Review Biochar II
Review Biochar II
review
a
Engineering Program Research Group, College of Engineering, University of
*Corresponding author.
University of Cartagena
Zaragocilla Campus
Cartagena, Colombia
Fax: 57-5-6698323
E-mail: [email protected]
1
Abstract
about raw materials and pyrolysis process focusing on different types of biomass. It
temperatures the biochar surface area decreases, limiting its use as adsorbent.
Most of the raw materials used to obtain biochar belong to the group of
Introduction
carbonyl, and quinines (Brewer et al., 2011; Beesley & Marmiroli, 2011; Yao et al.,
2010; Uchimiya et al., 2010). Organic carbon content of biochar can be as high as
2
90%, depending on the source material (Beesley et al., 2010). Figure 1 shows the
and peanut (Yuan et al., 2011), miscanthus (Kwapinski et al., 2010), corn stover
(Brewer et al., 2011), switchgrass and wheat straw (Bruun et al., 2011), sludge
wastewater (Hossain et al., 2011), and rice straw (Peng et al., 2011; Xiao et al.,
biomass has higher carbon content. Usually the increase in temperature results in
Biochar has generated great interest worldwide (Li et al., 2011) due to its use in
multiple applications such as soil improver (Barrow, 2012, Karhu et al., 2011;
Zheng et al., 2010; Hossain et al., 2010; Beesley et al., 2010; Tenenbaum, 2009;
Smith et al., 2010; Noguera et al., 2010), fuel (He et al., 2012), catalyst (Dehkhoda
et al., 2010), adsorbent for pollutants removal (Keiluweit et al., 2010; Cao et al.,
2010; Qiu et al., 2009) and carbon sequestration (Barrow, 2012, Vaccari et al.,
2011; Bruun et al., 2011; Hammond et al., 2011; Matovic, 2011; Woolf et al., 2010;
production and use of biochar permits the recycling of organic waste from
agriculture (Peng et al., 2011; Chen et al., 2011; Lee et al., 2010; Inyang et al.,
2010), livestock (Uchimiya et al., 2010; Cao et al., 2010) and sludge wastewater
(Chun et al., 2011; Zhang et al., 2011; Hossain et al., 2011; Tu et al., 2012).
3
1. Pyrolysis Process
oxygen limited conditions (Warnock et al., 2010). The pyrolysis process generates
three products: a liquid called bio-oil, syngas and one solid or biochar (Spokas et
al., 2009; Yoder et al., 2011). Syngas and bio-oil can be captured to generate
products of value instead of being emitted into the atmosphere, like a substitute for
Pyrolysis processes are classified into two major types, fast and slow, according to
the speed at which the biomass is altered. Fast pyrolysis, with a biomass residence
time of a few seconds, generates more bio-oil and less biochar than slow pyrolysis,
for which biomass residence times can range from hours to days (Woolf et al.,
the biochar yield (Peng et al., 2011). Slow pyrolysis minimizes the risk of producing
The process conditions for obtaining biochar influence its characteristics: slow
pyrolysis biochar properties tend to be similar, while fast pyrolysis biochar is more
heterogeneous (Smith et al., 2010). Depending on the type of pyrolysis and the
conditions under which it is carried out, such as low or high temperature, low or
high pressure, fast or slow speed, heating rate, particle size and biomass material,
the yields of each phase change noticeably (Spokas et al., 2009). Mahinpey et al.
