SELF-INTRODUCTION 2
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STEM packages
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Environmental Biotechnology Course, Stadium General, Biochar as a Adsorbing Material, 2
ndApril 2022, UNNES, Semarang, Indonesia
p a r t s
Biochar;
a basic
Torrefaction for
making biochar
Biochar Basics:
An Introduction about the What and Why of Biochar
Paul S. Anderson, PhD
AKA “Dr. TLUD” (TEE-lud) V.P. of Chip Energy Inc
Specialist in micro-gasification [email protected]
Slide-set modified and presented by:
Hugh McLaughlin, PhD, PE
Director of Biocarbon Research Alterna Biocarbon Inc.
[email protected] Version 1 of these slides was presented at the 2009 Northeast Biochar Symposium, November
13 at the University of Massachusetts Amherst
(Released for general distribution and use by others.)
• The placement of charcoal into soils.
• The presence of nearly pure carbon in soils, in the form of amorphous graphite.
• NOT carbon that is in living organisms.
• NOT fossil carbon, as in coal, oil, or natural gas.
Biochar Defined:
Biochar Defined:
Source: https://ucanr.edu/blogs/blogcore/postdetail.cfm?postnum=22132
Charcoal
[1]Briquettes
[1][1] https://www.finecooking.com/article/hardwood-charcoal-vs-charcoal-briquettes
[2] http://biomassmagazine.com/articles/5341/new-biomass-pellet-binder-from-nu-materials
Pellets
[2]His ancestors accomplished soil
improvements that modern science is
trying to
understand
and replicate.
Latosol vs. Terra Preta (Dark Earth)
Terra preta is excellent soil with high presence of charcoal (biochar).
Terra preta might be from “slash and char” practices, but
NOT from current “slash-and-burn” agricultural practices.
Summary of Biochar Properties
• Was biomass; now has charcoal-like properties.
• Significant carbon content, but more than just carbon that has been sequestered:
• Internal surface area and adsorption properties.
• CEC = cation exchange capacity, better fertilizer retention and less field runoff.
•Significant synergisms with soil microbes over time – nitrogen fixers
and other good “bugs.”
https://byjus.com/chemistry/factors-affecting-the-extent-of-adsorption/
https://sciencenotes.org/adsorption-vs-absorption-differences-and-examples/
Half-life of biochar is
~1400 years.
Conclusion #1
• There is something about abundant charcoal in soils that can be highly beneficial to
plants.
• The benefits last for at least hundreds of years.
• Biochar has potential for improving soils and feeding people, especially where soils are
weak.
• ONLY possible with charcoal:
• NOT by putting coal dust into soils.
• NOT by adding manure or other organic material.
Basic Forms and
Transformations of Carbon:
Elemental Carbon
C (solid)
Activated charcoal Regular charcoal Graphite
Carbon black (soot) Coke (from coal)
Oxide gases
C + O
CO & CO 2
Hydrocarbons
C + H
Coal, oil, gases
Biomolecules
C + H + O
Carbohydrates,
Sugars, Cellulose,
Lignin, & much
more in living and
dead biomass.
Basic Forms and
Transformations of Carbon:
Elemental Carbon
C (solid)
Activated charcoal Regular charcoal Graphite
Carbon black (soot) Coke (from coal)
Oxide gases
C + O
CO & CO 2
Hydrocarbons
C + H
Coal, oil, gases
Add H 2 O and photosynthesis by plants
Add Oxygen:
Gasification &
combustion
Loose Oxygen:
Become fossil fuels
Carbonization / Pyrolysis:
Create charcoal
& liberate gases
Biomolecules
C + H + O
Carbohydrates, Sugars, Cellulose, Lignin, & much more in living and dead biomass.
Add Oxygen:
Decay
From: http://www.techtp.com/Torrefaction%20for%20High%20Quality%20Wood%20Pellets.pdf, page 7 of 36
How does wood burn?
