Category Archives: BIOMASS NOW — SUSTAINABLE GROWTH AND USE

Bioethanol from lignocellulosic biomass — Malaysia perspective

Malaysia formulated the National Biofuel Policy with envisions to put the biofuel as one of the five energy sources for Malaysia, enhancing the nation’s prosperity and well being. This is in line with nation’s Five-Fuel Diversification Policy, a national policy to promote renewable energy (RE) as the fifth fuel along with fossil fuels and hydropower. The National Biofuel Policy was implemented in March 2006 to encourage the production of Biofuels, particularly biodiesel from palm oil, for local use and for export. However, in 2007, the Government has announced that the implementation of the whole biodiesel project has been put on hold indefinitely owing to the current high price of refined, bleached and deodorized palm olein.

Recently, the Government of Malaysia launched new strategy to promote the biofuel through the National Biomass Strategy 2020 on year 2011. The aim of National Biomass

Strategy 2020 is to create higher value-added biomass economic activities that contribute towards Malaysia’s gross national income (GNI) and creating high value jobs for the benefit of Malaysians. This Strategy outline the production of bioethanol produced from lignocellulosic biomass particularly the oil palm biomass as a starting point with extended to include biomass from other sources such as wood waste. The palm oil sector correspondingly generates the largest amount of biomass, around 80 million dry tonnes in 2010. This is expected to increase to about 100 million dry tonnes by 2020, primarily driven by increases in plantation area. A conservative estimation of utilising an addition 20 million tonnes of oil palm biomass for bioethanol has the potential to contribute significantly to the nation’s economy while at the same time reduce the green house gasses emission.

The National Biomass Strategy 2020 proposes a mandate of bioethanol blending of 10 percent in petrol fuel in Malaysia by 2020 to cut down the green house gasses emissions. This would generate a domestic demand for one million tonnes of bioethanol per annum with the first bioethanol from lignocellulosic biomass plant is expected to be commercially viable between 2013 and 2015 [34]. As a result, much attention has been focuses on generating bioethanol from oil palm biomass and wood waste.

As mentioned early, bioethanol utilization as automobile fuel is especially promising as the United States, Brazil and Europe has introduced. However, low-cost supply associated with high bioethanol yield of the bioethanol is indispensable for its wide use. The discussion of economic feasibility of bioethanol production from lignocellulosic biomass in Malaysia in this paper was based on the experimental data through laboratory worked done by [35] and [36] and comparison was made with sugarcane and corn.

Biomass Extraction Methods

Adina-Elena Segneanu, Florentina Sziple, Paulina Vlazan, Paula Sfarloaga, Iaon Grozesku and Vasile Daniel Gherman

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/55338

1. Introduction

Biomass represents an extremely valuable potential to obtain new clean energy sources and natural structurally complex bioactive compounds. Renewable energy can be produced from any biological feedstock, that contains appreciable amounts of sugar or materials that can be converted into sugar (e. g. starch or cellulose). Lignocellulose’s biomass-dendromass and phytomass is natural based material consisting of complex of heterogenic macromolecules with cell structure (celluloses, hemicelluloses and lignin) as well as numerous organic and inorganic structures with low molecule weight (Sun, 2002).

Long-term economic and environmental concerns have resulted in a great amount of research in the past couple of decades on renewable sources of liquid fuels to replace fossil fuels. Producing of cellulose and alcohol from biomass is important technological process. Conversion of abundant lignocellulosic biomass to biofuels as transportation fuels presents a viable option for improving energy security and reducing greenhouse emissions. Lignocellulosic materials such as agricultural residues (e. g., wheat straw, sugarcane bagasse, corn stover), forest products (hardwood and softwood), and dedicated crops (switchgrass, salix) are renewable sources of energy. These raw materials are sufficiently abundant and generate very low net greenhouse emissions. The use of biomass with low economic value, the waste from agriculture, forestry and wild flora as sources of clean energy, is a viable way to avoid potential conflicts with the biomass production for food, which represent the main concern of UE regarding the biofuels production from biomass.