(2009) examined the influence of pressure in the pyrolysis of wheat straw. The
4
experiments were performed at 10, 20, 30 and 40 psi. Reactor pressure had
Low temperature pyrolysis gives a material with more desirable soil improvement
performance of pyrolysis of rice straw (Xiao et al., 2010; Peng et al., 2011), pine
wood shavings, tall fescue grass (Keiluweit et al., 2010), wheat straw (Bruun et al.,
2011), wastewater sludge (Hossain et al., 2011) and Lemna minor (Muradov et al.,
2012) is shown in the Figure 2. For all biomass types used, with increasing
particles are difficult to stir up and process in the fluid bed, as they tend to settle to
the bottom of the bed where heat transfer and speed of thermal processing are
reduced (Lei et al., 2009). Generally, biochar is not a fully carbonized product
properties of biochar obtained from the fast pyrolysis of pitch pine, and reported
that biochar obtained at 400 and 500 °C was composed of a highly ordered
aromatic carbon structure. On the other hand, wastewater sludge biochar produced
5
Biochar is traditionally produced by burning wood in pits or temporary structures,
but a modern equipment pyrolysis reduces the air pollution related with this
practice. A portion of the gaseous product is burned to heat the pyrolysis chamber,
and the rest can provide heat or fuel for an electric generator (Tenenbaum, 2009);
also, the versatility of biochar technologies offers the potential for equitable
technology transfer and use in developing countries (Pratt & Moran, 2010).
very important to characterize their physical and chemical properties before use
(Yao et al., 2011; Uchimiya et al., 2010). Many biomass types have been used to
The sugar cane bagasse is the residue of sugar cane after the juice extraction.
the process; also, biochar is produced from undigested sugar cane bagasse (Yang,
2011). The biochar produced from digested residues had a higher pH, surface
6
more negative surface charge, compared with biochar of undigested sugar cane
digested cane bagasse may be efficiently used to improve soil quality, sequester
Biochar produced from corn stovers was characterized by two techniques: fast
pyrolysis at 450 °C and gasification at 700 °C. The results showed that biochar
obtained by fast pyrolysis, has a cation exchange capacity two times higher than
(Lee et al., 2010). Moreover, Chen et al. (2011) investigated the ability of biochar
produced from hardwood at 450°C and corn straw at 600 °C to adsorb Cu(II) and
presence of Cu(II) at concentrations above 1 mM. The results indicate that biochar
produced from agricultural residues may act as an effective adsorbent surface, but
care must be taken when using these adsorbents for the treatment of mixed waste
Peng et al. (2011) produced biochar from rice straw in a temperature range from
7
pyrolysis, decreased biochar yield and organic matter volatile, but increased the
The effectiveness of biochars produced from Eucalyptus spp. at 450 and 850 °C in
willow, pine and miscanthus and found that biochar amendments significantly
influenced seed germination and plant growth. Recently, biochar was obtained by
vapor-air mixture in a cyclone furnace to produce a tar-free liquid fuel (He et al.,
2012).
polyethylene, polypropylene and polystyrene with pine biomass and used tires.
They analyzed physico-chemical properties of chars obtained and reported that the
2.2 Algaes
Algal biomass has been studied as feedstock to produce biochar. The pyrolysis of
macroalgae can produce a range of chemicals and chars with various properties
8
(Ross et al., 2011). The study of pyrolysis of Fucus vesiculosus, Chorda filum,
reported that performance in the production of biochar is high and can be used in
the manufacturing of activated carbon or adsorbents (Ross et al., 2009; Ross et al.,
showing that seaweed biochar properties make it suitable for improving soil
conditions and as a tool to sequester carbon for a long time (Bird et al., 2011). In
slow pyrolysis of Tetraselmis chui, biochar was produced with a high cation
exchange capacity, high concentration of N, and a low C:N relation, which makes it
suitable as a soil remedial (Grierson et al., 2011). Grierson et al. (2009) have been
and 53% in the Chaetocerous muelleri under the same conditions. Algal biomass
pyrolysis at 350 °C and the product with the most biochar yield was characterized
by a high content of ash and carbon. Additionally, the nitrogen content makes it
suitable for use as a slow release source of nitrogen in the soil (Torri et al., 2011).
