• Types of feedstock biomass

• Physical and chemical structure of biomass

FEEDSTOCK AND PRETREATMENT

TECHNOLOGY

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Main types of feedstock
biomass
 Lignocellulosic materials: Agriculture residue, Forest
resource, MSW
 Whole crop : wheat, corn, straw, cobb
 Green crop : Switchgrass, alfalfa, herb
 Algae : macroalgae & microalgae

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Lignocellulosic biomass
 The major components are carbohydrates (cellulose and
hemicellulose) and lignin
 Small amounts extractives, that is proteins and inorganic
constituents are also found in lignocellulosic materials
 Cellulose retains the crystalline fibrous structure which
appears to be the core of the complex.
 Hemicellulose is positioned both between the micro- and
the macrofibrils of cellulose.
 Lignin provides a structural role to the matrix in which
cellulose and hemicellulose are embedded
 The composition of lignocellulosic material strongly
depends on its source and whether it is derived from
hardwood, softwood, or grasses
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This graphical representation of lignocellulosic biomass based on supercomputer models illustrates a new Oak Ridge National
Laboratory study about the inner workings of plant cell walls during bioenergy production. (Image credit: Thomas
Splettstoesser; http://www.scistyle.com) 5
Lignocellulosic biomass -
Physical Properties

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Physical Properties - Cellulose
 Typically represent 40–50 % of dry weight.
 Considered as a polymer of glucose, since cellobiose consists of
two molecules of glucose.
 Consist of crystalline and amorphous regions, in varying
proportions depending on both source and history
 The properties of cellulose depend on its degree of
polymerization, commonly a number of 800–10,000 units
 Cellulose molecules are in the form of fibrils, where the fibrils are
composed of microfibrils
 Most of the reactants penetrate only the amorphous regions and
it is only in these regions with a low level of order and on the
surface of the crystallites that the reactions can take place,
leaving the intracrystalline regions unaffected – thus
pretreatment is needed
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 Physical Properties -
Cellulose

Structural unit of cellulose (cellobiose)

Formation of microfibrils (fibers) of cellulose

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Physical Properties - Hemicellulose
 A heteropolymer of polysaccharides and polyuronides, is available in
almost all lignocellulosic materials along with cellulose.
 Has an amorphous structure with short chain polymers as a side
chain
 Because of the amorphous morphology, hemicelluloses are partially
soluble or swell in water
 The backbone of the chains of hemicelluloses can be a
homopolymer (generally consisting of single sugar repeat unit) or a
heteropolymer (mixture of different sugars).
 The composition of hemicellulose is dependent upon the plant tissue
and source; for example, hardwood hemicelluloses :xylans,
softwood hemicelluloses : glucomannans
 Relatively easily hydrolyzed by acids to their monomer components
i.e. glucose, mannose, galactose, xylose, arabinose, and small
amounts of rhamnose, glucuronic acid, methylglucuronic acid, and
galacturonic acid
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Physical Properties -
Hemicellulose

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Physical Properties - Lignin
 A cross-linked polymer of hydroxyphenylpropanoid units connected by
C–C and C–O–C linkages
 Located in the middle lamella, acting as cement between the plant cells,
and in the layers of the cell wall, together with hemicellulose, forming
an amorphous matrix in which the cellulose fibrils are embedded.
 It increases the mechanical strength properties, and makes plant
resistant against diseases and biodegradation by microorganisms.
 Linked with cellulose and hemicellulose, termed as lignin-
polysaccharide complex (LPC) or lignin-carbohydrate complex - make it
almost impossible to completely separate or purify cellulose or
hemicellulose from lignin
 Lignin content and composition vary among different plant groups.
 Softwoods (25–40 %), hardwoods (18–25 %) and agriculture residues
(10–20 %)
 Hydrophobic and highly resistant toward chemical and biological
degradation.
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Physical Properties - Lignin

