Category Archives: BIOMASS NOW — CULTIVATION AND UTILIZATION

Towards the Production of Second Generation Ethanol from Sugarcane Bagasse in Brazil

T. P. Basso, T. O. Basso, C. R. Gallo and L. C. Basso

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/54179

1. Introduction

Brazil and the United States produce ethanol mainly from sugarcane and starch from corn and other grains, respectively, but neither resource are sufficient to make a major impact on world petroleum usage. The so-called first generation (1G) biofuel industry appears unsustainable in view of the potential stress that their production places on food commodities. On the other hand, second generation (2G) biofuels produced from cheaper and abundant plant biomass residues, has been viewed as one plausible solution to this problem [1]. Cellulose and hemicellulose fractions from lignocellulosic residues make up more than two-thirds of the typical biomass composition and their conversion into ethanol (or other chemicals) by an economical, environmental and feasible fermentation process would be possible due to the increasing power of modern biotechnology and (bio)-process engineering [2].

Brazil is the major sugar cane producer worldwide (ca. 600 million ton per year). After sugarcane milling for sucrose extraction, a lignocellulosic residue (sugarcane bagasse) is available at a proportion of ca. 125 kg of dried bagasse per ton of processed sugarcane. Therefore, sugarcane bagasse is a suitable feedstock for second generation ethanol coupled to the first generation plants already in operation, minimizing logistic and energetic costs.

State-owned energy group Petrobras is one of the Brazilian groups leading the development of second generation technologies, estimating that commercial production could begin by 2015. Other organizations making significant contributions to next generation biofuels in Brazil include the Brazilian Sugarcane Technology Centre (CTC), operating a pilot plant for the production of ethanol from bagasse in Piracicaba (Sao Paulo) [3]. Recently, GraalBio (Grupo Brasileiro Graal) has stated publically that will start production of bioethanol from sugarcane bagasse in one plant located at the Northeast region of the country.

Pretreatment, hydrolysis and fermentation can be performed by various approaches. According to a CTC protocol, the process of manufacturing ethanol from bagasse is divided into the following steps. First, the bagasse is pretreated via steam explosion (with or without a mild acid condition) to increase the enzyme accessibility to the cellulose and promoting the hemicellulose hydrolysis with a pentose stream. The lignin and cellulose solid fraction is subjected to cellulose hydrolysis, generating a hexose-rich stream (mainly composed of glucose, manose and galactose). The final solid residue (lignin and the remaining recalcitrant cellulose) is used for heating and steam generation. The hexose fraction is mixed with 1G cane molasses (as a source of minerals, vitamins and aminoacids) and fermented by regular Saccharomyces cerevisiae industrial strains (not genetically modified) using the same fermentation and distillation facilities of the Brazilian ethanol plants. The pentose fraction will be used as substrate for other biotechnological purposes, including ethanol fermentation.

Researchers are focusing on cutting the cost of the enzymes and the pretreatment process, as well as reducing energy input. Production of ethanol from sugarcane bagasse will have to compete with the use of bagasse for electricity cogeneration. Depending on the efficiency of the cogeneration plant, about half of the bagasse is required to produce captive energy in the form of steam and energy at the sugar and ethanol facility. It is estimated that the surplus bagasse could increase the Brazilian ethanol production by roughly 50% [3].

Effect of SDS in biomass hydrolysates solution

SDS is a popular surfactant used in PHA recovery to disrupt the cells or remove a small amount of hydrophobic impurities from PHB granules [30, 31]. The purity of PHB granules can be increased from 96.4% to above 99% when a small amount of SDS was added in the base treatment. The surfactant left in the base solution, however, may have an adverse effect when the cell debris is reused in microbial PHB fermentation. An acid-base biomass hydrolysates solution containing 48.5 g/L of soluble solids and SDS were added into a glucose medium. The cell debris concentration was kept at 1.94 g/L, and SDS concentration was increased from 0.2 to 0.8 g/L with SDS. Controls without biomass hydrolysates and SDS were run in parallel. Table 2 gives the results of cell growth and PHA formation at different surfactant levels at 24 and 48 hours, respectively.

Biomass

SDS

24 hours

48 hours

hydrolysates

(g/L)

Cell mass

PHB

Cell mass

PHB

(g/L)

(g/L)

(wt%)

(g/L)

(wt%)

0

0

2.08 ± 0.02

36.8 ± 1.1

2.7 ± 0.02

44.4 ± 0.6

1.94

0.2

3.69 ± 0.06

49.7 ± 2.1

4.99 ± 0.04

60.6 ± 1.1

1.94

0.4

3.27 ± 0.05

39.6 ± 1.2

4.58 ± 0.04

53.8 ± 0.8

1.94

0.6

2.70 ± 0.04

33.9 ± 1.5

3.51 ± 0.03

50.3 ± 0.7

1.94

0.8

2.59 ± 0.04

17.8 ± 1.3

3.54 ± 0.03

25.8 ± 1.2

Note: flask cultures were maintained at 30 oC and 200 rpm in a rotary incubator.

