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Fundamentals of Charcoal

Production
Stefan Czernik
National Bioenergy Center
IBI Conference on Biochar, Sustainability and Security in a
Changing Climate
September 8-10, Newcastle, U.K.

Outline

Introduction
Charcoal
Biomass
Pyrolysis

Charcoal formation
Stoichiometric and thermodynamic potential
Biomass pyrolysis pathways

Optimum process conditions for charcoal


production

Technologies for producing charcoal

Conclusions

What is Charcoal?
Charcoal is a solid product of pyrolysis
of biomass carried out at temperature
above 300C.
Is black in color, retains morphology
of original feedstock, burns without
flame.
Is not a pure carbon or a single
compound.
Elemental composition:
C, H, O, N, S, ash
Proximate analysis:
fixed carbon >70% , volatiles, ash

Picture from Wikipedia

Has been produced for thousands


years.

Charcoal
Global charcoal consumption: 45 Mton/year
Africa

23 Mton/year

South America

17 Mton/year

WEC 2007 Survey of Energy Resources FAOSTAT-Forestry

(Ethanol global production:

60 Mton/year)

Cost of charcoal: $100- 400/ton


Applications: fuel, metallurgy, activated carbon
Emerging use as a soil amendment and a carbon
sequestrating material.
5.5 Gton carbon released annually by combustion of fossil fuels
can be offset by 7.5 Gton of charcoal used as soil amendment

Biomass
Biomass is a plant matter, renewable product of photosynthesis.
Includes trees, grasses, agricultural crops and residues, animal
wastes and municipal solid wastes.
World terrestrial biomass resources 120 Gton/year.
Field, C. B. et al., (1998) Science 281, 237-240.

Potential for 30 Gton/year charcoal.

Starch, fat, and protein rich


biomass
Lignocellulosic biomass:
trees, grasses, agricultural residues

Food supplies
<20% of total
biomass.
Non food
>80% of total
biomass.

Lignocellulosic Biomass
Average elemental composition: CH1.4O0.6
Cellulose: 38% - 50%
Most abundant form of carbon in
biosphere
Polymer of glucose

Hemicellulose: 23% - 32%


Polymer of 5- and 6-carbon
sugars
Xylose is the second most
abundant sugar in the biosphere

Lignin: 15% - 25%


Complex aromatic structure
p-hydroxyphenylpropene building
blocks

Extractives: 1% - 5%

Pyrolysis of Biomass
Thermal decomposition occurring in the
absence of oxygen.
At temperature above 300C biomass
polymeric building blocks undergo
crosslinking as well as partial
depolymerization and fragmentation to form
smaller molecules which are released as gases
and vapors that can react with residual solids
producing more condensed structures.
Pyrolysis always produces solid (charcoal),
liquid (water and organics), and gaseous (CO,
CO2, CH4, H2) products at proportions and
composition dependent on feedstock and on
process conditions.

Slow heating of biomass


Temperature

Solid Phase

Gas Phase

<200C

Drying

H2O

230C-250C

Retification

Acetic acid, MeOH

250C-280C

Torrefaction

Extractives

300C-500C

Devolatilization

Organics, H2O, gas

>500C

Carbonization

Tars, H2O, gas

Charcoal Yields
Stoichiometric:
CH1.4O0.6

CH0.2 + 0.6H2O
53.0% (100% C)

Thermodynamic:
Cellulose:
C6H10O5

3.74C + 2.65H2O + 1.17CO2 + 1.08CH4


27.7% (62.4% C)

Antal, M,J. and Gronli, M, Ind.Eng.Chem.Res 2003, 42, 1619-1640

Practical:
CH1.4O0.6

charcoal + gas + liquid


10-35% (15-60% C)

Biomass Pyrolysis Pathways


Secondary Processes

Primary Processes

Light HCs,
Aromatics,
& Oxygenates

Primary
Vapors

CO, CO2,
H2O

Liquid
Phase

Low P

Low P

Vapor
Phase

Olefins, Aromatics
CO, H2, CO2, H2O

Tertiary Processes
PNAs, CO,
H2, CO2,
H2O, CH4

High
P
Primary
Liquids

Condensed Oils

Tars

(phenols, aromatics)

High
P
Solid
Phase

Biomass

Charcoal

Coke

Pyrolysis Severity
Evans, R.J. and Milne, T.A., Energy & Fuels 1987, 1, 123-137.

