Pyrolysis

Pathways..
Thermal biomass conversion processes

Java: Integrated rice husk gasification –diesel generators to provide electricity to

local rice mills and light for households in > 100 villages.

Transportation of producer gas is a problem

• Traditional
application in
charcoal
production:
intention is to
produce a
smokeless fuel.
• Pits & mounds,
kilns (steel,
brick), retorts
 Pyrolysis: basics

• The decomposition of biomass by heating in

an oxygen-free or oxygen-limited environment
results in the production of three phases: gas,
condensable vapours (leading up to bio-oil)
and char.
Typical product yields of different
processes
 Torrefaction for “Bio-Coal”
• A mild form of pyrolysis at temperatures typically
ranging between 200 and 320 °C.

• During torrefaction, the biomass properties are

changed to obtain a much better fuel quality for
combustion and gasification applications.

• Torrefaction leads to a dry product with no biological

activity like rotting.

• Torrefaction combined with densification leads to a

very energy-dense fuel carrier of 20 to 25 GJ/ton
Torrified pellets compared to Coal
Product spectrum from pyrolysis
Compound classes in bio-oil
Thermal Stability regimes of C, H-C
and Lignin
• A: Drying
• C: Depolymerization
• D: Limited
devolatization and
carbonization
• E: Extensive
devolatization and
carbonization
 Fast pyrolysis

• Reaction conditions
• Dry feedstock (< 12 wt% moisture)
• Biomass heating up to 500°C in 1 - 2 s
• Small biomass particles (1-2 mm)
• Vapour residence time of 1 s (max. 5 s)
• Pyrolysis reactor configurations
‘Bubbling’ fluidised beds
Circulating fluidised beds (CFB)
Rotating cone
Ablative pyrolysis
Conceptual fast pyrolysis process
Conceptual fast pyrolysis process
 Conceptual fast pyrolysis process
1 Biomass type Affects product, can phase separate.
Biomass pretreatment Affects product
2 Drying Costly. Heat recovery is important.
3 Feed size and shape Small size necessary, 2-6mm
4 Reactor configuration Wide variety. Scale & cost important
5 Heat supply to reactor Endothermic. Heat transfer important.
Can use char or gas
6 Secondary cracking Minimise to maximise yield, but may help quality
7 Char separation Important as char has catalytic effect
Char used for reactor heat + export
8 Fractionation Avoid to prevent blockage.
Might control quality or derive chemicals
9 Quench performance Minimise volatile losses
10 EP performance Minimise aerosol losses. Alternatives possible
• Dried feed (<10% m.c)
and 1-2 mm size
• Vapors and Char are
separated in a cyclone.
• Reactor : roughly 10-
20% of total capital cost
• Good control and
efficient heat and mass
transfer
• Biomass particles are introduced into a
bed of hot sand fluidized by a gas,
which is usually a recirculated product
gas. High heat transfer rates from
fluidized sand result in rapid heating of
biomass particles.

• There is some dilution of the products,

which makes it more difficult to
condense and then remove the bio-oil
mist from the gas exiting the
condensers.

• The main challenges are in improving the

quality and consistency of the bio-oil.
 Circulating fluidized bed

• Biomass particles are introduced into a

circulating fluidized bed of hot sand.
Gas, sand, and biomass particles move
together, with the transport gas usually
being a recirculated product gas,
although it may also be a combustion gas.

• High heat transfer rates from sand

ensure rapid heating of biomass
particles.

• A fast separator separates the product

gases and vapors from the sand and char
particles.
Rotating Cone Reactor
 Bio-oil
• Combustible, HHV ~ 17-18 MJ/kg
• Rich in oxygenated compounds
• 10 to 25 wt% water
• Highly corrosive, pH ~ 2
• Not distillable
• Unstable (ageing = polymerisation of
bio-oil compounds)
• Immiscible with hydrocarbons
• Low cetane number (10 ~ 25)
Bio-Oil Applications
Application of fast pyrolysis products
 Bio-Oil stabilization and upgradation
• Physical
– Vapor Filtration
– Emulsion
• Chemical and catalytic upgrdation
– Hydrotreating (High pressure, low temp rxn)
– Gasification followed by FT
• Antioxidants addition
• Esterification
 Chemicals in Bio-oil
• Acetic acid
• Food flavorings
• Hydroxyacetaldehyde
• Levoglucosan
• Levoglucosenone
• Maltol
• Phenol Polyphenols
• Resins
• Sugars
 Food flavorings
• Fire-roasted
• Wood-fired brick oven
• Flat-iron-grilled
• Toasted oak
• Chargrilled
• Cast iron campfire
• Flame-kissed
• Pit-smoked
Biorefinery
Pyrolysis based Biomass Biorefinery
Biochar
 The CO2 solution
• By pyrolyzing biomass it becomes more recalcitrant and
can be used to store carbon in soil

• How much CO2 could be sequestered using purposeful

biochar production and application to soil?

