen
Bioheat
Wood burning
Bioelectricity
Combustion in Boiler to Turbine
Microbial Fuel Cells (MFCs)
 Biofuel substitutes for  Conventional Fuel

Ethanol Gasoline

Mixed alcohols Diesel

Methanol / MTG LPG

Fischer Tropsch Paraffin

Dimethyl ether Kerosene

Biocrude Crude oil

HYDROLYSIS

GASIFICATION
Biofuel Applications: Liquids

Ethanol and Butanol: can be

used in gasoline engines either at low
blends (up to 10%), in high blends in
Flexible Fuel Vehicles or in pure
form in adapted engines

Biodiesel: can be used, both

blended with fossil diesel and in pure
form. Its acceptance by car
manufacturers is growing
 Process for cellulosic bioethanol

 http://www1.eere.energy.gov/biomass/abcs_biofuels.html
 Why Butanol?
More similar to gasoline than ethanol
Butanol can:
 Be transported via existing pipelines (ethanol
cannot)
Fuel engines designed for use with gasoline without
modification (ethanol cannot)
Produced from biomass (biobutanol) as well
as petroleum (petrobutanol)
Toxicity issues (no worse than gasoline)
 Biodiesel from triglyceride oils

Methoxide

Methyl Ester
Triglyceride Glycerine

Triglyceride consists of glycerol backbone + 3 fatty acid tails

The OH- from the NaOH (or KOH) catalyst facilitates the breaking of the
bonds between fatty acids and glycerol
Methanol then binds to the free end of the fatty acid to produce a methyl
ester (aka biodiesel)
Multi-step reaction mechanism: Triglyceride→Diglyceride
→Monoglyceride →Methyl esters+ glycerine
 Syngas
• Comprised of hydrogen, carbon monoxide, carbon dioxide,
methane, higher hydrocarbons, and nitrogen
 Biodiesel Production
Methanol Raw Oil
Catalyst NaOH
Crude Biodiesel (methyl ester)
Crude glycerin Acid (phosphoric)
Excess methanol
Catalyst KOH
Catalyst Mixing Transesterification
Reaction Neutralization

Methanol Recovery

Recovered
methanol
Biodiesel,
glycerin

Phase Separation
gravity or centrifuge Crude Glycerine

Biodiesel,
impurities

Purification Wash water

(washing)

water
Fertilizer Fuel Grade
K3PO3 Biodiesel
Biofuel Applications: Gases

Hydrogen: can be used in fuel

cells for generating electricity

Methane: can be combusted

directly or converted to ethanol
 Bioheat Applications
Small-scale heating systems for
households typically use firewood
or pellets
Medium-scale users typically
burn wood chips in grate boilers
Large-scale boilers are able to
burn a larger variety of fuels,
including wood waste and refuse-
derived fuel

Biomass Boiler

(for more info: Dr. Harold M. Keener, OSU Wooster, E-mail  keener.3@osu.edu)
Bioelectricity Applications

Co-generation: Combustion
followed by a water vapor
cycle driven turbine engine is
the main technology at present

Microbial Fuel Cells

(MFCs): Direct conversion of
biomass to electricity
Key Cellulosic
H3CO
H3CO
HO OCH3 O
O O OH

Constituents OCH3 O
OCH3OCH3

OH
O
OCH3
HO

O
OH
O

HO
OH
O

HO O OH O O HO

Lignin: 15-25%
HO O OH
O
OH OH OH
OH OH O
OCH3 H3CO HO
OCH3
Complex aromatic structure OCH3OCH3
HO
O
OH
O
OH
O
OH
O HO
OH
O
O
Very high energy content O
OH OCH3
O OH
HO
O HO
OH O HO
O HO
O OH
O O
Resists biochemical conversion O
HO
OH
OH
OH
OH O
OH OH
O
OH O
OH OH
O

OH HO HO
O OH O HO OH O HO
H3CO HO

Hemicellulose: 23-32%
OH
O O OH
O O
OCH3 OH OH
O OH O OH O
HO HO
O OH
O HO O HO
Xylose is the 2nd most abundant 　　 OH
O
OH OH
O OH O
OH OH
O
OH
OH OH O OH O
　 sugar in biosphere O
HO
O HO
HO
O HO
HO OH OH
OH
O OH
O
Polymer of 5C and 6C sugars O
OH O
O
OH
OH O
O
OH
O HO HO
Readily hydrolyzed O
O
O HO
OH
O
OH O
O HO
OH
O OH
OH OH
OH O OH O
HO HO