The composition of biochar from microalgaes has been studied. In pyrolysis of the
algaes Macrocystis pyrifera, Laminaria digitata and Fucus vesiculosus, biochar had
from sodium alginate presents swelling and mesoporosity while the biochar from
calcium alginate does not present this behavior. Different ranges of temperature
9
and pyrolysis conditions have been used. The macroalgaes Undaria pinnatifida,
Laminaria japonica and Porphyra tenera were pyrolysed between 300 and 600 °C
and the major production of biochar was at 300°C (Bae et al., 2011). The pyrolysis
microwaves (Du et al., 2011). The biochar yield by microalgaes is higher in fast
Broiler litter was used by Uchimiya et al. (2010) to produce biochar. Pyrolysis was
carried out at 350 and 700 °C and biochar was activated with steam for the
immobilization of ions Cd(II), Cu(II), Ni(II), Pb(II) in water and soil. In both cases,
of heavy metals. The adsorption capacity of biochar is closely related to the type of
that ion exchange becomes less dominant in the immobilization of heavy metals by
Cao et al. (2010) studied the ability of dairy-manure derived biochar to adsorb Pb
and the organic pollutant atrazine. Two samples of biochar were prepared at 200
and 350 °C and were compared with activated carbon and dry manure. Dairy
organic pollutants. This is an advantage since biochar from dairy manure can
10
remove both organic pollutants and heavy metals in one place, while biochar from
(2012) reported that the manure-derived biochar was rich in soil nutrients such as
N, P, Ca, Mg, and K. They suggested that the mesoporous manure-derived biochar
Song & Guo (2012) produced biochar from poultry litter and they suggested
The sludge generated in wastewater treatment, once dried, has been used in
production of bio-oil and biochar. The pyrolysis of sludge from sewage treatment
plants and domestic water was carried out by Zhang et al. (2011) in a horizontal
reactor placed in a quartz tube furnace at 600, 800 and 1000 °C. The pyrolysis of
digested sludge from a treatment plant for domestic wastewater was carried out in
a range from 300 to 700 °C and increasing temperature decreased the nitrogen
Chun et al. (2011) developed a pyrolysis gasifier, with carbonization and activation
steps to convert dried sludge into activated char and gas fuel energy. Dewatered
China was used to obtain biochar. Sewage sludge-derived char was successfully
11
Hossain et al. (2011) studied the influence of pyrolysis temperature on production
in the biochar.
3. Biochar applications
and absorbs agricultural chemicals (Kim et al., 2012). The discovering of small
plots of fertile land in Amazonia, enriched with biochar and known as terra petra,
compared with others soils in region, suggested the idea that biochar can be added
to soil in order to increase its fertility (Kasozi et al., 2010; Bailey et al., 2011).
Organic material is important to maintain the main functions of soil, like fertility,
2011). Because of its high carbon content, biochar is used to increase soil
retain moisture, enhancing its ability to attract beneficial fungi and microbes, and
improving cation exchange soil to retain nutrients (Zheng et al., 2010). Application
of biochar in soil increases cation exchange capacity up to 40% and its pH to a unit
(Hossain et al., 2010). Karhu et al. (2011) showed that the addition of biochar to
soil in southern Finland increased its water holding capacity by 11%. Biochar helps
retain phosphorus and potassium in the soil, improving the efficiency of fertilizer
12
use. However, fertilization with biochar initially can take nitrogen from external
sources because the carbon from biochar decomposition uses nitrogen in the soil
(Tenenbaum, 2009).