The presence of lignin in lignocelluloses leads to a protective barrier that prevents plant cell destruction by fungi and bacteria for conversion to fuel. For the conversion of biomass to fuel, the cellulose and hemicellulose must be broken. The digestibility of cellulose present in lignocellulosic biomass is hindered by many physicochemical, structural, and compositional factors. The lignocellulosic biomasses need to be treated prior to fuel production to expose

© 2013 Segneanu et al., licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons. org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

cellulose. In present, there is many different type of pretreatment of lignocelluloses materials. Pretreatment uses various techniques, including ammonia fiber explosion, chemical treatment, biological treatment, and steam explosion, to alter the structure of cellulosic biomass to make cellulose more accessible. The purpose of the pretreatment is to remove lignin and hemicellulose, reduce cellulose crystallinity, and increase the porosity of the materials. Then, acids or enzymes can be used to break down the cellulose into its constituent sugars. Enzyme hydrolysis is widely used to break down cellulose into its constituent sugars. Pretreatment can be the most expensive process in biomass-to-fuels conversion but it has great potential for improvements in efficiency and lowering of costs through further research and development. Cellulose chains can also be broken down into individual glucose sugar molecules by enzymes known as cellulose. Cellulose refers to a class of enzymes produced by fungi, bacteria, and protozoans that catalyze the hydrolysis of cellulose. But, one of the main drawn back of convention chemical methods used in ethanol formation process is degradation of carbohydrates and formation of undesirable by­products, which severely inhibition of ethanol during the fermentation process: furfural, 5- hydroxymethylfurfural, uronic acid, levulinic acid, acetic acid, formic acid, hydroxybenzoic acid, vanillin, phenol, cinnamaldehyde, formaldehyde, and so (Nenkova et. al., 2011). Some inhibitors such as terpene compounds are present in the biomass-dendromass.

Lignin is a complex reticulated phenolic polymer that occurs in xylem of most terrestrial plants and is the second most abundant biopolymer in nature, corresponding to around 30% of the biosphere organic carbon. This macromolecule is one of the biggest wood components and also one of the most important. Even the lignin has a significant role in technology, in the bioethanol production process valuable chemical properties and functions from lignin and hemicelluloses are not fully recovery, the black liquor result from process being using specially for energy recovery. About half of wood components are dissolved into this black liquor. The dissolved organic compounds consist mainly in degraded lignin and also hemicelluloses and cellulose degradation products. Also, phenols derived from biomass are valuable and useful chemicals, due to their pharmacological properties including antiviral inhibitor (anti-HIV). These compounds with good antioxidant activity can be used to preserve food from lipid peroxidation and oxidative damage occurring in living systems (Martinez et. al., 1996; Mahugo Santana et. al., 2009; Nenkova, et. al.2011). Antioxidants can also prevent the loss of food color, flavor and active vitamins content, providing the stabilization of the molecules involved in such characteristics. They can also be used for the production of adhesives and for the synthesis of polymer.

It is well known that, biomass also contains many other natural products: waxes and fatty acids, polyacetylenes, terpenoids (e. g., monoterpenoids, iridoids, sesquiterpenoids, diterpenoids, triterpenoids), steroids, essential oils, phenolics, flavonoids, tannins, anthocyanins, quinones, coumarins, lignans, alkaloids, and glycosidic derivatives (e. g., saponins, glycosides, flavonoid glycosides) (Alonso et. al., 1998; Japon-Lujan et. al., 2006; Faustino, 2010; Fang et. al., 2009; Gallo, 2010; Carro, 1997; Kojima, 2004). In this regards, are needed more studies to recover these important compounds from biomass for use in pharmaceutical industry, food industry, and so.

Genetic improvement of willow for phytoremediation

to pathogens. However, in the context of phytoremediation, the ideal willow genotype must also: i) be adapted to specific pedo-climatic conditions; ii) be fast growing; ii) produce a large root biomass; iv) be resistant to a variety of contaminants; v) have a high concentration factor of contaminants; vi) be easy to establish, maintain and collect. The exceptional diversity of the genus Salix makes it an ideal candidate for breeding programs seeking to develop cultivars more efficient at phytoremediation.

