Physicochemical pretreatment - Steam

explosion
 Steam explosion (uncatalyzed or catalyzed) one of the most applied
pretreatment processes
 High-pressure saturated steam is injected into a batch or continuous reactor
filled with grinded biomass for a period of time, and then suddenly
depressurized, which makes the biomass undergo an explosive decompression
 Varying temperatures from 160 to 260ᵒC, pressures from 0.69 to 4.83 MPa, time
from 2 to 30 min , solids concentrations (about 50%)
 Result to hemicellulose and cellulose degradation and lignin matrix disruption
thus facilitating the subsequent hydrolysis of cellulose
 Steam explosion fractionates the biomass in two fractions:
1. a liquid fraction rich in monomeric and oligomeric sugars mainly from hemicelluloses
degradation
2. a solid fraction of digestible cellulose and lignin
 Important factors affecting the effectiveness of steam explosion pretreatment
depend on residence time, temperature, particle size, and moisture content

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 Physicochemical pretreatment - Steam
explosion
 Cause the formation of inhibitor molecules such as furfural and hydroxymethyl
furfural; both incubation times and temperatures are directly proportional to the
amount of these by-products
 It has potential for significantly lower environmental impact, lower capital
investment, more potential for energy efficiency, less hazardous process
chemicals and conditions and complete sugar recovery
 Addition of H2SO4 (or SO2) or CO2 [typically 0.3-3% (w/w)] in steam explosion
can decrease time and temperature, effectively improve hydrolysis, decrease the
production of inhibitory compounds, and lead to complete removal of
hemicellulose.
 The addition of the acid causes many drawbacks related to equipment corrosion,
higher amounts of degradation products and the necessary step of acid
neutralization with consequent formation of wastes.
 To remove these inhibitors it is compulsive to wash the pretreated biomass with
water, although this wash reduces the saccharification yields, removing soluble
sugars, such as those deriving from hemicellulose hydrolysis

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Physicochemical pretreatment - Steam
explosion

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Physicochemical pretreatment -
Steam explosion

Photographs showing the non-treated (30 mm hammer mill screen

size) and steam exploded barley, canola, oat and wheat straw grinds
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Physicochemical pretreatment -
Steam explosion

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Physicochemical pretreatment -
Ammonia Fiber Explosion (AFEX)
 During the AFEX pretreatment, biomass is treated with liquid anhydrous or
concentrated, > 70 % ammonia at temperatures between 60 and 100ᵒC and
high pressure (0.7 to 27 MPa) for a variable period of time typically 30 mins.
 After the residence time the pressure is released, vaporizing the ammonia
and allowing its recovery and recycling.
 In a typical AFEX process, the dosage of liquid ammonia is 1–2 kg of
ammonia/kg of dry biomass
 The ammonia causing swelling and physical disruption of biomass fibers,
partial decrystallization of cellulose, hydrolyses hemicellulose and
breakdown of lignin-carbohydrates linkages
 The AFEX pretreatment is more effective on agricultural residues and
herbaceous crops
 Low formation of inhibitors, even though some phenolic fragments of lignin
and other cell wall extractives may remain on the cellulosic surface

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Physicochemical pretreatment -
Ammonia Fiber Explosion (AFEX)

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 Physicochemical pretreatment – CO2
Explosion
 Similar to steam and ammonia fiber explosion; high pressure CO2 (supercritical)
explosion is injected into the batch reactor, and then liberated by an explosive
decompression
 Pretreatment at varying temperature 25-210⁰C, pressure 6-28 MPa, from 10-60 mins
 Upon an explosive release of CO2 pressure, disrupt cellulose and hemicellulose structure
and increase the accessible surface area of the substrate to enzymatic attack
 Has the ability to penetrate the crystalline structure of lignocellulosic biomass
overcoming the mass transfer limitations encountered in other pretreatments
 It is not suitable for biomass with high lignin content (such as woods and nut shells)
 In aqueous solution, CO2 forms carbonic acid, which favors the hydrolysis of
hemicellulose & cellulose
 Can operates at low temperatures compared to other methods which prevents
monosaccharides degradation, thus lower the inhibitors formation
 CO2 is nontoxic, noninflammable, leaves no harmful residues, and is inexpensive and
readily available.
 Yields of CO2 explosion are lower than those obtained with steam or ammonia explosion
 Due to low temperature, utilization cost of this process is potentially lower compared to
ammonia explosion
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Physicochemical pretreatment – CO2
Explosion