Table 2. Effect of surfactant SDS and biomass hydrolysates on cell growth and PHB formation

Compared with the controls of no biomass hydrolysates and surfactant, all the cultures containing the acid-base hydrolysates exhibited better cell growth. Particularly, the increase of cell concentration from 24 hours to 48 hours was the new cell mass formed in 24 hours from glucose and cell debris in the presence of SDS. The formation of PHB, however, was deteriorated at high SDS concentrations (0.6-0.8 g/L). At a low or moderate SDS concentrations (0.2-0.4 g/L), the positive effect from biomass hydrolysates was much higher than the negative effect of surfactant. The PHB concentrations, after 48 hours cultivation, were 2.4 to 3 g/l, in comparison with 1.2 g/L of the control. The results in Table 2 indicate that the dosage of SDS in PHA recovery should be controlled according to the amount of residual microbial biomass generated. The mass ratio of SDS to biomass hydrolysates should be less than 20% w/w or better at 10% w/w. In a typical PHB recovery process as shown in Figure 1, the amount of SDS used should be less than 2.9 g for 10% of acid-base cell debris or 5.8 g for 20% of acid-base cell debris. The consumption of SDS is therefore 4-8 % of PHB resin produced. It is much lower than the SDS dosages used in the conventional separations [30, 31].

2. Conclusion

Residual microbial biomass is an inevitable waste generated in downstream recovery of polyhydroxyalkanoates from microbial cells. With a separation technology based on sequential dissolution of no-PHB cell mass in aqueous solutions, the cell mass separated from the PHB-granules is decomposed and hydrolyzed into small molecule hydrolysates that can be assimilated by microbial cells as nutrients and/or carbon source. A type of biomass hydrolysates generated from continuing treatment in acid and base solutions exhibits the best nutrient value for cell growth and PHA formation. The acid-base hydrolysates contains two major water-soluble components derived from the cell proteins and lipids, respectively. When PHB-producing cells are fed with the hydrolysates in a glucose mineral solution, the cells grow faster and form more biopolyester in comparison with the controls that do not contain the hydrolysates. The glucose-based yields of cell mass and PHA bioplastics are significantly improved. SDS is an efficient surfactant to remove the small amount of hydrophobic residues for high PHB purity, but also a potential inhibitor to microbial PHA formation. When the amount of surfactant is less than 20% of an acid-base biomass hydrolysates, its negative effect is overwhelmed by the nutritional value of hydrolysates. Under these conditions, it is highly possible to reuse most of the residual biomass discharged from PHB recovery in the next microbial PHB fermentation. It therefore eliminates a waste stream from bioplastics production and saves the nutrients with improved PHA productivity and yield.

A first practical observer for k and a

Let us consider the new variable

T(t) = yi (0) — yi (0 + У2 (о) — У2 (0

that is measured on-line. From Proposition 1, one deduces that r(-) is bounded. One can also easily check the property

dT

— = (1 — k) a x(t) > 0 , Vf > 0 . Consequently, t(-) is an increasing function up to

Подпись: (6)t = lim T(t) < +ro

and t(-) defines a diffeomorphism from [0, +ro) to [0,T). Then, one can check that the dynamics of the variable s in time t is decoupled from the dynamics of the other state variables:

where a and в are parameters defined as combinations of the unknown parameters a and k: к

Подпись: aПодпись: в1 — it’

1

я(1 — к)

Подпись: sПодпись: ds d2s dT dT2

image059 image060

and from (4) one has (a, в) Є [a-, a+] x [в-, в+]. For the identification of the parameters a, в, we propose below to build an observer. Other techniques, such as least squares methods, could have been chosen. An observer presents the advantage of exhibiting a innovation vector that gives a real-time information on the convergence of the estimation.

^,,S) = § + M3A|i

and the pair (A, C) in the Brunovsky’s canonical form:

/0 1 0

A = 0 0 1 and C = (10 0) . (7)

0 0j

Подпись: x _ g3?'(yi) й ЫЛп У h ЫЛп)'
Подпись: a = la (УЬ g) в = їв (У1, g)

The unknown parameters a and в can then be made explicit as functions of the observation yi and the state vector g:

One can notice that functions <p(y1, •), la(y, •) and їв(y1, •) are not well defined on R3, but along the trajectories of (3) one has g3/g2 = —ви'(У1) and g2 = a — вц(У1), that are bounded. Moreover Assumption A2 guarantees that ц’ (y1) is always strictly positive. We can consider (globally) Lipschitz extensions of these functions away from the trajectories of the system, as follows:

Подпись:Подпись: Ц' (У1) ?'(Уі) У'(Уі)'g2 — h1 (У1, g)

Ігі(УіЛ)

У'(Уі) with

ІЧ (Уі/ g) = sat ^-^+y'(yi),-^“y'(yi),^ , h2 (У1, g) = sat (a— — в+ Ц(У1), a+ — ГЦ(У1), g2) .