To our knowledge, one of the rare efforts to understand the genetic and genomic bases underlying the potential of willow for phytoremediation is the three-year Genorem project (www. genorem. ca) launched by research teams at the Universite de Montreal and McGill University (Project Leaders Dr. B. Franz Lang and Dr. Mohamed Hijri, both of the Universite de Montreal) and involving over thirty scientists, students and staff. The project integrates traditional field and molecular biology experiments, employing recently developed life science technologies: genomics, proteomics, metabolomics and bioinformatics. GenoRem’s objectives include the development of guidelines for phytoremediation procedures respectful of the environment that will ultimately be useful to both government and corporate sectors. The transcriptomes of 11 willow genotypes will be sequenced, resulting in basic molecular information about the genes activated in willow when in presence of soil contaminants. GenoRem will also investigate the close relationship established between the willow cultivars studied and the associated soil microorganisms. Ultimately, project results will provide willow breeders with gene markers linked with increased phytoremediation potential.

Phytoremediation as a decontamination technology can be applied to large surface areas, causes less environmental disturbances and represents a significantly cheaper approach than traditional methods. However, treatment is lengthy (several years), and the methodologies appropriate for each type of contamination require refinement. While the biomass produced in the context of a phytoremediation project may potentially be contaminated, this does not affect its utilization as a product outside the food chain. Moreover, the highly concentrated ashes resulting from conversion of the biomass to fuel facilitate disposal and treatment of the contaminant, particularly for a large, diluted volume of contaminated soil. Hence the decontamination by means of phytoremediation is a less intensive technique.

4. Conclusions

Eastern Canada is one region where willow short-rotation coppice has been the focus of numerous research projects over the last 15-20 years. Most experimental data published during this period concerning Quebec have found a high biomass potential, due to a combination of several factors, including the very high biomass yield of certain willow varieties, favourable pedoclimatic conditions and the very low incidence of severe pests and diseases. These high biomass yields have encouraged some growers to choose willows as an alternative agricultural crop, leading to a dramatic expansion of land devoted to willow short-rotation coppice in the province, especially over the last five years. However, the future evolution of this crop’s production will most certainly be influenced by the development of an active market for such biomass, which would encourage farmers to grow willow over a much larger surface area. In particular, developments in the technology of feedstock transformation and marketing issues related to product potential both merit further study. The high potential of willow for bioenergy production and environmental applications, including phytoremediation, in the Quebec context has been clearly demonstrated.

Author details

Werther Guidi, Frederic E. Pitre and Michel Labrecque

Institut de Recherche en Biologie Vegetale (1RBV — Plant Biology Research Institute) — Universite de Montreal — The Montreal Botanical Garden, Montreal, Canada

Growing systems & population dynamics

Given the huge range in size, growth form and coppice ability in the willow genus, production systems for willow may vary from single-stemmed systems with less than 500 trees ha-1 and a rotation period of over 20 years, to systems which contain over 4*104 plants plant which generate over half a million shoots ha-1 in a one-year coppice cycle. In the remainder of this chapter, we focus on growing systems which are generated from cuttings, at a planting density of 1*104 to 1.5 *104 cuttings ha-1, and treated as a coppice system, undergoing multiple cutting cycles. In Scandinavian conditions, one season may be too short to replenish carbohydrate reserves in willow stubs after harvest, and a one-year harvest cycle may deplete a plantation and compromise its viability [21]. Cutting cycle lengths in Swedish practice have been 3 to 5 years, and with the introduction of faster growing clones, cutting cycle lengths now are being decreased to 2 to 4 years. In commercial practice, a double row system is employed (Figure 1). However, Bergkvist and Ledin [22] showed that planting design could be adjusted, within certain limits without losing yield potential, to the requirements of tractors and machines used in managing the Salix stand.

Figure 1. Machine planting of willow by means of a Woodpecker 601, using long rods and planting three double rows at a time (Photo: Nils-Erik Nordh).

The development of a population of willow stems is constrained by competitive interactions which lead to self-thinning, yield-density effects and to skewed size-frequency distributions of stems [23, 24]. Those effects of competitive interactions need to be accounted for when determining optimal plant spacing and harvest frequency. Especially in dense willow coppice, not only shoot mortality but also extensive stool mortality may occur [25], thereby leading to lasting gaps and production losses [26]. Studies on the long term dynamics of willow coppice have shown that an initial variability in plant size becomes enlarged over time, that self-thinning leads to mortality of the initially smallest stools [27], and that the competitive hierarchy between stools is preserved over harvest [26]. As soil factors are known to be important determinants of willow growth [28, 29, 30, 31], differences in soil at field scale likely underlie the initial size variability between plants. Differences in cutting quality also may cause an initial variability in growth performance between plants (see section 4.2). To be able to detect possible effects of cutting quality and to separate those from soil factors, it is advantageous to perform controlled experiments which allow the relative variation to be attributed to only a few factors. Verwijst et al. [32] compared the relative variation in shoot height of willow populations grown in the field with the relative variation of populations grown in boxes which had a standard soil and were treated as similar as possible with regard to fertilization and irrigation (Figure 2). The controlled experiments
showed a decreased relative variation and enhanced the detection of cutting quality traits with relevance for early establishment success.

