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Ep 10242
Ep 10242
Ep 10242
Waste Residues
Pascale Champagne
Department of Civil Engineering, Queen’s University, Kingston, ON K7L 3N6, Canada;
champagne@civil.queensu.ca (for correspondence)
Under the Kyoto Protocol, the Government of Can- tainable solid waste management strategy for a num-
ada has committed to reducing its greenhouse gas ber of livestock manure and other lignocellulosic
emissions by 6% from 1990 levels between 2008 and waste materials; contribute to the mitigation in green-
2012. Ethanol-blended gasolines have the potential to house gases through sustained carbon and nutrient
contribute significantly to these emission reductions. recycling; reduce the potential for water, air, and soil
Ethanol is derived from biologically renewable resour- contamination associated with land disposal of or-
ces and can be employed to replace octane enhancers ganic waste materials; and to broaden the feedstock
and aromatic hydrocarbons or oxygenates. To date, source of raw materials for the ethanol production
the ethanol production industry in Canada is com- industry. Ó 2007 American Institute of Chemical Engineers
prised mainly of small-scale plants producing ethanol Environ Prog, 27: 51–57, 2008
primarily from agricultural crops as feedstock. Keywords: bioethanol, manure, enzymatic hydroly-
Research interests in the area of bioethanol produc- sis, agricultural waste
tion from organic waste materials emerged in the late
1980. Significant advances in lignocellulosic material
extraction and enzymatic hydrolysis have been INTRODUCTION
reported in the last decade, however, continued Under the Kyoto Protocol, the Government of Can-
research efforts are essential for the development of ada has committed to reducing its greenhouse gas
technically feasible and economically viable large- emissions by 6% from 1990 levels between 2008 and
scale enzyme-based biomass-to-ethanol conversion 2012. Ethanol-blended gasolines have the potential to
processes. This research aims to develop and test an contribute significantly to these emissions reductions.
enzyme-based biomass-to-ethanol conversion process, Ethanol is an alternative fuel derived from biologically
which employs organic waste materials, such as live- renewable resources and can be employed to replace
stock manures, as alternative sources of cellulosic octane enhancers such as methylcyclopentadienyl
material feedstock. The source of the livestock ma- manganese tricarbonyl (MMT) and aromatic hydrocar-
nure, manure management practices and cellulose bons such as benzene or oxygenates such as methyl
extraction procedures have a significant impact on tertiary butyl ether (MTBE). A potential source for
the quantity and quality of the cellulosic materials low-cost ethanol production is to utilize lignocellulosic
derived. As such, raw feedstock materials must be materials (crop residues, grass, sawdust, woodchips,
carefully characterized to assess the impact of these sludges, livestock manure), but the feasibility of using
factors on the yield of bioethanol and residual end these materials as a feedstock is often limited by the
products. The success of cellulose-to-ethanol conver- cost of bioethanol production, which is relatively high
sion processes for cellulose extracted from these waste based on current technologies. The challenges are
materials as feedstock is generally a function of cellu- generally associated with the low yield and the high
lose fiber pretreatment, enzyme selection and operat- cost of the hydrolysis process. Research involving bio-
ing conditions. These will differ depending on the ethanol production from lignocellulosic waste materi-
source of the waste material feedstock. The long-term als have included crop residues [1–4], municipal solid
benefits of this research will be to introduce a sus- wastes [5–8], forest products wastes [9–11], leaf and
yard wastes [12], municipal sludges [13], as well as a
few studies involving dairy and cattle manures [14–16].
Ó 2007 American Institute of Chemical Engineers The current bioethanol production industry in Canada
from lignocellulosic materials is comprised of only a delignification to liberate cellulose and hemicellulose
few small-scale plants, producing ethanol mainly from from lignin. Second, depolymerization of the carbo-
agricultural crops as feedstock materials. Iogen Corpo- hydrate polymers (cellulose and hemicellulose) to
ration has developed a demonstration plant for the produce free sugars. Third, fermentation of mixed
conversion of wood, hay, straw and other agricultural hexose and pentose sugars to produce ethanol. In
crop residuals to ethanol. Other ethanol production addition, a preliminary step is often required when
plants currently in operation in Canada include: employing livestock manure and sludges as feedstock
Mohawk Oil Canada (wheat-based), Pound-Maker to obtain a better solids/liquid separation and to solu-
Agventures (wheat-based), Commercial Alcohols bilize and remove metals. Factors affecting the acid
(corn-based), API Grain Processors (wheat-based), and enzymatic hydrolysis of cellulose include poros-
and Tembec (forestry product-based). ity of the waste materials, cellulose fiber crystallinity,
In 1995, Dinel and Dumontet [17] introduced a and lignin and hemicellulose content. Hydrolysis can
concept of sustainable waste management termed Bi- be significantly enhanced by introducing physical and
ological and Chemical Integrated Recycling System. chemical fiber pretreatments including: grinding, py-
They proposed a series of possible extraction and rolysis, steam explosion, ammonia fiber explosion
fractionation procedures which would allow for the (AFEX), CO2 explosion, ozonolysis, acid hydrolysis,
recovery of a number of value-added products, alkaline hydrolysis, oxidative delignification, Organo-
including cellulose, from various lignocellulosic waste solv process involving extraction with hot aqueous
streams (see Figure 1). Livestock manures and ethanol and biological pretreatment of the lignocellu-
sludges contain large quantities of lignocelluloses, losic materials to remove lignin and hemicellulose
polysaccharides, proteins and other organic materials. and reduce fiber crystallinity. Enzymatic hydrolysis
The conversion of these materials to value-added can be improved through the optimization of sub-
products has been recognized as an attractive waste strate concentration, cellulase dosing, use of surfac-
management approach. In addition, the recovery of tants, enzyme mixtures, and enzyme recycling. Simul-
raw materials from organic wastes such as manures taneous saccharification and fermentation (SSF) is an
and sludges, and their conversion to value-added effective process configuration which removes glu-
products has the potential to reduce the microbial cose, an inhibitor to cellulase activity, thereby increas-
production of CO2 and CH4, thereby minimizing ing the yield and rate of cellulose hydrolysis [18].
