An Introduction to Biochar with an

Emphasis on its Properties and Potential

for Climate Change Mitigation

Jim Amonette
Pacific Northwest National Laboratory
Richland, WA 99352 USA

PNW Biochar Initiative Meeting

21 May 2009

PNNL-SA-66736
 Outline
What is Biochar?
How is it Made?
Pyrolysis and Hydrothermal Carbonization Processes
Feedstocks
Yields
What are its Properties?
Physical
Chemical
How can it be Used?
Energy
Soil Fertility
Carbon Sequestration
Where does it fit in the Environmental Technology Landscape?
Summary

JE Amonette 24Apr2009
 What is Biochar?
“Biochar is a fine-grained charcoal high in organic carbon
and largely resistant to decomposition. It is produced
from pyrolysis of plant and waste feedstocks. As a soil
amendment, biochar creates a recalcitrant soil carbon
pool that is carbon-negative, serving as a net
withdrawal of atmospheric carbon dioxide stored in
highly recalcitrant soil carbon stocks. The enhanced
nutrient retention capacity of biochar-amended soil not
only reduces the total fertilizer requirements, but also
the climate and environmental impact of croplands.”
(International Biochar Initiative Scientific Advisory
Committee)

JE Amonette 24Apr2009
 What is Biochar?

Product
Solid product resulting from advanced thermal degradation of
biomass
Technology
Biofuel—process heat, bio-oil, and gases (steam, volatile HCs)
Soil Amendment—sorbent for cations and organics, liming agent,
inoculation carrier
Climate Change Mitigation—highly recalcitrant pool for C,
avoidance of N2O and CH4 emissions, carbon negative energy,
increased net primary productivity (NPP)

JE Amonette 24Apr2009
 How is Biochar Made?

Major Techniques:
Slow Pyrolysis
traditional (dirty, low char yields) and modern (clean, high char yields)
Flash Pyrolysis
modern, high pressure, higher char yields
Fast Pyrolysis
modern, maximizes bio-oil production, low char yields
Gasification
modern, maximizes bio-gas production, minimizes bio-oil production,
low char yields but highly recalcitrant
Hydrothermal Carbonization
under development, wet feedstock, high pressure, highest “char”
yield but quite different composition and probably not as recalcitrant
as pyrolytic carbons

JE Amonette 24Apr2009
 Slow Pyrolysis—Continuous Auger Feed
Exhaust gas
and heat
Gas
Generator
turbine
Lignocellulosic Electricity Air
feedstock

Mill Gas
cleaner
and
Flue separator
Hopper Steam gas
Pyrolysis Pyrolysis
Dryer reactor gases

Cyclone
Feeder Combustor
Motor

Heat Char
Air
Biochar
storage

courtesy Robert Brown

JE Amonette 24Apr2009
 Fast Pyrolysis Fluidized Bed Reactor

Lignocellulosic Pyrolysis gases

feedstock

Vapor, gas,
Flue Cyclone
Mill char
gas products
Quencher

Hopper
Bio -oil
Pyrolysis Char storage
reactor
Biochar
Motor Feeder Bio-oil
storage

Fluidizing gas
Combustor

Air

Brown (2009)

JE Amonette 24Apr2009
 Pyrolysis

Competition between three processes as biomass is

heated:
Biochar and gas formation
Liquid and tar formation
Gasification and carbonization
Relative rates for these processes depend on:
Highest treatment temperature (HTT)
Heating rate
Volatile removal rate
Feedstock residence time

JE Amonette 24Apr2009
 Competition Among Pyrolysis Processes
Spruce Wood, Slow Pyrolysis, Vacuum
(Demirbas, 2001)
Factors favoring 90
biochar formation 80
Char
Gas
70
Lower temperature 60
Tar+Liquid

Yield, wt%
50
Slower heating rates 40

Slower volatilization 30
20
rates 10
0
Longer feedstock 200 300 400 500 600 700 800 900
residence times High Heating Temperature, C

In general, process is Eastern Red Maple Wood, Fast Pyrolysis, High Purge Rate
(Scott et al., 1988)
more important than
feedstock in 90
80
Char

determining products 70
Gas
Liquid

of pyrolysis 60
Yield, wt%

50
40
30
20
10
0
200 300 400 500 600 700 800 900
JE Amonette 24Apr2009
High Heating Temperature, C
 Wood Char Yields from Pyrolysis

Figure from Amonette and Joseph (2009) showing data of Figueiredo et al. (1989), Demirbas (2001), Antal et al.
(2000), Scott et al. (1988), and Schenkel (1999) as presented by Antal and Gronli (2003),.