Treatment

As willow is a relatively new crop, advances in willow breeding generate a steady increase in potential and attainable yield [33, 34]. This increase in biomass yield is estimated to be 50 to 100% since the 1970s’. This means that spacing, harvest frequency and fertilization have to be adapted to the rapidly evolving new plant material, in order to avoid mortality and ensure a high productivity also during the later cutting cycles. Most of the planted willow stands in Sweden consist of monoclonal stands or blocks of monoclonal units. However, such monoclonal stands are vulnerable to pathogen adaptations [35] and it has been shown that clone mixtures may be effective against the spread of diseases [36]. However, the relative competitive power of willow clones does differ, which means that certain clones may be outcompeted by other ones in mixtures of clones. If a mixture consists of only a few clones and one of the components is attacked by a pathogen, the susceptible clone is likely to be outcompeted by the others, thereby causing gaps, a delayed stand closure and lower productivity in later cutting cycles [37]. Furthermore, as clone-site interactions have been reported for willow, and the performance of clones in mixtures can not be predicted from their performance in pure stands [24], successful clone combinations are expected to be highly site specific.

Trace contaminants

The Anthropocene period is characteristic by rapid urbanization, industrialization, mining activities, metal ore refining, agricultural chemicals, liquid and solid wastes, resulting in heavy metal pollution of water and land resources. There has been an increasing load of heavy metals (Cu, Zn, Cd, Cr, Hg and Ni) in the aquatic ecosystems, which in turn are being assimilated and transferred within food chains by the process of biomagnification. The problem with the heavy metals is their non-biodegradable nature. The conventional methods used to remove metal ions include chemical precipitation, lime coagulation, ion exchange, reverse osmosis solvent extraction, aeration, chemical oxidation, electrodialysis, ultra filtration, and chlorination (Rich & Cherry 1987).

Research was carried out recently to evaluate the metal accumulation in charophytes. Hence, Bibi et al. (2010) investigated the effects of Cd, Cr and Zn on the growth of Nitella graciliformis and their bioaccumulation in the plant under laboratory conditions. Charophyte specimens were exposed to different Cd, Cr and Zn concentrations, and it was observed that the heavy metals concentrations in the plant increased with the increasing metals concentrations in the mediums. As a result, negative growth occurred and the internode elongation was reduced when exposed to these metals at any concentration, however, intracellular Nitella gracilliformis has a potential for accumulating Cd, Cr and Zn. Bibi et al. (2010) concluded their investigation by stating that their study should be an integral part of the sustainable development of ecosystems and pollution assessment programs.

Absorption processes are being widely used for the removal of heavy metals from aqueous solutions. According to Shaikh Parveen & Bhosle Arjun (2011), use of various products has been widely investigated in the recent years as an alternative for the currently expensive methods of water treatment, and some natural products can be effectively used as a low cost absorbent. The above mentioned authors conducted batch studies of Hydrilla sp. and Chara sp. to evaluate the uptake of Cr from aqueous solutions. They found out that about 91.7% removal was obtained with 2 mg L-1 of Chara sp. at 2 mg L-1 Cr concentration after a period of seven days at pH 4. Their results also indicated that the metal removal increased as the days were extended, however, with the increasing contact time Hydrilla sp. proved to be better than Chara sp. in the Cr removal.

Bioprocess control

The bioprocess control has different goals and objectives, function of bioprocess characteristics and imposed performances. In spite of high non-linearity linear control theory and basic controllers (on/off, PID) are still applied in most industrial applications.

