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Faculty of Agricultural and Environmental Sciences, Macdonald Campus of McGill University, 21 111 Lakeshore, Ste Anne de Bellevue,
Quebec H9X 3V9, Canada
b
Department of Civil Engineering and Applied Mechanics, Macdonald Engineering Building, 817 Sherbrooke Street W., Montreal,
Quebec H3A 2K6, Canada
article info
The cement industry produces about 5% of the global anthropogenic carbon dioxide (CO2)
Article history:
emissions. Global demand for cement is forecast to grow by 4.7% annually, which will
increase CO2 emissions. One way to mitigate the CO2 generated during cement
20 September 2011
combustion of organic residues, with Portland cement. Biocement requires less energy
intensive clinker, with its related carbon emission, to produce a good cementing agent.
Small scale biocement production in tropical areas has shown that blending cement with
bio-silica can have environmental, economic and technical benefits. It is also found that
a number of crops grown in temperate regions of Canada with high silicon concentration
and calorific content have the potential to make biocement. In addition, the combustion
process can be integrated into energy production to simultaneously gain the energy and
the bio-silica ash. The results indicated that switchgrass, barley, oat and sunflower
produce silicon-rich residues and could be good candidates to consider for both energy and
biocement production in Canada.
2011 IAgrE. Published by Elsevier Ltd. All rights reserved.
1.
Introduction
emissions of carbon dioxide, the main cause of global warming (Worrell et al., 2001).
There are three strategies to reduce CO2 emissions from
the cement industry: (1) improve energy efficiency, thus use
less fossil fuel, (2) replace fossil fuel with renewable energy
sources such as biofuel and other biomass feedstocks, and (3)
substitute part of Portland cement with other cementitious
materials such as bio-silica (Initiative, 2005). The third option
is the main focus of this paper.
Typical raw materials in cement production are limestone
or chalk (CaCO3), sand (SiO2), clay (SiO2, Al2O3, and Fe2O3), iron
ore (Fe2O3), and gypsum (CaSO4). Limestone and clay are
* Corresponding author. Tel.: 1 514 398 7943; fax: 1 514 398 7990.
E-mail address: joann.whalen@mcgill.ca (J.K. Whalen).
1537-5110/$ e see front matter 2011 IAgrE. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.biosystemseng.2011.09.010
352
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
Nomenclature
CCA
PMSA
RHA
RSA
SCBA
SCSA
2.
OPA
SDA
BLA
SSA
VGA
WSA
353
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
Table 1 e Chemical composition of ash produced from organic residues following combustion at the specified temperature
and duration. Values for Portland cement are included for reference.
Organic
residue
Loss on
Combustion Combustion
time, h
ignition, % temperature, C
Sawdust
67.20
4.09
2.26
9.98
5.80
0.08
0.11
4.67
NDa
ND
Paper mill
sludge
Rice husk
25.70
18.86
0.87
43.51
5.15
1.56
1.31
ND
ND
ND
93.2
0.4
0.1
1.1
0.1
0.1
1.3
3.7
650
ND
Vetiver grass
57.48
3.73
1.71
5.45
1.24
0.12
15.49
11.76
900
Corn cob
66.38
7.48
4.44
11.57
2.06
0.41
4.92
1.30e1.47
650
Sugar cane
straw
Oil palm shell
59.06
4.75
3.18
19.59
2.25
0.73
4.75
2.05
800
63.6
1.6
1.4
7.6
3.9
0.1
6.9
9.6
ND
ND
54.24
75.90
50.6
22.0
4.55
4.13
12.8
6.0
1.05
1.22
7.21
3.0
12.54
7.47
1.93
65.0
2.39
1.85
1.48
1.0
ND
0.21
0.32
0.2
ND
5.62
1.70
0.8
7.22
ND
ND
1.29
670
600
700
1400
5
2
3
e
Wheat straw
Bamboo leaf
Sewage sludge
Portland
cement
Reference
Elinwa and Mahmood
(2002)
Mozaffari et al. (2006)
Chindaprasirt et al.
(2008)
Nimityongskul et al.
(2003)
Adesanya and Raheem
(2009a)
Martirena Hernandez
et al. (1998)
Chindaprasirt et al.
(2008)
Biricik et al. (2000)
Dwivedi et al. (2006)
Pan et al. (2003)
Nimityongskul et al.
(2003)
a ND, no data.