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Physicochemical pretreatment – Wet
Oxidation
 Treatment of biomass in the presence oxygen/air (as catalyst) and water at high
temperature and pressure
 Is performed for 5-15 min at temperatures from 170 to 200⁰ C and at pressures from 10 to
12 bar O2
 Addition of oxygen at temperatures above 170 C makes the process exothermic reducing
the total energy demand
 All biomass fractions are affected, hemicelluloses degrade substantially but does not
catalyze the hydrolysis of solubilized hemicellulose
 This technology has been widely used for ethanol production followed by simultaneous
saccharification and fermentation
 Phenolic compounds are not end products during wet oxidation because they are further
degraded to carboxylic acids, formic and acetic being the major degradation products
 Furfural and HMF production is lower as compared to steam explosion or LHW
 Addition of carbonate (Na3CO2) resulted in alkaline wet oxidation reducing even more the
formation of toxics as the formate ion is oxidized causing an increase in pH that helps to
neutralize the carboxylic acids formed during the pretreatment and prevents the pH drop.
 Costs of oxygen and alkaline catalyst are considered one of the main disadvantages for
wet oxidation development technologies 43
 Physicochemical pretreatment –
Liquid Hot Water (LHW)
 Is a hydrothermal pretreatment that uses water at high pressures to maintain the liquid state at
elevated temperatures (160-240 C) for variable residence times from seconds to one hour and
solids concentration < 20 wt %.
 In this process biomass is immersed in liquid water
 Most of the hemicellulose is solubilized, cellulose and lignin are not significantly affected and
remain in the solid phase.
 Lignin is partially depolymerized and solubilized, but complete delignification is not possible by
hot water alone, because of the recondensation of soluble components originated from lignin.
 To avoid the formation of inhibitors, the pH should be kept between 4 and 7 because at this pH
hemicellulosic sugars are retained in oligomeric form and monomers formation is minimized
 The amount of sugars released from this method will depend upon the type of biomass and lignin
ratio in the overall biomass composition
 Advantages :
 Cost-savings potential as catalysts are not required and low corrosion allows the construction of low-cost
reactors.
 The solubilized hemicellulose and lignin products are present in lower concentrations, due to higher water
input, and subsequently concentration of degradation products is reduced.
 In comparison to steam explosion, higher pentosan recovery and lower formation of inhibitors are obtained
 Disadvantages :
 Water demand and energetic requirement are higher
 It is not developed at commercial scale. 44
Chemical pretreatment

 Acid pretreatment
 Dilute
 Concentrated
 Alkali pretreatment
 Ionic liquids
 Organosolv

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Chemical pretreatment- Ionic
Liquids (ILs)
 ILs are salts, typically composed of a small anion and a large organic
cation, exist as liquids at room temperature and have very low
vapour pressure.
 The notable characteristics of ILs are their thermal and chemical
stability, nonflammability, wide liquid temperature range, and good
solvating properties for various types of materials
 Pretreatment is usually performed at 3–5 % solid loading,
temperature of 110–160 C, duration of 15 min to 5 h, and at
atmospheric pressure.
 The biomass is then reprecipitated by the addition of water and
washed a number of times before enzymatic hydrolysis
 Pretreatment with ILs is based on dissolution of cellulose