More sophisticated control should rely on models able to correctly represent the biosystems behavior. Due to the complexity of the biological systems, basic models, which are nice to use and help to simplify the underlying mathematics, are not able to reflect the real situations. The large sets of parameters from the complex models need to be experimentally identified, and consequently the e, and consequently the experiments should be carefully designed to provide this valuable information. Taking into account the time-to-market, which must be as short as possible the accepted control solution could be suboptimal based on classical robust control.

Bioprocess reproducibility and living cell systems variability reduction from run to run is to be carefully studied. The media composition optimization and the successful application of PAT (process analytical technologies combining the techniques for in-process monitoring, data-based modeling process control) will contribute to the quality of production improvement.

In bioindustry, bioprocesses are subject to a number of local and / or supervisory control structures. Local controllers are used to get the set-point control of different physical / chemical parameters (e. g. temperature, pH and dissolved oxygen concentration), while supervisory control is necessary for optimizing the feed in a fed batch process or the dilution rate in a continuous one [23].

Various simple feed-control strategies have been applied in the past [12, 24, 25]: (a) Simple indirect feedback methods: nutrients (indirect variable) are fed to the bioreactor by an on-off controller when a direct (on-line measured) variable deviates from its set point, e. g., feeding of ammonium by monitoring the pH (pH-stat), or nutrient feeding to keep the dissolved oxygen concentration constant (DO-stat). (b) Predetermined feeding strategies; this is a feed­forward strategy based on prior process knowledge, e. g., exponential feeding to grow at a constant biomass-specific growth rate. (c) Direct feedback; a substrate concentration can be directly controlled by nutrient feeding when it is measured on-line by sensors inside or outside the bioreactor. (d) Feed control by state estimation; the estimation of key-process parameters from on-line measurements can be applied and the control is based on the evolution of the growth rate or the substrate concentration.

Other advanced feed-control strategies may be applied when additional process information is available: feed-forward model-based control; feedback model-based control (an extended Kalman filter simultaneously estimates a state variable and adapt the controller); fuzzy control; neural — network control (for predictive control); expert systems (for supervisory control).

A. Bioprocess control with a priori model (model based process control)

The bioprocess control based on a priori model (BCAPM) can be seen as the on-line application of optimal control, where control actions are regularly re-calculated based on a

image069

global process model and process information. The global model is used to calculate optimal control actions by a prediction of future outputs over a limited time horizon.

image070Подпись: YesChange set of
experimental data and
repeat the flux
determination process

Figure 2. Determination of metabolic flux distribution [14]

For the time being, the unstructured deterministic models (the cells are considered as black­box units) are very used in the bioprocess control [26]. In the future an increase of the structured models role is expected, as a consequence of modern analysis methods development, as well as of the capacity to more adequately describe the phenomena.

The basic concepts of BCAPM consider two main ideas [27, 28]: (1) the explicit use of an a priori model to predict the process output(s); (2) the calculation of the future control actions by minimizing a global objective function.

The problem can be solved in different ways: (a) for a linear, time-invariant model, and in the absence of constraints, an explicit analytic solution of the above optimization problem can be obtained; (b) with linear constraints, the above optimization problem is a Quadratic­Programming problem, which can be numerically solved; (c) in the presence of a nonlinear model or nonlinear constraints, a non-convex optimization problem must be solved at each sampling period. So iterative optimization algorithms, (e. g. the Nelder-Mead method) can be used in order to converge to local minima.

There are two major problems which limit the application of BCAPM to bioprocesses [29]: (1) the model must predict the process variables evolution with sufficient precision; (2) given a nonlinear process model, the nonlinear optimization problem is solved for each (sampling) period; hence, the bioprocess model must be linear during these time periods.

The first item obstructs the application of BCAPM to complex or partially known systems, without defined global models. The second item blocks the application to performable systems; otherwise the control techniques are not properly used, due to the short sampling time periods (the second issue can be avoided by reason of large time constants characteristic to bioprocesses).

Recent developments in on-line measurement techniques, parameter and state estimation, in addition to the search of improved quality control, motivated the development of BCAPM. Now the technique was upgraded with better results. For instance [30] the applied BCAPM for feed control in the production of monoclonal antibodies allows to improve the yield with 43%.