Soot

CO, H2,
CO2, H2O

Biomass Pyrolysis Processes


Char

Liquid

Gas

CARBONISATION
low temperature
long residence time

35%

30%

35%

FAST PYROLYSIS
moderate temperature
short residence time

12%

75%

13%

GASIFICATION
high temperature
long residence time

10%

5%

85%

How to Enhance Charcoal


Formation?
Charcoal is a product of both primary (char) and
secondary (coke) reactions
Increasing charcoal yields requires minimizing the
carbon losses in the form of gases and liquids and
promoting the desired pathways:

primary solid-phase dehydration,


decarboxylation, and decarbonylation
reactions

secondary conversion of pyrolysis vapors to


solids

Charcoal Yields
Charcoal yields depend on feeedstock and
on process conditions:
Cellulose, hemicellulose, lignin and ash
content

Pyrolysis temperature
Process pressure
Vapor residence time
Particle size
Heating rate
Heat integration (biomass burn off).

TGA of Biomass Polymers


heating at 10C/min to 600C in nitrogen

Beech wood xylan


Aspen lignin

Cellulose (cotton linters)

TGA of Poplar Wood


heating at 10C/min to 600C in nitrogen

Beechwood xylan
Aspen lignin

Cellulose (cotton linters)

Increasing Charcoal Yield


The charcoal yields will increase with:

High hemicellulose, lignin and ash content in biomass

Low pyrolysis temperature (<400C)


(but also lower fixed carbon content)
High process pressure (1 MPa)
(higher concentration of pyrolysis vapor increases rate of
secondary reactions)
Long vapor residence time (extended vapor/solid contact
promotes secondary coke forming reactions)
Low heating rate (slower formation and escape of organic
vapors)
Large biomass particle size (low thermal conductivity of
biomass results in slow heat and mass transfer rate within
particles)
Optimized heat integration (minimized biomass burn off)

Heat for Charcoal Production


<280C

Endothermic (drying, depolymerization


and devolatilization)

300C-500C

Exothermic (char formation)

>500C

Endothermic (char carbonization)

Heat for the process can be provided:

directly as the heat of reaction

by flue gases from combustion of by-product


and/or feedstock directly to the reactor

by flue gases through the reactor wall

Charcoal Production
Batch processes:

Yield

Earth pits and mounds

>10%

Brick, concrete, and metal kilns

20-25%

Retorts

30%

Continuous processes:
Retorts (Lambiotte)

30-35%

Multiple hearth reactors (Herreshoff)

25-30%

Novel processes:
Flash carbonization

40-50%

Earth Mound Charcoal Production


A - fuelwood
B - carbonisation zone
C - charcoal zone

Swedish earth kiln with chimney


Simple technologies for charcoal making
FAO Forestry Paper 41, Rome 1987.

Release of pyrolysis gas and vapor to atmosphere


No heat recovery; significant wood burn off for process
energy
Low yield; environmental pollution

Lambiotte Retort
Continuous operation
Wood moves down in
countercurrent with hot flue
gases from combustion of
pyrolysis gas
Cool charcoal is retrieved at
the bottom through a lock
mechanism
Pyrolysis liquid are
condensed and used as byproduct
Pyrolysis gas is heated in the
bottom section then burned
FAO Forestry Paper 63, Rome 1985

Flash Carbonization
Batch operation; 10 tons/day
charcoal.
Biomass loaded to a canister
then heated up to 350C at
0.7 MPa for 30-90 min.
Charcoal yield 40-50%
(70-80% fixed carbon).
Catalytic afterburner for tars
eliminates smoke from reactor
effluents.
Capital cost $200,000.
HNEI Flash Carbonization
Demonstration Reactor

Conclusions

Charcoal is a product of primary and secondary


reactions occurring during pyrolysis of biomass.
High yields of charcoal are favored by:
high lignin content and large particle size of
biomass,
low temperature and high process pressure
low heating rate and long vapor residence time
in the reactor,
heat integration of the process
Production processes have to include by-product
recovery or use for process energy to decrease
detrimental environmental impact of traditional
methods.