The monomeric building units of lignin

Structure of lignin

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Lignocellulosic biomass -
Chemical characteristics
 Four main types of bonds recognized in the
lignocellulosic complex :
 Ether
 Ester
 Carbon-to-carbon
 Hydrogen bonds.
 These four bonds are the major types of bonds that
provide linkages within (intrapolymer linkages) and
between the different components of lignocellulosic
material to form complex (interpolymer) linkages

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Lignocellulosic biomass -
Chemical characteristics

Linkages between the monomer units and polymers to form lignocellulose

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Pretreatment - Introduction
 An essential step in the biological conversion to ethanol
 Pretreatment is responsible to :
1. separate the components of the lignocellulosic biomass
2. reducing the crystallinity of the material
3. making the cellulose accessible
4. the removal of lignin and hemicellulose
 The mechanism for making the cellulose more accessible to enzymes
depends on the nature of the raw material and pretreatment employed.
 The mechanisms can be one or combination of the following :
 Removing hemicellulose
 Removing lignin
 Degrading cellulose crystalline structure
 The aim : hydrolysis can be achieved more rapidly and with greater yields.
 Considered as one of the most expensive processing steps ( up to 33% of the
production cost)
 There are needs to develop tailor-made effective pretreatment methods for
different types of lignocellulosic biomass 16
 Cellulose Pretreatment gives
Lignin enzyme accessible substrate

Amorphous
Pretreatment
Region

Crystalline
Region

Hemicellulose

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Factors need to be considered:

1. The type of lignocellulosic biomass under use and the

desired final products
2. Ability to improve in the hydrolysis rate of
lignocellulosic biomass
3. Ability to minimize the degradation or loss of
carbohydrate
4. Ability to minimize the formation of byproducts that
are inhibitory to the subsequent hydrolysis and
fermentation processes
5. High product yields at low enzyme loadings or
fermentation operations with minimal treatment cost.
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Factors need to be considered
(cont):
6. Low or minimal chemical consumption for
pretreatment, neutralization, and subsequent
conditioning.
7. Possibility of recycling and reusing of the chemical used
in the pretreatment.
8. Minimal waste production.
9. Limited size reduction needs since milling is an energy
intensive and expensive process.
10. Fast reactions and/noncorrosive chemicals to minimize
pretreatment reactor cost.
11. Pretreatment should facilitate recovery of lignin for
conversion to valuable byproducts
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TAKE 5!

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TOXIC COMPOUNDS GENERATED DURING
PRETREATMENT
 Severe conditions during pretreatment can lead to generation of
some toxic compounds (inhibitors)
 Could affect the subsequent hydrolysis and fermentation steps
(enzymes and microorganisms)
 The nature and concentration of the toxic compounds depend
on:
 the raw material (hardwood, softwood, herbaceous biomass, etc.),
 the pretreatment and conditions employed (temperature, residence
time, pressure, pH, etc.)
 the use of catalysts
 It can be divided into three groups:
 furan derivatives (sugar degradation products)
 weak acids
 phenolic compounds (lignin degradation products)

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Furans

 Main furan derivatives are 2-furaldehyde (furfural) and 5-

hydroxymethylfurfural (HMF) generated from pentoses and
hexoses degradation respectively
 Pretreatments which employ acids as hydrolytic agents and
utilize high temperature and time to reaction will produce
furfural and HMF at higher levels
 Most of the fermenting microorganisms are able to reduce furans
to their corresponding less toxic alcohols
 If furans are present at high concentration, they exert an
inhibitory effect :
 Prolong the lag phase
 Reducing the ethanol productivity

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Weak acid

 Main weak acids generated during pretreatment are:

 acetic acid - from the acetyl groups in hemicelluloses
 formic acid - from furfural and HMF degradation.
 levulinic acid – from decomposed HMF
 The undissociated form of weak acids can cause
acidification of cytoplasm and cellular death
 pH control is necessary for minimizing acids toxicity

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Phenolic compound

 Identified phenols are aldehydes, ketones, or acids such as

4-hydroxybenzaldehyde, vanillin, synringaldehyde, syringic acid,
and cathecol
 Toxic because they affect the integrity of biological membranes
 The concentration and type of phenolic compounds is highly
dependent on the raw material - lignin content and chemical
structure difference