B. Bioprocess adaptive control

When the process characteristics change during time, the operation conditions must also be changed: controller parameters and set point values. Moreover, optimal bioprocess evolution is commonly determined off-line, the process conditions are not perfectly known, and the process model is not well defined. Furthermore, it can be a lot of changes in process conditions in conjunction with different microorganisms’ life cycles (when the cell concentration increase in time in a batch bioprocess, the oxygen set point must be increased). Hence, there is a need for some feedback mechanisms based on on-line measurements. On-line adaptation is possible when the state variables can be measured online10 (directly using hardware sensors or indirectly by soft sensors [31, 32]).

The adaptive control structures are based on the design of different estimation algorithms which are able to determine the off-line parameter values. Many control algorithms were developed based on minimal knowledge about bioprocess kinetics (the minimal modeling concept) [33-36].

A typical adaptive control system is presented below:

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Figure 3. Adaptive control structure

There are two classes of adaptive control (where the adaptation is attained on the basis of on-line parameter observers) [37]: (1) the process changes can be measured — therefore it is possible to systematically adjust the controller settings, based on the measured / anticipated bioprocess changes; (2) the process changes cannot be measured / predicted — hence the controller settings are automatically adjusted by a loop optimizer.

Morphology and cellular characterization of biogranules

observations. At the initial development stage, the biomass was composed more of loosely clumped sludge, which can easily break up into pieces under vigorous shaking. Within a week, the anaerobic seed granules underwent morphological changes from spherical in shape and black in color with average diameter of 1 mm into smaller grey granules due to exposure to the shear force during the aerobic react phase. On day 30, two different types of granules were clearly observed in the reactor as shown in Figure 4.

Figure 4a shows mainly irregular-shaped with yellow colored biogranules (Type A) that are solely developed from the activated sludge. In Figure 4b, the anaerobic granules that have fragmented into smaller pieces have formed different sizes of biogranules (Type B) containing pieces of anaerobic granules. The outer layer of the latter were yellow in color indicating the domination of aerobic or facultative microorganisms while the darker spots within the granules indicate the presence of anaerobic fragments originated from the anaerobic granules. The formation of Type A biogranules can be elucidated by the mechanisms explained by Beun et al. (1999). The development was initiated from the mycelial pellets that were retained in the reactor due to high settling velocity. These mycelial pellets eventually become the support matrix for the bacterial growth. Bacteria that were able to attach to this matrix were retained and suppressed the growth of filamentous microorganisms and became the dominant species in the reactor.

Figure 4. The morphological development of biogranules (scale bar at steady-state equals to 1mm). Pictures were taken using a stereo microscope with magnification of 6.3X. (a) Biogranules developed from the activated sludge. (b) Biogranules developed from anaerobic granules patches.

The formation of Type B granules has been discussed by Linlin et al. (2005). These biogranules were formed through a series of physical and morphological changes. The anaerobic granules initially disintegrated into smaller size flocs and debris when exposed to aeration forces in the reactor column. Some of the granules and debris that were too small were washed out with the effluent while the heavier ones were retained in the column and acted as nuclei for the formation of new granules. Having these combinations of aerobic and anaerobic portions within the biogranules will increase the possibility of complete degradation through the anaerobic/aerobic degradation process. Figure 5 shows the obvious morphological differences between sludge particles with average sludge particles of 0.02 ± 0.01 mm (Figure 5a) during the initial stage of the experiment and matured biogranules (Figure 5b) at the final stage with average diameter of 2.3 ± 1.0 mm.

The microstructure of the biogranules was examined using SEM (Figure 6). The SEM observation of the mature biogranules shows the domination of non-filamentous coccoid bacteria. The bacteria are tightly linked and embedded to one another and form a rounded shape on the surface of the biogranule and covered with extracellular polysaccharides substances (EPS) (Figure 6a). Figure 6b shows the presence of cavities between the clumped bacteria. These cavities are anticipated to be responsible to allow a smooth mass transfer of substrates or metabolite products into and out of the granules (Tay et al., 2003 and Toh et al., 2003).