• Wood, consists of hemicellulose, cellulose and lignin
• Hemicellulose gasifies at 250 – 300C
• Cellulose splits into char and volatiles between 300C and 450C
• Lignin splits into char and volatiles between 300C and 750C
• Volatilization cools the remaining solid, but the gases burn and generate radiant heat (yellow to blue light)
• Eventually, oxygen can react with the remaining char to make CO2, H2O and ash, plus more heat (red light)
• Putting it all together, we can summarize this in the next
two slides that are easier to understand:
D
drying (A) Extensive Devolatilisation
and carbonisation
(E)
Limited devolatilisation
and
carbonisation (D)
depolymerisation and
recondensation (C)
A E
D
C
E
A D
C
glass transition/
softening (B)
Hemicellulose Lignin Cellulose
100 150 200 250 300
Tem pe rat ure (°C )
Hemicellulose Lignin Cellulose
100 150 200 250 300
Tem pe rat ure (°C )
TOR REF AC TION
Pyrolysis & Carbonization Reactions of Wood
*Below 288 C = Torrefied Wood
*Above 325 C = Biochar
The combustion flame (“C”) burns gases and provides heat to sustain pyrolysis (“P”). Ash is held in the charcoal until “G” (char-gasification) releases it. When “C” goes out, visible smoke shows condensing gases.
A match shows the simple
production of charcoal
Making charcoal
• the first synthetic material produced by man.
• used to draw on the walls of caves, and
• used to transport fire (embers) to new locations.
• later used for smelting tin to make bronze tools.
• easier to do than any of the coal – oil – gas options:
• Converting wood to charcoal is done by heating in an atmosphere of limited oxygen.
• Known as “Pryolysis” or “Carbonization”, we do it every time we
make a fire with wood.
57% of carbon 33% of carbon 0% + 6% + 4% of carbon
(35 wt %) (40 wt %) (25 wt %)
Charcoal retains ~ 20% of the weight and 30% of the energy of the biomass, so ~70% of the energy is released as usable vapors.
Created by photosynthesis using solar energy + CO 2 + H 2 O
Chemical changes as wood becomes
biochar:
MODIFIED ULIMATE ANALYSES OF CHARS
0%
20%
40%
60%
80%
100%
W oo d P ell ets - A W oo d C hip s - B
To rre fie d F ir - C
Gr as s P ell et Ch ar #1 - D Gr as s P ell et Ch ar #2 - E
St raw C ha r # 1 - F St raw C ha r # 2 - G
St raw C ha r # 3 - H
Ga sif ier C ha r # 1 - I Ga sif ier C ha r # 2 - J
W oo d P ell et Ch ar - K M ac N ut Sh ell C ha r - L
Bi oc ha r B ran d # 1 - M
Ju nip er Bio ca rbo n # 1 - N As pe n B ioc ar bo n - O
Ce da r B ioc arb on - P Ju nip er Bio ca rbo n # 2 - Q
Ju nip er Bio ca rbo n # 3 - R Fir B ioc arb on - S
W ei g h t p er ce n t o f d ry s am p le
Res ident Carbon Res ident H & O Res ident Nitrogen Mobile Carbon Mobile H & O Mobile Nitrogen As h (acid s oluble) As h (non-s oluble)
Source: McLaughlin, Anderson, Shields & Reed (2009). All BiocharsAre Not Created Equal…terrapreta.bioenergylists.org
Conclusion #2
• Charcoal is made by the thermal
transformation of biological matter, mainly carbohydrates.
• Plant biomass seems to create the best biochar – both woods and grasses.
• All biochars are not equal – both starting biomass and carbonization conditions
influence the final biochar properties.
Basic Forms and
Transformations of Carbon:
Elemental Carbon
C (solid)
Activated charcoal Regular charcoal Graphite
Carbon black (soot) Coke (from coal)
Oxide gases
C + O
CO & CO 2
Hydrocarbons
C + H
Coal, oil, gases
Add H 2 O and photosynthesis by plants
Add Oxygen:
Gasification &
combustion
Loose Oxygen:
Become fossil fuels
Carbonization / Pyrolysis:
Create charcoal
& liberate gases
Biomolecules
C + H + O
Carbohydrates, Sugars, Cellulose, Lignin, & much more in living and dead biomass.