Images from www.news.cornell.edu and Adam

• Black carbon is particularly effective for sorption
of planar, hydrophobic, aromatic compounds, such
as polycyclic aromatic hydrocarbons and planar
polychlorinated biphenyls, that are able to engage
in face-to-face orientation with the graphene
planes.
• Pyrolysis temperature impacts the degree of
carbonization: the development of surface area
and aromaticity in the source material.
• Polarity, aromaticity, surface area, and
pore size distribution can control the
sorption of nonpolar and polar solutes on
300–700°C plant biochars.
 Environmental benefits
• Combating climate change
• Improving soil
• Scrubbing air pollutants
• Reducing pollution of waterways

large specific surface area, porous structure, surface functional

groups, and high mineral content
 Not all Biochars are created
Equal
Biochar properties are determined by pyrolyis conditions

• Prominent Factors:
– Temperature
• Residence time
– Pressure
– Fluidizing agent
– Degree of oxidation

• Mechanisms:
– O, H, C, and minerals (K, Ca, N, P, Al, S,…) are volatilized at different rates
– The remaining C molecules rearrange

Image from ”Biochar: Environmental Management” (edited by Lehmann and Joseph, 2009)
 Characterizing Chars

According to According to
Structure Function

Physical and Phenomenological

chemical abilities to improve
characterisitics plant growth and
microbial processes

Ability to store carbon

Important objectives for researchers

• To detect structural (chemical) differences in

biochars using advanced analysis techniques
• To detect structural (chemical) changes after
incorporation into soil using advanced
analyses
• To measure the stability of biochars using
laboratory incubation and natural abundance
carbon isotopes
 Hypotheses
• The production method influences biochar’s
stability and structure
– Higher temperature chars are expected to be more recalcitrant,
consisting of aromatic rings instead of O-alkyl carbon, affecting
surface properties of the biochar and its behavior in soil
– More intensive pyrolysis methods will lead to more stable biochars
– Structural characteristics will affect stabilization behavior of the
char (binding to organic matter and clay)
• Two C4 feedstocks

140 x corn cob 280 x miscanthus

 Characterization Methods

• Elemental Analysis
– Weight % of C, H, O, N, S
• Proximate Analysis
– Moisture content
– Volatile content
– Free carbon remaining
– Ash (mineral content)
TG
Figure from Morten Grønli

– Mass change of a material as a function of temperature

DSC
– Thermal stability and decomposition
Effect of Temperature on Char Yield
 van Krevelen plot
(H/C versus O/C ratios) of biochars
Effect of temperature on Biochar pH
Effect of feedstock type on biochar pH
Effect of temp on S. area
Biochar sorption for metals
 Biochar functional properties
• The positive response from application of biochar to
soil could be due to a host of potential reactions
related to biochar such as –
• retention of soil nutrients,
• removal of soil constraints limiting plant growth
(increasing soil pH),
• toxin neutralisation,
• enhanced soil physical properties (water retention),
• reduced soil strength,
• Improved N fertilizer-use efficiency
 Biochar advantages
• Biochar per unit of carbon has a much greater
ability than that seen for soil, for absorbing
cations) partially due to –
– combined effect of larger surface area
– greater charge density and
– increased negative surface charge affected by the
pyrolysis conditions.
 Does one size fits all in case of
Biochar?
• Most studies have been done under laboratory
conditions and in the short-term (< 2 years).
• There is a broad spectrum of biochars and a
lack of standardization among the currently
available biochars, leading, in part, to the
divergent effects. Hence, a rigorous definition
and standardization of what a good biochar is,
needs to be established.
• It is very pertinent to assess the economic and
logistical feasibility of biochar applications at
larger scales under field conditions.

The claims of its benefits have been exaggerated !

 Current research in Biomass
Pyrolysis
• High-value carbon materials, including
activated carbon, carbon nanotubes,
graphene, carbon foam, and carbon
quantum dots