EKC 464

Biorefinery
Engineering
Pretreatment Techniques for Biomass
(Part 2)
Dr. Fadzil
Liquid hot water treatment
• Use water at elevated pressure and • Advantages
temperature to maintain its liquid form in • Low cost
order to promote disintegration of biomass • No chemicals / catalysts required
polymers structure. • Low inhibitors in solid fraction (rich with cellulose)
• Hemicellulose is extracted into water phase • Disadvantages
and cellulose remain unaffected due to higher • High temp & pressure
crystallinity. • Less effective for degradation of lignin (check)
• Able to dissolve saccharides for starch based
feedstock.
• Residence time few hours, temperature 160-
240°C.
Biological Pretreatment
• Degradation of biomass polymers by the act
of microorganisms. i.e., fungal.
• Fungi capable for producing enzymes that can
degrade lignin, hemicellulose, and
polyphenols.
• i.e.; Brown-rot fungi able to degrade
hemicellulose and cellulose.
• i.e.; White-rot fungi able to degrade lignin.
• i.e.; Soft-rot fungi able to degrade both lignin
and cellulose.
• Enzyme produced by fungi include, lignin
peroxidase, polyphenol oxidase, manganese
peroxidase, and laccase.
Biological Pretreatment
• Advantages
• Low cost
• Low energy requirement
• Environmental friendly process
• No inhibitors produced
• Disadvantages
• Slow process – residence time of 10-14
days
• Requires careful growth conditions
• Requires large space
Ref: http://isroi.com
 • Exploit the use of conditions and
compounds that affect the physical and
Physicochem chemical properties. (combination of
physical & chemical treatments)
ical • i.e.;
Treatment • Steam-explosion
• Ammonia fiber / Freeze explosion
• For lignocellulose based
Steam Explosion
• Disintegrate the biomass polymeric structure
by rapid expansion (explosion)
Water Steam
• Biomass is treated at high pressure and
temperature for short period of time and then
rapidly depressurized. The structure of biomass
fibrils is disrupted and forms fine fibre.
• Residence time 1 to 10 minutes, Temp 190-
270°C.
• Acids or bases can be added to promote
depolymerization of the lignin, hemicellulose
and cellulose.
Steam Explosion
• Advantages
• Fast process
Water Steam
• Give fine fibers which increases digestibility of
enzymatic hydrolysis and fermentation process.
• No chemical catalyst required.
• Low formation of inhibitors
• Disadvantages
• High pressure, explosion hazard
• High energy requirement (for steam generation)
• Batch process
• Not effective for lignin/hemicellulose/cellulose
degradation/removal.
Ammonia Fibre Explosion
• Disintegration of polymeric structure assisted by
rapid expansion with ammonia as chemical agent.
• Biomass is treated at high pressure and
temperature for short period of time and then
rapidly depressurized. The structure of biomass
fibrils is disrupted and forms fine fibre.
Ammonia gas
• Residence time of 30 minutes, Temp 60-100°C. (less
than steam explosion)
• Ammonium gas help to depolymerize lignin, break
lignin-carbohydrate linkage, removal of acidic
groups and partial degradation of hemicellulose.
Ammonia Fibre Explosion
• Advantages
• Fast process
• Give fine fibers which increases digestibility of
enzymatic hydrolysis and fermentation
process.
• Greatly depolymerize lignin and partial
Ammonia gas
removal of hemicellulose.
• Low energy (operated below 100°C)
• Disadvantages
• High pressure, explosion hazard
• Batch process
• Costly and recycling of ammonium is needed.
• May cause degradation of sugar to furfural
and hydroxymethyl furfural (inhibitors)
Chemical Pre-treatment Summary
Thermochemical Acid – Depolymerize hemicellulose and cellulose
Alkali – Depolymerize lignin
Base & sodium bisulfite – Depolymerize lignin and hemicellulose
Organosolv - Depolymerize lignin and hemicellulose
Wet oxidation – Oxidize lignin
Hot water – Disrupt polymeric structure

Physicochemical Steam explosion – Disintegrate biomass fibrils

Ammonium Fibre Explosion – Disintegrate biomass fibril & degrading lignin

Continuous Pretreatment Process
• Chemical Pretreatment can be Packed
Further purification /
Hydrolysis /
operated continuously by continuous bed Fermentation

feed of chemical-solvent solution

through packed-bed of biomass.
• Can be applied for most of the
chemical pretreatment process
• i.e.;
• Acid pretreatment
• Base pretreatment
• Sulfite pretreatment
• Organosolv pretretment Solvent & Catalyst
Feed
• Wet oxidation pretreament
Continuous Pretreatment Process
with recycle solvent/chemical
W
• Chemical Pretreatment can be Packed
bed
operated continuously by recycling
the chemical solution through Condenser

packed-bed of biomass.
• Can be done if involving volatile Q
Distillation

chemical agents or solvents where

can be recovered through distillation.
• i.e.;
• Ammonium recycle percolation (alkali Recycle of Chemical/Solvent
pretreatment) – ammonia is volatile.
• Orgnanosolv – Organic solvent is Catalyst / Solvent Further purification /
Feed
volatile Hydrolysis /
Fermentation
Pretreatment combination
• Acid & alkali
• Organosolv (Organic solvent & acid/alkali/salt)
• Steam explosion & oxidation (O2, O3, CO2 gas)
• Steam explosion & acid/alkali
 For Thermochemical
Conversion
Ideal • Physical pretreatment
Pretreatment for • Thermal pretreatment
Biochemical & For Biochemical
Thermochemica Conversion
l Conversion
• Physical pretreatment
• Chemical pretreatment
• Biological pretretment
Challenges of Biomass
Pretreatment for Biochemical
Conversion Process

• To reduce the generation of waste (salt/waste

water) from pretreatments
• To reduce the formation of inhibitors during the
chemical pretreatment
• To increase conversion of lignocellulose structure
to digestible sugars
• To reduce the temperature of pretreatment
process
• To minimize the use of chemical catalyst in the
process
 Thermal
• Drying process for removing water
content
Others Physical
pretreatment • Physical separation of non digestible
s material (i.e., water/solid filtration,
fruit peel/starch, corn cob/corn
crop, etc)
• Physical extraction (i.e., oil
extraction from crops by filter press)
The pretreatment will
be more effective if

• Performing physical pretreatment on

biomass prior to chemical treatments
• Combine chemical pretreatment in series