Add Oxygen:
Decay
Timelines for Carbon
Transformations & Permanence CO 2
Biomass
(living and dead)
Natural short-term cycle of growth and decay (including biomass burning) is Carbon Neutral: C=
Fossil Fuels Biocarbon
Biochar in Soils
Hundreds or thousands of years as long-term carbon sequestration: C-
100 million
years ( C- ) 100 minutes ( C- )
Optional human activity, creating Terra Preta
Burn it. Burn it.
200+ years of fossil fuel consumption is Carbon Positive:
C+
Storing carbon is
Carbon Negative: C-
Timelines for Carbon
Transformations & Permanence CO 2
Biomass
(living and dead)
Natural short-term cycle of growth and decay (including biomass burning) is Carbon Neutral: C=
Fossil Fuels Biocarbon
Biochar in Soils
Hundreds or thousands of years as long-term carbon sequestration:
100 million
years ( C- ) 100 minutes ( C- )
Optional human activity, creating Terra Preta!!!
Burn it. Burn it.
200+ years of fossil fuel consumption is Carbon Positive:
C+ in enormous proportions!!!
Storing carbon is
Carbon Negative: C-
C-
Ice age Ice age Ice age Ice age
285 in 1950
> 380 in 2010
< 300 in 1950
Most recent Ice Age
Shows ONLY 400,000 years. “Civilization” is less than 10,000 years old.
Global Temperature and Atmospheric CO2 over Geologic Time
Late Carboniferous to Early Permian time (315 mya -- 270 mya) is the only time period in the last 600 million years when both atmospheric CO2 and temperatures were as low as they are today (Quaternary Period ).
Temperature after C.R. Scotese http://www.scotese.com/climate.htm CO2 after R.A. Berner, 2001 (GEOCARB III)Source: http://www.geocraft.com/WVFossils/Carboniferous_climate.html
Today
Conclusion #3
• Global warming can be debated, but the increase in
atmospheric CO 2 levels is clearly measured and due to human activities.
• The Earth is very capable of existing with much higher CO 2 levels, but our current human society probably
could not.
• The only current reasonable method for human action to remove significant amounts of atmospheric CO 2 is through biochar for carbon sequestration.
• And Conclusion # 1 states that Biochar is being shown
to improve poor soils, so put char into soils!
Potential Sources of Biochar
Chart of Potential Sources of Biochar
Source: McLaughlin, Anderson, Shields & Reed (2009). All Biochars Are Not Created Equal…terrapreta.bioenergylists.org
Type =>
Issue
Incidental Traditional Gasifier Other Modern Industrial Processes
Applic a-tion
Fire
Residual
Lump Charcoal
Biomass to Energy
By or Co- product
Sole product
Description (Highly general- ized)
Fireplace Forest fire Incineration
Primitive kilns
Modern kilns
Downdraft Updraft
Top-Lit UpDraft
(TLUD)
Traditional retort Specialized retort Fast Pyrolysis
Biocarbon for energy Biochar for soil Bio-Gas & Bio-Oil
Oxygen? Oxic - Uncontrolled Oxic = limited oxygen and
Anoxic = no oxygen
Oxic Anoxic (usually) Anoxic and Oxic
Commercial for biochar?
No. Basically destructive.
Yes. Established product – for cooking
Biochar is NOT the primary objective.
Initial efforts & biochar is NOT the primary goal
Initial efforts
End of the Beginning about Biochar Basics
• Further discussions can cover issues of:
• Production of biochar, including cook stoves.
• Application of biochar.
• Impact of biochar on plants and soil microbes.
Or is this the Beginning of the End?