Cellulose: 38-50% OH
O
OH
O HO
OH
O
OH
O
OH
O HO

OH O HO OH O
Most abundant form of C in OH O
O HO
OH
biosphere OH O
OH OH
O

HO
Polymer of glucose OH
O
O HO

OH
Resistant to hydrolysis OH O
Biomass constituents  
Hemicellulose
• Complex polysaccharides present in the cell wall, which consist of
branched structures and vary with biomasses.
• It is a heteropolymers, composed almost entirely of sugars including
hexoses (D-glucose, D-galactose and D-mannose) as well as pentose
(D-xylose and L-arabinose) and may contain sugar acids (uronic acids)
namely, D-glucuronic, D-galacturonic
• Backbone chain - primarily xylan β (1/4)-linkages that include D-
xylose (nearly 90%) and L-arabinose (approximately 10%)
• The hemicelluloses of softwood are typically glucomannans, while
hardwood hemicellulose is more frequently composed of xylans
• Average MW of < 30,000 kDa.
Cellulose
• Structural linear component consisting of a long-chain of glucose
monomers linked β (1/4)-glycosidic bonds that can reach several
thousand glucose units in length
• The extensive hydrogen linkages among molecules lead to a
crystalline and strong matrix structure
• Requires 320 °C and pressure of 25 MPa to shift from a rigid
crystalline structure to an amorphous structure in water
Lignin
• Aromatic and rigid biopolymer with MW of 10 kDa
• Bonded via covalent bonds to xylans (hemicellulose portion) conferring
rigidity and high level of compactness to the plant cell wall.
• Composed of three phenolic monomers of phenyl propionic alcohol
namely, coumaryl, coniferyl and sinapyl alcohol.
• Softwood barks (30-60%) > hardwood barks (30-55%) > grasses and
agricultural residues (10-30% and 3-15%, respectively)
Pretreatment
Mechanical pretreatment
• Size reduction - Milling, grinding, chipping, cutting
• Modify biomass structure to break the crystalline structure of cellulose
• Increases biomass surface area for further process
• Extrusion – Thermal + mechanical (shear) force by screw rotation
• Single or twin screw
• Advantages – Low cost; Good process control; No sugar degradation; Flexible;
High continuous output
• Can be combined with chemical treatment with either alkali or acid, steam
explosion, ammonia fiber explosion, vacuum extrusion, and bio-extrusion
Irradiation
• High energy radiations are used to disrupt the chemical bonds of the
biomass
• (1) Microwaves; (2) Gamma rays; (3) Electron beam; (4) Ultrasonication
• May result in characteristics changes, in cellulose crystallinity,
depolymerization of lignin, and hydrolysis of hemicelluloses
• Advantages: Less energy requirement; Easy handling; Selectivity
Liquid hot water pretreatments
• Also termed as hydrothermolysis, aqueous or steam/aqueous
fractionation, uncatalyzed solvolysis and aquasolv
• Use pressure to maintain the water in the liquid state at elevated
temperatures of 200–230 °C for up to 15 min
• 40% and 60% of biomass dissolved - 4–22% cellulose, 35–60% lignin
and 100 % hemicellulose.
• Over 90% of hemicellulose recovered as monomeric sugars when acid
was used to hydrolyze the resulting liquid
Acid pretreatment
Ozonolysis (O3)
• Effective oxidative pretreatment with high reactivity but poor selectivity
of the substrate
• Studied for wood chips, grass, straw, pulps, bagasse, and microalgae
• O3 generates highly reactive hydroxyl radicals (OH+) in the presence of
water, which increases its reactivity with different macromolecules
• Reacts with insoluble lignin fractions in acidic solvents, which in turn
enhances solubility in acid and further degradation of lignin
• Costly as large amount of O3 is needed
Steam explosion
• Biomass is rapidly heated by high-pressure steam and held for a period
of time to promote hemicellulose hydrolysis, and terminated by an
explosive decompression
• Water act as acid at high temperature
• Hemicellulose is hydrolyzed by the acetic and other acids released
 Advantages Disadvantages
• No excessive dilution of the resulting • Generally low energy content
sugars • Competition for the resource
with food, feed, and
applications like particle
board or paper
• Generally higher investment
costs for conversion into final
energy in comparison with
fossil alternatives
Fungal pretreatment
• Fungi – Brown, white, and soft-rot fungi
• Degradation of lignin, hemicelluloses, and a small quantity of cellulose
• Advantages: Simple technique; Low energy consumption;
Environmentally friendly; Low inhibitor for ethanol fermentation
• Diadvantages: Substantial holocellulose (cellulose and hemicellulose)
loss; Long pretreatment time
Conversion Processes
Biological conversion
Fermentation (methanol,
ethanol, butanol)
Anaerobic digestion (methane)
Anaerobic respiration (bio-
battery)
Chemical conversion
Transesterification (biodiesel)
Thermal conversion
Combustion
Gasification
Pyrolysis
 Conversion
Photosynthesis Biomass processes Biofuels and Bioenergy Application

Heating
Heat
Wet biomass Anaerobic Biogas
(organic waste, manure) H2, CH4
C6H12O6 + 6O2
fermentation

Electrical devices
Electricity
Gasification Fuel gas
Solid biomass Combustion
(wood, straw)
Pyrolysis
Pyrolytic oil
Hydrolysis

co2
Sugar and starch plants Hydrolysis Ethanol
Sugar Butanol
6CO2 + 6H2O

(sugar-cane, cereals)

Liquid biofuels
Extraction fermentation

Transport
Oil crops and algae Crushing Methyl ester
(sunflower, soybean) Pure Oil
Refining (biodiesel)
Transesterification
Factor that influence the choice of conversion process