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Chemical pretreatment- Ionic
Liquids (ILs)
 The chemistry of the IL can also be tuned to dissolve the hemicellulose
and lignin, thus making it suitable to dissolve the different components
 Imidazolium-based ILs reported as good methods to dissolve large
amounts of cellulose
 A high yield of cellulose saccharification (80–96 %) has been reported
for IL pretreatment of switchgrass, triticale straw, maple wood, corn
stover, kenaf, bagasse, and eucalyptus
 The low vapor pressure of IL and similar solvents make them more than
99% recoverable in a number of operations, thus reducing costs of
solvent usage.
 Very high price of ILs is the main disadvantage
 As they are recycled and reused, the efficiency of the ILs for
pretreatment decreases
 ILs have negative effects on cellulase activity and affect the final yield
of cellulose hydrolysis.
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Chemical pretreatment- Ionic
Liquids (ILs)
 Efficient removal of these compounds from pretreated materials is
necessary
 ILs trapped inside the treated material reduces the washing efficiency
and increases the amount of water required.
 Removal of Ils:
 Distillation or evaporation can be used to remove volatile antisolvents easily because
most ionic liquids are practically nonvolatile and they have good thermo-stabilities
 Precipitation Using Antisolvents – adding an antisolvent such as water to precipitates
cellulose from the ionic liquid
 Membrane Filtration Precipitates from ionic liquid pretreatment of biomass can be
separated using membrane filtration

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Chemical pretreatment- Ionic
Liquids (ILs)

Pine Wood Fibers in Ionic Liquid

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Chemical pretreatment-Organosolv
 This method consists in the use of an organic liquid (ethanol, methanol, ethylene
glycol, acetone, glycerol, tetrahydrofurfuryl alcohol, etc.) and water,
 The organic solvent is mixed with water in various portions, added to the biomass and
then heated to temperatures ranging 100-250 C.
 The main fractions obtained after pretreating biomass are:
 cellulosic fibers
 solid lignin obtained after removal of the volatile solvent
 liquid solution of hemicellulosic sugars, mainly xylose
 Acids (HCl, H2SO4, oxalic, or salicylic) can also be added as catalysts if the process is
conducted at temperatures below 185-210 C
 The addition of a catalyst can enhance the selectivity of the solvent with respect to
lignin
 Organosolv pretreatment produces a highly digestible cellulose substrate from
almost all kind of raw materials, and lignin with the potential of high-value utilization
can be recovered after pretreatment.
 The solvent must be removed prior to fermentation, because the solvent itself can be
an inhibitor for the enzymatic hydrolysis and the fermentation step.

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Chemical pretreatment-Organosolv
 Solvent is removed by evaporation and condensation, removal and recovery of the
solvent is required for reducing its cost and environmental impact as well
 For economic reasons, low-molecular weight alcohols with lower boiling points such
as ethanol and methanol are favored
 One of the drawbacks when employing organosolvents is related with the significant
amount of furfural, HMF, and soluble phenols from lignin obtained after
pretreatment

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Biological pretreatment
 Microorganisms such as brown-, white-, and soft-rot fungi are
used to degrade lignin and hemicellulose in waste materials
 Brown rots mainly attack cellulose
 White root fungi and soft rots attack both cellulose and lignin
 Lignin degradation by white-rot fungi occurs through the action
of lignin-degrading enzymes such as peroxidases and laccase.
 These enzymes are regulated by carbon and nitrogen sources.
 White-rot fungi are the most effective for biological
pretreatment of lignocellulosic materials such as Phanerochaete
chrysosporium, Ceriporia lacerata, Cyathus stercolerus,
Ceriporiopsis subvermispora, Pycnoporus cinnarbarinus, and
Pleurotus ostreaus

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Biological pretreatment

 Advantages :
 a safe and environmentally friendly method since no
waste stream generated
 process that does not require high energy
 no use of chemicals
 no requirement for pressurized and corrosion-resistant
reactors
 minimal inhibitors productions

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Biological pretreatment

 Disadvantages:
 The rate of biological pretreatment is too slow , thus
require long time to high degree lignin delignification
(weeks to months)
 the requirement of careful growth conditions
 the large amount of space to perform biological
pretreatments
 some of the carbohydrate fraction is consumed by the
microorganism

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THANK YOU

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