3.
Bio-silica and energy potential from
combustion of plant by-products
3.1.
354
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
Table 2 e Compressive strength of mortar containing organic residues. Values for 0% ash were included for reference.
Organic
residue
Ash
content, %
Age
days
Compressive
strength, MPa
Compressive strength
with 0% ash, MPa
Reference
Sawdust
Paper mill sludge
Rice husk
Vetiver grass
Corn cob
Sugar cane
10
10
20
20
8
10
28
28
28
28
28
28
18.1
62
58.5e103
55.1
20e36
42.1
23.1
58
57.0e100
68
21e44
36.1
20
6
20
15
28
28
3
28
57.5e102
29
62
47
57.0e100
26
70
41
improve soil quality, bedding for livestock, as fuel, and for the
manufacture of particleboard. Canada is the second largest
producer of sawmill products (boards, dimension lumber,
timber, poles, and ties from logs) in the world. In 2009, Canada
processed an estimated 32 106 m3 of sawn wood (Food and
Agriculture Organization of the United Nations, 2011).
Sawdust can be used in biocement manufacturing, both as
a fuel and as cement replacement material. Recent studies on
the use of sawdust ash (SDA) for biocement production have
shown that it is cost effective and offers a large potential
market for SDA (Sumaila & Job, 1999; Udoeyo & Dashibil, 2002).
Yet most studies have focused on sawdust as a fuel due to its
high calorific value and there has been limited investigation of
the pozzolanic properties of SDA and its viability as a cement
replacement. Elinwa and Mahmood (2002) reported that SDA
was a silicon-rich residue (67.2% SiO2) with appreciable
quantities of Al2O3 and Fe2O3 (Table 1). They obtained SDA by
open burning and grinding, then mixed the SDA powder with
Portland cement in various ratios (by weight), ranging from 0%
SDA:100% Portland cement to 30% SDA: 70% Portland cement.
With an increasing ratio of SDA: Portland cement, the average
consistency of the paste increased. In another study, a blend
of 10% SDA: 90% Portland cement showed good performance,
3.2.
Paper mill sludge is the residue left over from the paper
recycling process and is of interest for biocement production
because it contains vegetable fibres. It is used as a soil
conditioning agent, and as a bulking agent in compost and
fuel. The pulp and paper industry is one of the most important
industries in North America, ranking fifth largest in the U.S.
economy (Nemerow & Dasgupta, 1991). Each Canadian pulp
mill produces an average 40 t (oven-dry) of sludge per day
(Clean Air Clean Water Pulp Info Centre, 2010), which can be
used both as fuel and in biocement. Paper mill sludge has
a high content of cellulose fibres and a gross calorific value of
about 15e18 MJ kg1, making it a good biofuel (Table 3). It also
contains calcium carbonate, china clay, and residue chemicals that could promote the pozzolanic reaction. The
Table 3 e Energy obtained upon combustion of organic residues at the corresponding moisture content.
Organic
residue
Calorific
valuea
MJ kg1
Type
Moisture, %
Reference
Sawdust
Paper mill
sludge
Rice husk
Vetiver grass
Corn cob
Sugar cane
Oil palm shell
Wheat straw
Sewage sludge
Fossil fuel (coal)
17e18
14.7e17.6
ND
Gross
ND
Dry
14.7
16.3
17
17.6
17.5
17
17.5
15-27
ND
ND
ND
Gross
Gross
ND
ND
Dry
Dry
Dry
Dry
10
Dry
ND
Dry
a The calorific value is the energy content, or heat value, released when the organic residue is burnt in air.
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
3.3.
355
3.4.
Vetiver grass is a perennial grass cultivated widely in the tropical regions of the world. It is used for soil and water conservation and medicine production. Nimityongskul, Panichnava, and
Hengsadeekul (2003) investigated the potential of using vetiver
grass ash (VGA) as an additive in cement. Dried vetiver grass was
combusted in a ferrocement incinerator at 900 C. Vetiver grass
is self-burning and it does not need extra fuel after the igniting
stage. Because VGA proved to have pozzolanic properties, it was
blended with Portland cement in the proportions of 20, 40
and 60%, by mass. Biocement made with VGA considerably
improved mortar resistance against acid attack, probably
because calcium hydroxide reacts with the silica in VGA to form
CeSeH gel. The coefficient of water permeability increased as
the amount of VGA in the mixture increased. Moreover, VGAPortland cement mortar had better resistance to water permeability than cement from Portland cement alone (Nimityongskul
et al., 2003).