Figure 5. Pictures of sludge particles during the initial stage of the experiment (a) and matured biogranules at the 66 days of the experiment (b). Pictures were taken using a stereo microscope with magnification of 6.3X (scale bar equals to 1 mm)

Figure 6. FESEM microstructure observations on mature biogranules under the magnification of 10,000K. (a) Coccoid bacteria tightly linked to one another. (b) Cavities that appear between bacteria clumped inside the biogranules

Characteristics of Animal Slurry as a Key Biomass for Biogas Production in Denmark

Jin M. Triolo, Alastair J. Ward, Lene Pedersen and Sven G. Sommer

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/54424

1. Introduction

Climate change has become an important global issue and animal manure has been pointed out as a major source of greenhouse gas (GHG) emissions. The Danish government targets animal manure as a key biomass with the aim of producing renewable fuels and reducing GHG emissions. Animal manure is a mixture of excreta and materials added during management. Apart from the major part of animal slurry which is feces and urine, animal slurry is composed of many materials, i. e., sand, water from cleaning, small branches and straw from the bedding materials. Thereby a wide variation of characteristics can be found depending on different management systems, animal type and diet, etc. which make for difficulties in the estimation of manure quality for biogas production.

There is no doubt that in the future the world’s energy supply market will be dominated by renewable energy, since there is no alternative. While combustion is the most common method to gain energy from plant biomass such as wood and wood chip, the high content of water in animal slurry suits wet fermentation for conversion to energy, since direct combustion is not appropriate for most animal manures. Direct combustion dry matters (DM) content must be at least 45% [1]. Animal slurry is typically in a liquid form where DM typically contains 1-10% [2]. The production of energy through combustion can be made by enriching fiber fractions by separation technology. Fiber rich animal slurry through separation technology can potentially replace 3.6 PJ of coal energy, which corresponds to 4.3 % of the yearly Danish energy consumption, if one third of the Danish manure is separated [3,4]. The European Commission made a considerable effort by making mandatory national targets for renewable energy shares of final energy consumption in 2020 with the goal: Increasing energy efficiency by 20% by 2020 and reducing GHG emissions at least 20% within the same period [5]. To commit to the targets of the European Commission, the Danish government targets animal slurry as a key element, setting an ambitious goal of increasing the utilization of animal manure for energy production from current levels (5%) up to 40% by 2020 [6].

© 2013 Triolo et al., licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons. org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Facing an "aggressive growth" of biogas production using animal slurry as prime feedstock, it is of great importance to understand critical barriers of characteristics of animal slurry on economic viability. Further, it is of current interest to find solid organic residues as co­substrate, in order to bring the best synergy by overcoming barriers of animal slurry. Biomass is the term given to all organic matter. Its production worldwide is estimated at 146 billion metric tons per year, composing mostly of wild plants [7-9]. The energy of biomass originates from solar energy through photosynthesis, which converts water and CO2 into organic materials in plant biomass. It comprises i. e., plant, wood, energy crop, aquatic plants. Whereas plants store energy in the form of organic materials from solar energy directly, animals generate excreta through metabolizing and digesting. Hence, animal slurry has unique characteristics compared to other biomasses, since during digestion the relatively easily degradable organic matter is utilized while recalcitrant carbon concentrations are increased by animal digestion [10], which limits subsequent anaerobic degradability (BD) and biogas potential. Moreover, the quantity of organic polls in liquid slurry is often too small to perform economically viable operations [10,11].

Hence, the aim of this study is intensive investigation and identification of critical barriers in characteristics of animal slurry. The study was carried out using diverse animal slurry collected from 20 different farms in Denmark, firstly focusing on the Biochemical Methane Potential (BMP) of animal slurry with respect to the total feedstock fresh weight, organic fractions (VS) and DM. Physicochemical characteristics were determined to qualify animal slurries as prime substrates for biogas reactors, and the results were applied to construct algorithms to assess potential methane yield. This study finally highlights the characteristic digestibility of animal slurry compared to plant lignocellulosic biomass. The study further aims to improve our suggested model to predict BMP [10]. In accordance with the objective of the study, quantification of nutrients and characterization of indigestible organic pools of a wide range of animal slurry will be carried out.

Biodiesel

Biodiesel refers to a liquid fuel alternative to petroleum diesel which can be used alone or blended with petroleum diesel. Similarly to bioethanol blends, blends of 20% biodiesel (B20) or lower can be used in diesel equipment without or with only minor modifications. Biodiesel can be produced from animal fat or oil from plants such as soybean and Jatropha, or from microalgae and fungi.