• With the rising CO 2 level, living conditions of most of humanity will be affected, and current cultural structure and political stability are unlikely to continue for another 100 years.
• Issues of atmospheric CO 2 concentrations will not be resolved without
conscious and significant actions by all the fuel-intense nations of the
World – and actions on the ground everywhere.
take 5
?
https://www.intechopen.com/chapters/55175
STEM packages
37
Environmental Biotechnology Course, Stadium General, Biochar as a Adsorbing Material, 2
ndApril 2022, UNNES, Semarang, Indonesia
p a r t s
Biochar;
a basic
Torrefaction for
making biochar
Thermal treatment of high moisture content biomass using fresh dairy manure
Sitty Nur Syafa binti Bakri
乳牛ふんを用いた高含水率バイオマスの半炭化
Environmental Biotechnology Course, Stadium General, Biochar as an Adsorbing Material, 2 nd April 2022
UNNES, Semarang, Indonesia
39
Torrefaction of fresh dairy manure in an
industrial rotary kiln combustion type reactor
Reaction mechanism of fresh dairy manure Torrefaction of fresh dairy manure in an
industrial rotary kiln combustion type reactor
Reaction mechanism of fresh dairy manure
study
background Highlights
Part II
Part I
Introduction 40
Biomass has become an alternative choices for energy sources
feedstock
treatment product
Schematic overview of biomass for energy sources [1]
Renewable, e.g Bioenergy & Biofuel issues
food & land competition
Issues of corn as a sources of food or fuel [2]
[1] Bohdan Volynets, Farhad Ein-Mozaffari, Yaser Dahman @ https://www.energytoday.net/renewable-energy/biomass-processing-ethanol-pretreatment-enzymatic-hydrolysis-fermentation-rheology-mixing/
[2] Brendan McLaughlin @ http://foodorfuel.weebly.com/
Alternative for biomass feedstock -Agriculture waste 41
livestock manure?
Reduce food & land competition
For managing or producing the raw manure into a product ,
pretreatment is important Challenge High moisture content
[2]Raw manure
Poor biological stability need treatment
[1] State of the World’s Land and Water Resources for Food & Agriculture” (SOLAW) @ http://chinawaterrisk.org/resources/analysis-reviews/agriculture-a-prosperous-ever-after/#sthash.EhNWp5Ii.dpuf
➢ High demand for livestock [2] ;
➢ Protein sources,
➢ shifts in diet that consume more meat
➢ rising in world population
➢ Eventually increase the livestock manure
Key factor
➢ Enough Supply
➢ Env. Problem
[1]
Pre-treatment of raw manure through TORREFACTION 42 torrefaction ?
Dried sample Wet sample
[1][1] photo credit of dairy manure: Laboratory of Agriculture Bio-system Engineering, Graduate School of Agriculture, Hokkaido University
a slow heating process by supplying heat with a temperature range between 200-300 ℃ with certain residence time to produce solid product
no study has been reported for direct usage of wet / high moisture content
biomass
❶ Reduce step process (e.g drying, grinding) ❷ Reduce cost If applicable;
Torrefaction studies with high moisture content biomass such as
livestock manure, sludge, food waste has been conducted*
technical issue in torrefaction
Research question, Hypothesis and Objective 43
[1] photo credit : Kinsei Sangyo Ltd.
Objective: Investigate the capability of high moisture content biomass to become a solid product through torrefaction
Is it possible to conduct a torrefaction with direct usage of high moisture content biomass?