3.5.
356
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
3.6.
Sugar cane straw and bagasse are the wastes from sugar and
alcohol factories and are often recycled as fuel for heat
generation and vaporisation in these factories. Sugar cane is
used as animal feed, fertiliser, alcohol production and bioplastic. Brazil is the leading producer of sugarcane worldwide (Food and Agriculture Organization of the United
Nations, 2011). Sugar cane waste is a potential fuel with
a gross calorific value of 17 MJ kg1 when dry (Table 3). Wet
zdemr,
waste has a lower calorific content (Kilicaslan, Sarac, O
& Erm, 1999). To date, no information could be found
describing the simultaneous use of sugarcane by-products as
biofuel and cement replacement material.
Frias, Villar-Cocina, and Valencia-Morales (2007) calcined
sugar cane straw and bagasse residues at 800 and 1000 C.
They designated the resultant sugar cane straw ash (SCSA)
and sugar cane bagasse ash (SCBA) as potential cement
replacement materials because of their high content of
amorphous silica and associated pozzolanic activity. The
maximum activation was reached by calcined at 800 C. The
pozzolanic activity of SCBA increased with smaller particle
size, improving the performance and compressive strength of
3.7.
3.8.
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
3.9.
4.
Sewage sludge is an organic residue generated by municipalities following secondary and tertiary treatment of wastewater streams. It is used as a soil amendment and fertiliser to
improve the yield of selected crops, as well as a fuel in
co-combustion with other fuels or types of waste. Sewage
Type
Si-accumulator Intermediate Si-excluder
Si content (%)
Si/Ca ratio
Degree of Si
accumulation
>1.0
>1.0
0.5e1
0.5e1
<0.5
<0.5
e
357
358
Table 5 e Silicon accumulator plants adapted to temperate and cold temperate regions of North America. Production values (yield and organic residues) are from Canada
only.
No.
Species
Common
name
Switchgrass
Perennial
ND
Chalky bluestem
Red fescue
Rice cutgrass
Clavate bent
Mannagrass
Chinese silver
grass
ND
Ryegrass
Annual
ND
Perennial
Perennial
Annual
Perennial
Perennial
Annual
Perennial
Annual Canadian
organic residue
production, kt
Used
as fuel
Used as
raw material
for cement
No
0.52e
0.50e
0.53e
0.27e
0.27f
0.39e
0.34g
2582.9
9517.2
9392.9
275.5
758.4
41471.5
1805.5
Fuel alcohol
Fuel alcohol
Fuel alcohol
Oil fuel
Fuel alcohol
Fuel alcohol
Fuel pellet
No
No
Yesc
No
No
Yesd
No
Wide range
ND
ND
ND
Fuel pellet
No
Temperate
Temperate
Temperate
Cold temperate
Cold temperate
Temperate
Cold temperate
Temperate
Temperate
Cold temperate
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
No
No
No
No
No
No
Biomass fuel
No
No
No
No
No
No
No
No
No
No
No
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
a
b
c
d
e
f
g
No
2.16
1.48
1.40
1.20
6.97
2.53
2.96
3.20
2.11
1.15
Annual
Annual
Annual
Annual
Annual
Annual
Annual
Aegilops squarrosa
Lolium perenne
ND
Temperate
Temperate
Cold temperate
Cold temperate
Temperate
Temperate
Wide range
Cold temperate
Cold temperate
Temperate
Oat
Barley
Corn
Sunflower
Rye
Bread wheat
Flax
16
17
NDb
4.40
4.20
ND
2.08
1.53e2.71
1.23
1.38
1.04
1.44
High silica
in ash shives
1.79
Annual
plants
Panicum bisulcatum
Andropogon virgincus
Festuca rubra
Leersia oryzoides
Agrostis clavata
Glyceria acutiflora
Miscanthus sinensis
Climate
Wild rice
Native
9
10
11
12
13
14
15
Harvest
Index
Average Si
content, %
Cultivated plants
1
Zizania latifolia
Zizania aquatic
Zizania palustris
2
Avena sativa
3
Hordeum vulgare
Zea mays
4
Helianthus annuus
5
Secale cereal
6
Triticum aestivum
7
Linum usitatissimum
Panicum virgatum
Annual Canadian
production, a kt
Life
cycle
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
5.