• Type and quantity of biomass feedstock

• What you have and how many you have?
• The desired form of the energy (end-use requirements)
• What you want?
• Environmental standards
• What is the rules and regulations?
• Economic conditions
• How much money you have?
• Project specific factors
• What technology you possess?
Thermochemical conversion
• Availability of industrial infrastructure to supply thermochemical
transformation equipment that is highly developed
• Short processing time
• Reduced water usage
• Able to produce energy from plastics wastes which cannot be digested
by microbial activity
• Independent of environmental circumstances for production purposes
Direct combustion
• Burning of biomass in air
• Convert chemical energy stored in biomass into heat, mechanical
power or electricity via stove, furnace, boiler, steam turbine, turbo-
generator
• Produces hot gases at temperature around 800 – 1000 °C
• Feasible only for biomass with moisture content < 50 %
• Net bioenergy conversion efficiencies range from 20 - 40 %
• Co-combustion in coal-fired power plant is an attractive option due
to their higher conversion efficiency
 Pyrolysis
• Heating the biomass in the absence of air/O2
• Start at 350 - 500 °C and goes up to 700 °C
• Convert biomass to liquid (bio-oil or bio-crude), solid (biochar) and
gaseous (syngas) fraction
• Different condition leads to formation of product in different proportions
• Liquid product need to be upgraded due to high O2 and H2O content
• Less stable and less miscible in conventional fuels
Slow pyrolysis
• Biomass is pyrolyzed at slow heating rate (5-7 °C/min)
• Leads to less liquid and gaseous product, while more char production
•
Fast pyrolysis
• Rapid heating of biomass at 300 °C/min
• To produce high-grade bio-oil
• Offer high heating rate, rapid devolatilization, easy control, easy
product collection
• Reactor designed for fast pyrolysis - entrained flow reactor, wire mesh
reactor, vacuum furnace reactor, vortex reactor, rotating reactor,
circulating fluidized bed reactor, etc.
Flash pyrolysis
• Reaction time – several seconds or even less
• Very high heating rate
• Reactors – Entrained flow reactor and fluidized be reactor
• Small particle size (105-250 µm)
• Flash hydro-pyrolysis – Done in hydrogen atmosphere. Carried out at
pressure up to 20 Mpa
• Rapid thermal process - Heat transfer process with very short heat
residence time (between 30 ms and 1.5 s). Done at 400 - 950 °C. Rapid
depolymerization and cracking of feedstock. Rapid reaction eliminate side
rxns and give products with comparable viscosity to diesel oil
Flash pyrolysis
• Solar flash pyrolysis – Use concentrated solar radiation. Energy from
solar tower, dish connector, solar furnace, etc
• Vacuum flash pyrolysis – Vacuum condition limits the secondary
decomposition rxns (further cracking and recondensation). Give high
oil yield and low gas yield due to removal of condensable products.
Gasification
• Convert biomass into a combustible gas mixture (syngas) by the
partial oxidation of biomass at high temperature, typically in the
range 500-1400 °C, from atmospheric pressures up to 33 bar
• The reactions are as follows
Gasification
• Biomass gasification able to recover more energy and higher heat
capacity compared to combustion and pyrolysis
• Gas composition of syngas produced depends on type of gasifier,
gasification agent, catalyst type and size of particle
Types of gasifier and their advantages
Type of gasifier Advantages
Fixed bed gasifier • High tolerance of ash content.
• Able to withstand high moisture content feedstock.
• Low tar accumulation.
• Minimum sensitivity towards feedstock size and quantity
Fluidized bed gasifier • High heat transfer rate.
• Thorough mixing of feedstock and bed material.
• Moderate requirements of gasification medium
Entrained flow • Flexibility types of feedstock.
• Short processing time.
• Uniformity of temperature throughout reactor.
• Low tar production in gas.
Plasma • Capable to treat both hazardous and non-hazardous wastes.
• Nontoxic method to destroy hazardous waste.
• Easy removal of ash as slag.

Lee et al., 2019

Gasification
• Biomass gasification able to recover more energy and higher heat
capacity compared to combustion and pyrolysis
• The low calorific value (CV) gas produced (about 406 MJ/Nm3) can
be burnt directly or used as fuel for gas turbines and gas engines
• Biomass integrated gasification/combined cycle (BIG/CC) –
Combination of gasification and combustion/heat recovery for high
overall conversion efficiencies (40-50 %)
• Advantage – The gas is cleaned before being combusted, allowing more
compact and cheaper gas cleaning equipment
Hydrothermal liquefaction (HTL)
• HTL method utilizes biomass that contains high moisture that could
minimize the cost of drying or dewatering phase
• Production of bio-oil at low temperature and elevated pressure with or
without catalyst in the presence of hydrogen
• Utilizes subcritical water (SCW) at medium temperatures ranging
from 250 - 374 °C and operating pressure from 40 - 220 bar
Biochemical conversion
Pretreatment
Hydrolysis
Anaerobic fermentation
Transesterification