wet biomass can be torrefied to produce solid product
Question
Hypothesis
Material and method
❖ Material
Dairy manure (10kg, 84.1% w.b)
❖ Temperature
200, 250, and 300 °C
❖ Measurement parameters
Time, color changes, mass yield,
moisture content, ash-free solid, ash and higher heating value (HHV)
❖Apparatus
Industrial Rotary kiln combustion type reactor
wet dairy manure
[1][1]
photo credit : Laboratory of Agriculture Bio-system Engineering, Graduate School of Agriculture, Hokkaido University
44
Moisture (%,w.b) 84.1 ±0.2 Ash-free solid (%,d.b) 85.3 ±0.1
Ash (%,d.b) 14.7 ±0.2
HHV (MJ/Kg) 17.6 ±0.2
Table 1 The properties of fresh dairy manure in this study
4 5
the kiln
the chimney
the hopper
Industrial rotary kiln combustion type reactor
Result & Discussion -Time of heat treatment 46
Total time of torrefaction
T1 T2 T4 T3
43.06 40.17 46.42
31.35
28.37 23.35
22.6
19.65 18.18
18.57
0 20 40 60 80 100 120
200 250 300
T im e ( mi nu te )
Temperature (℃) 0
20 40 60 80 100 120
200 250 300
T im e ( mi nu te )
Temperature (℃) 115.58
88.19 87.95
Bakri, SNS.et al.Torrefaction of high moisture content biomass in an industrial rotary kiln reactor. 2018. Journal of the Japanese Society of Agricultural Machinery 80 (2).
Result & Discussion –Torrefied manure 47
T1 T2 T3 T4
200 ° C Raw
*M.C = moisture content
Bakri, SNS.et al.Torrefaction of high moisture content biomass in an industrial rotary kiln reactor. 2018. Journal of the Japanese Society of Agricultural Machinery 80 (2).
48
T1 T2 T3
250 ° C Raw
Result & Discussion -Torrefied manure
Bakri, SNS.et al.Torrefaction of high moisture content biomass in an industrial rotary kiln reactor. 2018. Journal of the Japanese Society of Agricultural Machinery 80 (2).
49
T1 T2 T3
300 ° C Raw
Result & Discussion -Torrefied manure
Temperature of torrefaction is key parameter that determines the color changes
Bakri, SNS.et al.Torrefaction of high moisture content biomass in an industrial rotary kiln reactor. 2018. Journal of the Japanese Society of Agricultural Machinery 80 (2).
General stages of torrefaction process
[1]Result & Discussion – stages of torrefaction 50
T1 T2
T4 T3
= heating and drying
= post-drying
= torrefaction
T1 T2 T3
Drying and decomposition
Involved *
Nhuchhen, D. R., Basu, P. & Acharya, B. (2014). A comprehensive review on biomass torrefaction. International Journal of Renewable Energy &
Biofuels, 1-56.
➊ The wet dairy manure was successfully converted to a solid product or torrefied manure (hypothesis proven).
➋ The effect of temperature is well observed at 250-300 ºC in comparison to 200 ºC for every parameters.
➌ Due to high moisture content, the heat treatment is not a one straight continuous process instead, non-continuous. At least three times of non-continuous heat treatment were required to complete the torrefaction (T1, T2, T3 successively)
➍ On the basis of the characteristics and properties of solid torrefied manure, drying and decomposition process were strongly involved.
Conclusion – I; torrefaction in an industrial rotary kiln reactor 51
52
Torrefaction of fresh dairy manure in an
industrial rotary kiln combustion type reactor
Reaction mechanism of fresh dairy manure Torrefaction of fresh dairy manure in an
industrial rotary kiln combustion type reactor
Reaction mechanism of fresh dairy manure
Background study
Highlights
Part II
Part I
Background : Drying and decomposition 53
On the basis of the characteristics and properties of solid torrefied manure, drying and decomposition process were strongly involved.
[1]
Bakri, SNS.
et al.Torrefaction of high moisture content biomass in an industrial rotary kiln reactor. 2018. Journal of the Japanese Society of Agricultural Machinery 80 (2).
General stages of torrefaction process
[1]Technical issue : non-continuous torrefaction 54 technical issue
Drying and decomposition of high moisture content biomass is not easily determine from the rotary kiln reactor
Torrefaction was conducted non-continuously
When?
T2? T3 ?