2.1.1. Biodiesel from vegetable oil

Conventionally, the biodiesel is produced from vegetable oil with the presence of alcohol/alkaline/acid catalyst. This process is known as transesterificaiton or alcoholysis as shown in Figure 5 [67].

The vegetable oil is converted to esters and glycerol by reacting with an alcohol which can be ethanol, methanol or butanol. During this reaction, catalysts (e. g. alkalis, acids or enzymes) are required to improve the reaction rate and yield. Alkalis including NaOH, KOH and carbonates etc. are usually used as catalyst when feedstock containing less than 4% fatty acids. Acids, which are normally used when feedstocks contain more than 4% free fatty acids, include sulfuric acid, hydrochloric acid and sulphonic acids etc. Lipase, an enzyme that catalyses the hydrolysis of fats, can be used as a biocatalyst [68].

A review by Ma and Hanna [69] summarized the parameters significantly influencing the rate of transesterificaiton reaction which include temperature, ratio of alcohol to oil, type of catalyst and catalyst concentration. The ester yield is increased by rising the transesterificaiton temperature; however, it will increase the risk of forming methanol bubbles when the temperature is close to methanol’s boiling point. The ratio of alcohol to oil depends on the type of catalyst used which is approximately 6:1 for alkali catalyst and 30:1 for acid catalyst [70]. Enzyme used as a catalyst is becoming more attractive nowadays because it tolerates free fatty acid and water contents in the oil to avoid soap formation and thus results in an easier purification of biodiesel and glycerol [68]. However, the relatively high price of enzyme catalyst makes its utilization in the commercial production of biodiesel challenging.

Nowadays, 90% of U. S. biodiesel is made from soybean oil. The price relationship between vegetable oils and petroleum diesel is key influential factor to the profitability of biodiesel industry. Because of the increasing price of vegetable oils, biodiesel industry is suffering uncomfortable situations [71]. As a result, alternative non-food feedstocks and the associated technologies are becoming the focused research in biodiesel area.

Jatropha curcas is an agro-forestry crop growing in tropical and sub-tropical countries, such as India, Sahara Africa, South East Asia and China. This crop grows rapidly and takes 2-3 years to reach maturity with economic yields [72]. Lu et al. reported a higher than 98% biodiesel yield by a pre-esterification using solid acid followed by a transesterificaiton using KOH [73]. A high yield of 98% (wt) is also reported by Shah et al. [74] which is obtained from Jatropha oil using Pseudomonas cepacia lipase. Kumari et al. [75] also documented a relatively high yield of 94% (wt) biodiesel yield from Jatropha oil using lipase from Enterobacter aerogene. They also reported negligible loss in lipase activity even after repeated use for several cycles.

Distillation

Distillation is a common separating technology in the chemical industry. This method separates the components successively according to their different volatilities, and it is essential for the separation of liquid mixtures. Atmospheric pressure distillation, vacuum distillation, steam distillation, and some other types of distillation have been applied in bio­oil separation.

Due to its complex composition, the boiling of bio-oil starts below 100 °C under atmospheric pressure, and then the distillation continues up to 250-280 °C, whereupon 35-50% of residue is left (Czernik & Bridgwater, 2004).

The thermal sensitivity of bio-oil limits the operating temperature of distillation. In view of the unsatisfactory results obtained by atmospheric pressure distillation, researchers have employed vacuum distillation to lower the boiling points of components, and bio-oil could thereby be separated at a low temperature. Characterization of the distilled organic fraction showed that it had a much better quality than the crude bio-oil, containing little water and fewer oxygenated compounds, and having a higher heating value.

Steam distillation is performed by introducing steam into the distilling vessel, to heat the bio-oil and decrease its viscosity, and finally the volatile components are expelled by the steam. In a study combining steam distillation with reduced pressure distillation, bio-oil was first steam distilled to recover 14.9% of a volatile fraction. The recovered fraction was then further distilled by reduced pressure distillation to recover 16 sub-fractions (Murwanashyaka et al., 2001). In this process, a syringol-containing fraction was separated and syringol with a purity of 92.3% was obtained.

Due to its thermal sensitivity, it is difficult to efficiently separate bio-oil by conventional distillation methods. Molecular distillation seems to offer a potential means of realizing bio­oil separation, because it has the advantages of low operating temperature, short heating time, and high separation efficiency.