JE Amonette 24Apr2009
 Feedstocks

Essentially all forms of biomass can be converted to biochar

Preferable forms include: forest thinnings, crop residues (e.g., corn
stover, alfalfa stems, grain husks), yard waste, paper sludge,
manures, bone meal
Trace element (Si, K, Ca, P) and lignin contents vary
Lignin content can affect char yields

Lignin Content, Temperature, and Char Yield

Slow Pyrolysis, Vacuum (Demirbas, 2001)

50
y = 0.39x + 26.76
45
R2 = 0.99
40
Husks, Shells, Kernels
Char Yield, wt%

35
30
25 Corn Cob Wood y = 0.33x + 15.29
R2 = 0.96
20
15
Char (277 C)
10 Char (877 C)
5
0
0 10 20 30 40 50 60
Biomass Lignin Content, wt%

JE Amonette 24Apr2009
 What are the Properties of Biochar?
Pine Wood Char

Oak Wood Char

Corn Cob Char

JE Amonette 24Apr2009
 Physical Properties

Slow
Fast
Gas

JE Amonette 24Apr2009
 Physical Properties Change with HTT
a
)

b
)

Downie et al., 2009 Kercher and Nagle, 2003

JE Amonette 24Apr2009
 Physical Structure and
Chemical Properties Depend
on Carbon Bonding Network

Radovic et al., 2001

13CCP-MAS NMR
Amonette et al., 2008
JE Amonette 24Apr2009
 X-ray Diffraction Analysis

Slow Pyrolysis and Hydrothermal Chars

Gasification and (steam present)
Fast Pyrolysis Chars Combustion Char (high mineral content)

JE Amonette 24Apr2009
 Chemical Properties

Slow
Fast
Gas

Slow Pyrolysis chars produced in presence of steam at 475°C tend to

be acidic (carboxylic acid groups activated)
Fast Pyrolysis chars produced in absence of steam at 500°C tend to
be slightly basic
Gasification chars produced in presence of steam at 700°C tend to be
very basic and make good liming agents
JE Amonette 24Apr2009
 Surface Chemistry
1200
NaOH Analyte
Slow Pyrolysis (steam)
Na2CO3 Analyte
1000
NaHCO3 Analyte
Fast Pyrolysis (no steam)
HCl Analyte
800

Gasification (steam) 
600

400

200

0
OKEB PBEB PCEB PCN OAK PNNL‐M PNNL‐P PNNL‐S HW OK (CSA)  WS  CSB 

‐200

JE Amonette 24Apr2009
 pH-Dependent Exchange Capacities
Oak Feedstock

1000
OKEB Slow Pyrolysis (steam), 475°C
800 OAK
Ion Sorption Capacity, meq/kg

OK (CSA)
600

400
Fast Pyrolysis, 500°C

200
Gasification (steam), 700°C

0
0 2 4 6 8 10 12 14
-200

-400

-600

pH

JE Amonette 24Apr2009
 How can Biochar Technology be Used?

Generate Carbon-Negative Energy

Soil Amendment
Carbon Sequestration

JE Amonette 24Apr2009
 Comparison of Biochar Production Methods

Carbonization Products Net Energy Fossil C Solid C

Method Released, (Coal) Offset Production
GJ/t C Efficiency Efficiency
Fast CH4, CO2, Bio- 22.0 0.65 0.15
Pyrolysis Oils, H2O, Char

Slow Char, tars, CH4, 17.7 0.53 0.5

Pyrolysis CO2, H2O

Hydrothermal “lignite”, H2O 5.5 0.16 1.0

Conversion

Combustion CO2, H2O 38.4 0.97 0.01?

JE Amonette 24Apr2009
 The Biofuel N2O Problem
Recent work (Crutzen et al., 2007, Atmos.Chem. Phys.
Disc. 7:11191; Del Grosso, 2008, Eos 89:529) suggests
that globally, N2O production averages at 4% (+/- 1%) of
N that is fixed
IPCC reports have accounted only for field measurements
of N2O emitted, which show values close to 1%, but
ignore other indicators discussed by Crutzen et al.
If 4% is correct, then combustion of biofuels except for
high cellulose (low-N) fuels will actually increase global
warming relative to petroleum due to large global warming
potential of N2O
Biochar avoids this issue
Ties up reactive N in a stable pool
Eliminates potential N2O emissions from manures and other
biomass sources converted to biochar
Decreases N2O emissions in field by improving N-fertilizer use
efficiency and increasing air-filled porosity
JE Amonette 24Apr2009
 Soil Amendment