The leaching of nutrients from agricultural soils reduces their fertility, accelerates
their acidification, increases fertilizer costs for farmers, reduces crop yields, and
negatively affects the quality of surface water and groundwater. Laboratory results
leaching of nutrients (Laird et al., 2010). Fellet et al. (2011) studied the effects of
biochar application in mining waste and showed that the changes promoted by the
with the content of biochar in the substrates and the bioavailability of Cd, Pb, Tl
However, some inconveniences have been reported in the use of biochar as a soil
amendment. Nag et al. (2011) researched the effect of the use of biochar in
bioavailability and persistence in soil of atrazine and trifluraline. The biochar was
obtained from wheat straw at 450°C and annual ryegrass was used in the
13
3.2 CO2 capture
There is a great disequilibrium between carbon release into the atmosphere and
the adsorption of it; this promotes a continuous increase of carbon dioxide in the
anthropogenic carbon dioxide has increased by more than 3% yearly, and climate
gases coming from anthropogenic sources must keep themselves under a specific
limit, which indicates that in the future the net emissions of these gases must
approximate zero (Woolf et al., 2010). A list of seven options to mitigate climatic
change has been reported: capture and storing of carbon, energetic efficiency,
change to fuel containing low levels of carbon, nuclear energy, renewable energy,
increase of biological sinks and reduction of other greenhouse gases not only
carbon dioxide. Of these options, only the increasing of biological sinks and the
capture and storing of carbon from pyrolysis of biomass can reduce carbon dioxide
from the atmosphere (Matovic, 2011). The production of biochar has been
suggested as a viable way to capture and store atmospheric carbon dioxide (Woolf
et al., 2010; Vaccari et al., 2011; Roberts et al., 2010). The captured carbon
converts into a more stable substance (Steinbeiss et al., 2009). The characteristic
time of the storing of biochar carbon has been estimated from hundred to milliards
14
If 10% of net primary productivity of biomass in the world was converted to biochar
with a yield of 50%, and assuming 30% of required energy to carry out the process,
4.8 Gt of C could be sequestrated per year. That is approximately 20% more than
3.3 Sorbent
Biochar has an excellent capacity of adsorption because of its high surface area,
dangerous organic compounds (Cao et al., 2010; Keilluweit et al., 2010), including
aqueous solutions and because of its great surface area and its microporous
structure; it is an effective adsorbent of cationic and anionic dyes (Qiu et al., 2009).
shows surface area of biochar produced from miscanthus (Kwapinski et al., 2010),
rice straw (Xiao et al., 2010), broiler litter (Uchimiya et al., 2010; Uchimiya et al.,
2011), corn stover and switchgrass (Brewer et al., 2011), pine wood shavings and
tall fescue grass (Keiluweit et al., 2010), poultry litter (Song & Guo, 2012), pitch
pine (Kim et al., 2012) and Lemna minor (Muradov et al., 2012). It is notable that
15
Biochar produced from different biomass types has the capacity to adsorb
pesticides and others organic pollutants (Chen & Chen, 2009). Biochar obtained
from vegetal wastes can eliminate residues of pesticides like atrazine and simazine
in aquatic environments, reducing their pollution (Zheng et al., 2010). Chen & Yuan
(2011) evaluated the effect of pine biochar in soils polluted with polynuclear
soil emended with biochar. The mechanisms and the affinity of adsorption depend
soil.