Canadian plants with potential for
biocement production
A variety of plant residues contain sufficient Si to generate
amorphous bio-silica for biocement production. Much of the
research to date has focused on crops grown in the tropics and
sub-tropics. In those areas, the plant residue is incinerated,
then the ash is blended with conventional cement, effectively
replacing up to 40% of the Portland cement in the mixture.
Concrete strength, durability and resistance to acidity/
humidity were generally optimal in blended cement with
10e20% ash from organic residues. Due care is needed in the
combustion process to ensure the maximum ash recovery, and
pozzolanic content of at least 70% of SiO2, Al2O3 and Fe2O3 in an
amorphous form. Additionally, grinding the ash can optimise
pozzolanic reaction. These considerations could be helpful as
a starting point in generating bio-silica from temperate plant
species and subsequently producing biocement.
The challenge ahead is to adapt practices that work in the
tropics/sub-tropics to the Canadian context, and to optimise the
efficiency of the biocement production process. One major gap
in the research is how to utilise the calorific value of organic
residues in the preparation of bio-silica for biocement. The best
scenario is that organic residues are first used as biofuel in an
industry process and the remaining ash is then collected for
further processing and incorporation into biocement. The key
parameter is the combustion temperature in this secondary
process. When organic residues are used as bio-fuels, ash is
produced by self-combustion, but the combustion temperature
might not be high enough to oxidise silicon sufficiently into
amorphous bio-silica with the desired pozzolanic reactivity.
Therefore, heat treatment of organic residue ash is necessary.
The energy required in this process is much lower than in
clinker production. If successful, the entire process produces
zero waste and emits much less CO2. Organic residues are utilised to their greatest potential when exploited for both energy
production and biocement production. The following discussion considers both aspects in selection of Canadian plants.
Selecting Canadian plants with a potential for biocement
production is a necessary first step. To produce bio-silica from
plant residues, it would be best to first select silicon accumulator species, and then devise methods to increase their Si
content by increasing plant transpiration and the Si content of
soil. The silicon content of soil can be increased by application
of silicate fertiliser (Jones & Handreck, 1967).
Silicon-accumulating plants can be discriminated from
non-accumulating plants by the Si content and the Si/Ca
ratio (Ma & Takahashi, 2002). Based on these physiological
relationships, we categorised plants according to their
potential to acquire Si, as silicon accumulators, intermediate, or silicon excluders, using the criteria stated in
Table 4. Plant species with Si content > 1% and Si/Ca
ratio > 1 were selected, as they warrant further investigation regarding their use for biocement production in Canada. Although most Si-accumulating plants grow in tropical
regions (e.g., rice), a few plants adapted to temperate and
cold temperate regions are Si accumulators (Table 5).
Among the 17 plant species listed in Table 5 are cultivated
and non-cultivated (indigenous) species that grow well in
359
6.
360
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
are large and would generate substantial quantities of residues; (2) agricultural producers often leave crop residues in
the field to conserve soil organic matter and prevent soil
erosion, thus would need economic incentives to collect
part or all of their residues and transport it to a processing
facility for biocement production and energy generation; and
(3) technical specifications are lacking regarding the optimal
conditions for combustion of temperate plant residues to
generate amorphous silica and energy. Consequently, the
Canadian cement industry does not have sufficient information to judge the potential of biocement as an alternative to
conventional cement production.
We identified switchgrass, barley, oat and sunflower as
plants that have the potential to simultaneously generate
energy and produce bio-silica for biocement, and therefore
would be the best candidates for further research in Canada.
The technical feasibility of the process and resulting biocement still needs to be fully evaluated.
This review serves as a case study for other temperate
regions. Since the availability of crop residues suitable for biocement is controlled by environment (adapted cultivars, climate
and soil conditions) and economic factors (i.e., farmers decisions based on crop market prices), knowledge of crop acreages
is helpful. A survey of the Si content and calorific value of the
major crops and native plant species is an important first step in
developing a local research program for biocement.
Acknowledgements
Thank you to Hollie Johnson for proof-reading and editorial
correction, and to two anonymous reviewers for helpful
comments. Research was supported by the National Science
and Engineering Research Council (Canada).
references
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2
361
362
b i o s y s t e m s e n g i n e e r i n g 1 1 0 ( 2 0 1 1 ) 3 5 1 e3 6 2