Biochar typically increases cation exchange capacity, and hence

retention of NH4+, K+, Ca2+, Mg2+
N from original biomass, however, may not be readily available
P, on the other hand, is generally retained and available
Liming agent
Enhanced sorption of organics (herbicides, pesticides, enzymes)
(Good? Bad?)
Some evidence for increased mycorrhizal populations, rhizobial
infection rates
Used as carrier for microbially-based environmental remediation
Lowers bulk density

JE Amonette 24Apr2009
 Identification of best biochar type for soil
application
Criteria
Near-neutral pH
High ion exchange capacities (CEC and AEC)
Moderate hydrophobicity to retain organics
High stability to oxidation
Low volatile content
Pre-treated with NH4+ to avoid induced N deficiency
Recommendation
Steam-activated
Carbonized (i.e., treated to higher temperature to remove
volatiles)
Slow pyrolysis probably better

JE Amonette 24Apr2009
 Carbon Sequestration
Why?
Decrease atmospheric
GHG levels Atmosphere
597 + 211

Stop acidification of
oceans by CO2 7.

absorption 2

We only have one Earth Vegetation, Soil, and

Detritus
2477 - 34
Fossil Fuels
3700 - 319

How? Surface Ocean

900 + 22

Create stable C pool

using biochar Intermediate and Deep Ocean
37100 + 120

Use energy to offset

fossil-C emissions
Avoid emissions of N2O Pre-industrial values (1750)
Anthropogenic changes (2005)
Adapted from IPCC AR4 WGI with updated inventory and flux data

and CH4
Increase net primary
productivity (NPP)

JE Amonette 24Apr2009
 Observed and Projected Global Warming

JE Amonette 24Apr2009 IPCC (2007) WG1-AR4, SPM, p. 6, 14

 Factors Affecting Global Warming (100-year
timeframe)

JE Amonette 24Apr2009
IPCC (2007) WG1-AR4, p. 136
 Properties of Key Greenhouse Gases

Atmos. Relative Global Global Global

Half-life, Radiative Warming Warming Warming
yr Efficiency Potential Potential Potential
(20-yr) (100-yr) (500-yr)

CO2 30-325* 1 1 1 1

CH4 8.3 26 72 25 7.6

N2O 79 214 289 298 153

CFC- 69 23000 11000 10900 5200

12

H2O ~0.011 ~0.4 Due to its short half-life

(precipitation!), H2O is a feedback
gas, rather than forcing warming

*Decay rate has several pathways with different rates. About 22% of the
CO2 is very long lived. The first two half-lives are 30 yr and 325 yr.
IPCC (2007) WG1-AR4, SPM, p. 3
JE Amonette 24Apr2009
 Projected Atmospheric Carbon Levels and
Associated Global Warming
Cumulative Anthropogenic C in Atmosphere (GtC)

2500
Atmospheric concentration
of CO2, ppm
2000

1250
1500

850
1000
600

500 Irreversible warming threshold?

379
280

0
B
t

B1

A2
50

an

A1
17

st

00

00
00
n

21

21
Co

21
05
20

IPCC (2007) WG1-AR4, SPM, p. 14, modified to show

zone where irreversible warming of Greenland ice sheet is
JE Amonette 24Apr2009 projected to occur (ibid., p. 17)
 What to do . . .

Eliminate the C-positive, accentuate the C-negative!

Minimize fossil fuel inputs
Improve energy efficiency
Point-source capture/sequestration of CO2
Replace with biofuels, nuclear (???$$$)
Maximize terrestrial sink (diffuse
capture/sequestration)
Afforestation
Low-input and perennial cropping systems
Implement C-negative energy technologies
Biomass combustion with CO2 sequestration
Biomass pyrolysis with biochar production/CO2 sequestration

JE Amonette 24Apr2009
 Creating a Stable Carbon Pool with Biochar

JE Amonette 24Apr2009
 Human-Appropriated Net Primary Productivity
29% of all C fixed by photosynthesis aboveground
(ca. 10.2 GtC/yr) is currently used by humans!
Of this 1.5 GtC/yr is unused crop residues,
manures, etc.
An additional 1.8 GtC/yr) is not fixed due to prior
human activities (e.g., land degradation) and
current land use
Current fossil-C emissions are ca. 8 GtC/yr
Increased productivity and expanded use of
residues from biochar production could have a
significant impact on global C budget