T2 T3
Continuous heat treatment is
necessary T1
A continuous torrefaction studies with high moisture content biomass such as livestock manure, sludge, food waste has been conducted*. no study has been reported for direct usage of
wet / high moisture content biomass
Nhuchhen, D. R., Basu, P. & Acharya, B. (2014). A comprehensive review on biomass torrefaction. International Journal of Renewable Energy &
Biofuels, 1-56.
Research question, Hypothesis and Objective 55
Do drying and decomposition processes strongly involved in the torrefaction reaction of high moisture
content biomass?
drying and decomposition processes of wet biomass can be determined through
a continuous torrefaction
Question
Hypothesis
Objective: study the reaction mechanism of high moisture content
biomass through a continuous torrefaction
Material and method
❖ Material
Dairy manure (100 g, 86.1% w.b)
❖ Temperature
200, 250, 300 and 350 °C
❖ Measurement parameters (real-time data) Mass (Mass balance)
Sample temperature (thermocouple sensor) Gas emission (photoacoustic gas monitor)
❖ Apparatus
Heat-resistant wire basket (10 (W) x 10 (L) and 10 (H) cm)
Laboratory oven
wet dairy manure
56
Wired-basket test
➊ A thermogravimetric (TGA)-like experiment
➋ The wet manure put inside the heat-resistant wire basket
➌ heat-resistant wire basket hung onto the mass balance
➍ Real time data recorded for mass, sample temperature and gas
emission
Schematic diagram of the experiment with a laboratory oven [1]
57
Sitty Nur Syafa Binti Bakri, Kioto Ito and Kazunori Iwabuchi. 2017. Investigation of torrefaction reaction on high moisture content biomass using dairy manure. Proceedings of ASABE Annual International Meeting. 16-19 July, Spokane, USA. (doi:10.13031/aim.201700083)
Result & Discussion - Mass reduction of laboratory oven 58
drying decomposition
Sitty Nur Syafa Binti Bakri, Kioto Ito and Kazunori Iwabuchi. 2017. Investigation of torrefaction reaction on high moisture content biomass using dairy manure. Proceedings of ASABE Annual International Meeting. 16-19 July, Spokane, USA. (doi:10.13031/aim.201700083)
𝑣 𝑡 =
𝑚 (𝑡− 𝑛
2 ) −𝑚
(𝑡+ 𝑛 2 )
𝑛 (1)
Result & Discussion - Mass reduction rate graph 59
m = Mass at time t= time
N = interval time
FOUR consecutive stages observed
General stages of torrefaction process
[1]Sitty Nur Syafa Binti Bakri, Kioto Ito and Kazunori Iwabuchi. 2017. Investigation of torrefaction reaction on high moisture content biomass using dairy manure. Proceedings of ASABE Annual International Meeting. 16-19 July, Spokane, USA. (doi:10.13031/aim.201700083)
Result & Discussion - Mass reduction rate graph 60
FOUR consecutive stages observed
but not at 200℃
< 240℃ ;
Low impact of biomass torrefaction
[1]Sitty Nur Syafa Binti Bakri, Kioto Ito and Kazunori Iwabuchi. 2017. Investigation of torrefaction reaction on high moisture content biomass using dairy manure. Proceedings of ASABE Annual International Meeting. 16-19 July, Spokane, USA. (doi:10.13031/aim.201700083)
Result & Discussion - Sample temperature and CO2 emission 61
From sample temperature and CO2 emission, a process of drying and decomposition are confirmed
FOUR consecutive stages observed
Result & Discussion - Sample temperature and CO2 emission 62
FOUR consecutive stages clearly observed at 250-350
oC
but not at 200
oC
only drying process for 200
oC
Sitty Nur Syafa Binti Bakri, Kioto Ito and Kazunori Iwabuchi. 2017. Investigation of torrefaction reaction on high moisture content biomass using dairy manure. Proceedings of ASABE Annual International Meeting. 16-19 July, Spokane, USA. (doi:10.13031/aim.201700083)