The adsorption of catechol and humic acids in biochar from oak, pine and grass
has been studied. The equilibrium of catechol sorption was reached after 14 days
and was described by a kinetic diffusion model; while, humic acids required just a
day and followed a pseudo kinetic second order. The capacity of sorption of
catechol was higher at high temperatures (Kasozi et al., 2010). Biochar can be
used to adsorb organic compounds, and its capacity of sorption has been superior
aqueous solution, biochar derived from a fast pyrolysis system using rice-husk was
modified with acid and alkali and the surface area showed significant effects on
16
contaminated soils and the enhancement of adsorption of Pb(II) increased with the
Song et al. (2012) investigated the effects of wheat straw biochar on the sorption,
biochar was 42 times higher than that by soil. Biochar amendment of soil resulted
in a rapid reduction in the bioavailability of HCB, even for the 0.1% biochar
application rate, suggesting that wheat straw biochar could be used in immobilizing
from water by capturing ions of heavy metals, for example, biochar was six times
2010). Biochar from sugar beet wastes has been used to remove Cr(VI) from
aqueous solutions in function of pH, contact time and mass of biochar. The maxim
capacity of adsorption for Cr(VI) was 123 mg/g in acid media and the equilibrium
was reached at 16 hours (Dong et al., 2011). In another case, biochar from sugar
beet previously anaerobically digested was used to evaluate the capacity of the
3.4 Catalyst
sulfonation with concentrated sulfuric acid and fuming sulfuric acid. The catalyst
17
prepared with concentrated sulfuric acid was very active in esterification of fat
acids and conversion was increased with reaction time. Sulfonated biochar has
to reduce the fat acid contained in vegetal oils. Heterogeneous catalysts were
biochar catalysts showed a low capacity of being reused under high temperature
and pressure conditions (Yu et al., 2010). Sewage sludge-derived char has been
al., 2012). Lemna minor bio-char exhibited appreciable catalytic activity in biogas
reforming. The treatment of bio-char with CO 2 at 800 °C increased its surface area
Biochar can also be used as a fuel because of its heat value. Different biomass
types like willow, pine and miscanthus (Kwapinski et al., 2010), soft wood
(Schwaiger et al., 2011), rice straw (Xiao et al., 2010), algae of family Tetraselmis
chui (Grierson et al., 2011), Chlamydomonas reinhardtii (Torri et al., 2011) and
mixtures of plastic wastes and used tires (Bernardo et al., 2012) have been studied
notable that the heat value of biochar is similar to that of coal. Phan et al. (2008)
characterized the products of slow pyrolysis of municipal waste and reported that
18
biochar stores between 38 and 55% of the energy contained in raw material, while
Table 1 summarizes the published research about biochar, used biomass, pyrolysis
Conclusions
Research carried out about the production and application of biochar has found
that fast pyrolysis between 400 and 600°C increases biochar fraction in products;
adsorbent of metals and organic pollutants. The most used raw materials to obtain
biochar are from the lignocellulosic biomass group. The main application of biochar
has been in soil amendment and carbon sequestering, contributing in the reduction
the use of residual biomass, which would ordinarily be buried in landfills becoming
an environmental liability.
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Table 1. Biomass and method of production of biochar
Source of Method of
Application
Biomass production
Mixture of wood
Yu et al.,
waste, white wood, Fast pyrolysis Catalyst
2010
bark, and shavings
Pressurized
Mahinpey et
Wheat straw pyrolysis at Energy use
al., 2009
500°C
Fast pyrolysis
Application on acidic Bird et al.,
Algae from 307 to
soils 2011
512°C
Dong et al.,
Sugar beet tailing Pyrolysis at 300°C
Hexavalent chromium
2011 Yao et
30
removal al., 2011
Reducing
carbofuran in soil
Soil amendment,
Fast pyrolysis Bruun et al.,
Wheat straw atmospheric carbon
from 475 to 525°C 2011
sequestration.
Pinus ponderosa,
Pyrolysis from 100 Keiluweit et
Festuca Environmental sorbent
to 700 °C. al., 2010
arundinacea
Agricultural-use, carbon
Pyrolysis from 300 Song & Guo,
Poultry litter sequestration and
to 600 °C. 2012
environmental sorbent
31
80
60
Canola straw
Corn straw
Soybean straw
%Carbon
40
Peanut straw
Miscanthus
Switchgrass
Wheat straw
20 Sludge waste
Rice straw
0
200 250 300 350 400 450 500 550 600 650
Temperature (°C)
32
100
80 Sludge waste
Wheat straw
% Yield
40 Rice straw
Wastewater sludge
20 Lemna minor
0
200 300 400 500 600 700 800
Temperature (°C)
33
400
Miscanthus
Broiler litter
300
Rice straw
Corn stover
Surface area (m²/g)
200 Switchgrass
Pitch pine
Lemna minor
0
0 100 200 300 400 500 600 700 800 900
Pyrolysis Temperature (°C)
34
Figure 4. Heat value of biochar.
35