Haberl et al., PNAS 2007

JE Amonette 24Apr2009
 Carbon Sequestration using Biochar

Slow pyrolysis biochars are highly Estimates of Half-life in Soils

(Slow Pyrolysis Biochars)
recalcitrant in soils with half-lives of
100-900 years 1400
Cheng et al. (2008)

Sensitivity analysis suggests that 1200

half lives of 80 years or more are 1000

Kuzyakov et al. (2009)

sufficient to provide a credible C sink

Time, years
800

Recent evidence using 14C-labeled 600

biochar shows no evidence for 400

enhanced rates of soil humic carbon
200
degradation in agricultural soils
(Kuzyakov et al., 2009) 0
5 10 15 20 25 30 35

No evidence for polyaromatic Mean Annual Temp, C

hydrocarbon (PAH) contamination

has been seen
Down-side risks seem very small

JE Amonette 24Apr2009
 IBI Estimates of Global Biochar Impact

JE Amonette 24Apr2009
 The last resort ?
To balance the C cycle, annual
human harvest of fixed biomass
would have to double from about
8.2 Gt C currently (Haberl et al.,
2008) to more than 15 Gt C. This
would amount to harvesting about
40% of above-ground biomass C,
and is comparable to levels of
biomass C appropriation seen in
India today (Haberl et al., 2008).

The annual diversion of 11.3% of

global biomass carbon (7 Gt C,
roughly one-fifth of all above-ground
biomass C produced) to a pyrolysis
industry would have a profound See James Lovelock Interview
impact on the global ecology and http://www.guardian.co.uk/science/video/2009/
would be considered a last resort. apr/22/james-lovelock-gaia-space-biochar

JE Amonette 24Apr2009
 Methane and Traditional Methods

Woody Biomass
Traditional methods No Energy Recovery
without energy 36% Biochar Yield
600
recovery generate 30% Biochar Yield
methane 500
20% Biochar Yield
10% Biochar Yield

Global Warming Mitigaion Potential,

Some decrease in

g CO2-Ceq/kg dry biomass

mitigation potential 400 Modern
Slow
results Pyrolysis
300
Difference in biochar
yield is far more 200
important Traditional kilns
w/ no energy recovery
These methods still 100

yield a positive result

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
CH4 Emissions (Percent of all C Emissions)

JE Amonette 24Apr2009
 Impact of Energy Recovery

All Sustainable Biomass

Recovery of energy 70% Pyrolysis Energy Recovery Efficiency

released during 600

pyrolysis improves
mitigation potential 500
Modern

Global Warming Mitigaion Potential,

significantly Slow

g CO2-Ceq/kg dry biomass

Pyrolysis
400
Modern pyrolysis
methods should be 300
implemented wherever
possible 200
36% Biochar Yield
Economic decision 30% Biochar Yield
Traditional kilns
w/ no energy recovery
100
20% Biochar Yield
10% Biochar Yield
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
CH4 Emissions (Percent of all C Emissions)

JE Amonette 24Apr2009
 Where does Biochar Fit?
Offers a flexible blend of biofuel energy, soil fertility enhancement,
and climate change mitigation
Limited by biomass availability and, eventually, land disposal area
How much biomass can be made available for biochar production vs.
other uses?
Crop-derived biofuels cannot supply all the world’s energy needs
Maximum estimates suggest 50% of current, 33% of future
Biodiversity (HANPP)?
N2O?
Perhaps best use of harvested biomass is to make biochar to draw
down atmospheric C levels and enhance soil productivity, with energy
production as a bonus (but not the driving force).
This will require government incentives (C credits/taxes?) and a
change in the way we value cropped biofuels

JE Amonette 24Apr2009
 Further Information and Acknowledgments
International Biochar Initiative
(www.biochar-international.org)
New book: Biochar for Environmental Management:
Science and Technology, Earthscan, 2009 (in press)
North American Biochar Conference 2009
University of Colorado at Boulder, August 9-12, 2009

Research supported by
USDOE Office of Fossil Energy through the National Energy Technology
Laboratory
USDOE Office of Biological and Environmental Research (OBER) through
the Carbon Sequestration in Terrestrial Ecosystems (CSiTE) project.
Research was performed at the W.R. Wiley Environmental Molecular Sciences
Laboratory, a national scientific user facility at the Pacific Northwest National
Laboratory (PNNL) sponsored by the USDOE-OBER.
PNNL is operated for the USDOE by Battelle Memorial Institute under contract
DE AC06 76RL01830.

PNNL-SA-64398
JE Amonette 24Apr2009
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