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Main toxic compounds produced during different
pretreatment technologies of lignocellulose

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 Pretreatment Methods
Physical Physicochemical Chemical Biological
pretreatment pretreatment pretreatment pretreatment
 Drying and
concentration
 Milling/grinding
(e.g. ball milling,
hammer milling)
 Ozonolysis
 Irradiations (e.g.
 Steam explosion  Acid hydrolysis  Fungal
Ultrasonic,
 Ammonia fiber (dilute acid) delignification
microwaves,
explosion (AFEX)  Alkaline hydrolysis  Enzymatic
electron beams)
 CO2 explosion  Oxidative pretreatment
 Extrusion
 Liquid hot water delignification
(subjecting the
 Organosolv process
biomass to
heating, mixing,
and shearing)
 Granulometric
Separation

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Physical pretreatment - Drying and
concentration
 The moisture content of a material is associated to its water activity
 Reduce in water activity can prevent deterioration, microbial
growth, chemical redox processes, and reduce enzymatic activity.
 Reduces the volume and weight of the material, thus reducing
transportation, packing, and storage costs
 Liquid content of a residue may be removed by mechanical
processes such as centrifugation or pressing or by thermal drying
methods
 Crop residues may be dried on the field ( if weather is adequate)
 For residues produced in the industry, e.g. sugarcane bagasse or
EFBs, the drying may be done using flue gases or steam from the
plant .
 For these operations, the driers are usually either drum or pneumatic
driers.
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Physical pretreatment -
Milling/grinding
 Size reduction is one of the most effective methods to reduce
crystallinity of lignocellulose in order to increase the enzyme
accessible surface area and reduce the degree of polymerization
 The advantages of the particle size reduction include:
1. increasing the ratio surface/volume
2. standardizing the particle size
3. improving the homogeneity of the substrate
 Particle size uniformity will provide a uniform process for
fermentative and hydrolysis processes
 The power requirement is relatively high depending on the final
particle size and the biomass characteristics
 Strong structure of forest biomass makes its size reduction very
energy intensive

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Physical pretreatment - Extrusion
 In extrusion, materials are subjected to heating, mixing, and
shearing, resulting in physical and chemical modifications during
the passage through the extruder.
 The advantages:
 the ability to provide high shear
 rapid heat transfer
 effective and rapid mixing
 Screw speed and barrel temperature are believed to disrupt the
lignocellulose structure causing defibrillation, and shortening of
the fibers, and in the end, increasing accessibility of
carbohydrates to enzymatic attack
 Recently employed for increasing the enzymatic hydrolysis yields
of switchgrass, corn stover, wheat bran and soybean hull

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Physical pretreatment -
Granulometric Separation
 After drying and size reduction, the material classification in
different granulometries is required to:
 achieve a better material homogenization
 ensure less influence particle in the future process.

 The common method is the mechanical separation

 Fractions classified according to the meshes of the screen are
obtained
 Particles larger than the desired size may be recycled to the mill,
while very small particles may be separated for other processes such
as burning

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Physical pretreatment - Irradiation
 Microwave Pretreatment
 Combines both thermal and nonthermal effects generated in aqueous
environment
 Microwave uses the ability of direct interaction between a heated object
and an applied electromagnetic field to increase heat
 Advs: reduction of process energy requirements, uniform and selective
processing and capacity of starting and stopping the process
instantaneously
 The electromagnetic field helps to accelerate the destruction of
crystalline structures and changes the super molecular structure of
lignocellulosic material
 Recent studies employing acetic and propionic acids shown those acids
as good agents leading to swelling of cellulose, increasing the surface
area and reducing its crystalline structure (gong et al., 2010).
 The short length of the process as well as the low inhibitor production is
reflected in high cost effectiveness.
 However, the feasibility of using a pretreatment method that involves
microwave irradiation and chemicals in commercial scale is unknown

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