potential environmental impacts and the strain on
nonrenewable resource reserves. However as feed-
stocks, organic wastes often have a complex physical DELIGNIFICATION OF AGRICULTURAL WASTE MATERIALS
and chemical composition which has made it difficult Rivers and Emert [3] studied the effects of substrate
to utilize, and the limited research efforts to convert composition, cellulose crystallinity, and particle size
these materials to higher-value chemicals and energy on the yields of enzymatic hydrolysis using bagasse
on a commercial scale have been unsuccessful [14]. and rice straw. They concluded that each type of
Bioethanol production utilizing lignocellulosic lignocellulosic feedstock requires a specific pretreat-
materials generally takes place in three phases. First, ment in order to optimize enzymatic hydrolysis. The
ture of substrate became more accessible to the the glucose yield reached 54.2% and 37.0% for wet
enzyme due to the drying. The highest glucose yield and dry substrates, respectively, which supported the
was noted for KOH-treated and ground poultry ma- value of acid and alkaline pretreatments for effective
nure. With a conversion of 27.6, this represented a glucose conversion from enzymatic hydrolysis. More-
twofold increase in yield compared to that of over, the results implied that considerable cellulose is
unground manure. These results suggested that by contained in the primary sludge on a dry mass basis,
grinding the poultry manure, the substances that cov- and cellulosic material recovery and conversion to
ered the cellulose were broken up, thus, exposing ethanol might present a valuable waste management
the surface of the cellulose. In addition, reducing the alternative when employed as a wet feedstock. This
particle size of the substrate also created a larger sur- is contrary to what was noted with poultry manure,
face area for reaction. Thus, the substrate became which demonstrated a higher glucose conversion
much more accessible to the enzyme. As a result, the when dry substrate was used. This might indicate that
glucose yield increased significantly. the cellulose in primary sludge was more readily ac-
The cellulose content in primary sludge is mainly cessible to the enzymes and that drying and grinding
from waste paper, however, the cellulosis fraction might not be required to improve the enzymatic hy-
must be separated from the noncellulosic compo- drolysis as it was using with poultry manure.
nents prior to the enzymatic hydrolysis to maximize
glucose yield [23, 24]. Pretreatment approaches for CONCLUSIONS
primary sludge include KOH, HCl, and HCl followed Preliminary research using organic waste materials
by KOH alkaline delignification (see Figure 6). Figure as lignocellulosic feedstock for ethanol production
7 presents the glucose yields from primary sludge fol- has shown great promise to date, however, further
lowing various feedstock material and fiber pretreat- research is essential to investigate its application
ments. Both wet and dry substrates were tested for beyond the laboratory-scale. For instance, cellulose
each of them. All the trials were conducted at 408C extraction procedures and fiber pretreatments should
for a period of 24 h. Results indicated that when be optimized as a function of feedstock to maximize
KOH pretreatment was performed on primary sludge, the enzymatic hydrolysis and fermentation processes.
the conversion for wet substrate increased from Enzyme recycling and the use of simultaneous sac-
31.1% to 35.4%, which represented a 4.3% increase in charification and fermentation to integrate the ethanol
glucose yield. However, compared to that of crop production process and achieve higher reaction rates
residues, which achieved an almost ten-fold increase at lower costs would also be beneficial to the devel-
in the conversion percentages, the KOH pretreatment opment of this waste management strategy.
was not as effective on the primary sludge. Similarly,
when the primary sludge was treated with HCl, the FUTURE RESEARCH NEEDS AND ANTICIPATED
glucose yield increased to 42.6% for wet substrate, SIGNIFICANCE OF RESEARCH
which was 11.5% higher than that observed without The research will result in the development of an
acid and alkaline treatment. This suggested that innovative waste management approach that uses ag-
through HCl pretreatment, which would remove met- ricultural waste materials as a renewable resource for
als, enzyme inhibition due to metals may have been the extraction of a value-added product, cellulose,
reduced, resulting in a higher glucose yield from the and its conversion to bioethanol. This alternative
enzymatic hydrolysis. When both acid and alkaline strategy would be of great benefit to the agricultural
pretreatments were performed on the primary sludge, industry where traditional manure management prac-