Then one obtains a construction of a practical observer.

Proposition 3. There exist numbers > 0 and C1 > 0 such that the observer

Подпись:Подпись: (g1 — У1)(8)

guarantees the convergence

Подпись: (9)max (|a(t) — a|,в(т) — в) < he-^1 т||g(0) — g(0)|| for any 61 large enough and т Є [0, T).

Proof. Consider a trajectory of dynamics (3) and let O1 = {y 1 (t) }t>0. From Proposition 1, one knows that the set O1 is bounded.

Define Kg1 = — (301 362 б3 )T. One can check that Kg1 = —P—1CT, where Pg1 is solution of the algebraic equation

61 P6l + ATPei + P6l A = CTC.

Consider then the error vector e = £ — £. One has

Подпись: / (A + % C)e + Подпись: de dr 0 0

ф (уь £) — Ф (У1/£)/

where ф(yi, • ) is (globally) Lipschitz on R3 uniformly in yi Є Oi. We then use the result in [10] that provides the existence of numbers C1 > 0 and q1 > 0 such that

for 01 large enough. Finally, functions la (y, •), Ip (y1, •) being also (globally) Lipschitz on R3 uniformly in yi Є 0, one obtains the inequality (9). |

Corollary 1. Estimation of a and k with the same convergence properties than (9) are given by

k(r),d(r)=sat(k-,k+, &{T) ),sat(a-,a+,1+/X{T))

y y 1 +4?)) f(T) )

Remark. The observer (8) provides only a practical convergence since r(t) does not tend toward +ro when the time t get arbitrary large. For large values of initial x, it may happens that y(t) > t for some times t > 0. Because the present observer requires the observation y1 until time t, it has to be integrated up to time min(r(t), t) when the current time is t.

5.1. A second observer for m and x

We come back in time t and consider the measured variable z = y 1 + y2. When the parameters

T

a and в are known, the dynamics of the vector Z = [z z ‘i can be written as follows:

/

Подпись: Z = AZ +with z = CZ

Подпись: Ф(УЪ Z, ^ в)/ Z32 and i/>(i/i, Z,rt,^) = ^ +Z2?»(yi)(Myi) -«)

Parameter m and variable x(-) can then be made explicit as functions of y1 and Z:

m = Zm(yi, Z) = ?'(Уі) — 7^ , x = — fZl Z2

Functions f(y1, •, a, в) and lm(y 1, •) are not well defined in R3 but along the trajectories of the dynamics (3), one has Z3/Z2 = y(y1) — m and Z2 = —x/в that are bounded. These functions can be extended as (globally) Lipschitz functions w. r.t. Z:

f(yh Z, a, в) = h3 (У1, Z )Z3 + min(Z2, z(0)2/e2 )ц'(У1 )(eP(y1) — a)

lm (УЪ Z) = У(У1) — h3 (У1, Z)

with

Proposition 4. When a and в are known, there exists numbers b2 > 0 and C2 > 0 such that the observer

image072 Подпись: (ll)

/0 302

for any 02 large enough and t > 0.

Proof. As for the proof of Proposition 3, it is a straightforward application of the result given in [10]. 1

Influence of SSL Size on Rack Loading Operations

If the yield of switchgrass in a commercial-scale operation averages 4 ton/ac (8.96 Mg/ha), this equates to approximately 9 bales/ac (22 bales/ha). It is suggested that the minimum size of a SSL contain the bales from 60 ac (24.5 ha) is 540 bales, and the maximum size SSL approximately stores bales from 1,200 ac (487 ha) 10,800. If 70% of the theoretical loading (30 racks/d) is achievable, the contactor will load 21 racks times 16 bales/rack is equal to 336 bales per day. The minimum size SSL will remove all of the bales in about 540/336, which is

1.6 days. The maximum size SSL will be loaded out in 10,800/336 = 32 days.

Cost of SSL operations at the smaller SSLs will be higher because of the mobilization charge to move equipment and crew to the next SSL for a fewer days of operation. It is probable that the load-haul contract offered by the biorefinery for each individual SSL will consider the haul distance and SSL size and thus the per-ton price will be different for each SSL.

Biomass Digestion to Produce Organic Fertilizers: A Case-Study on Digested Livestock Manure

Alessandra Trinchera, Carlos Mario Rivera, Andrea Marcucci and Elvira Rea

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/53869

1. Introduction

Biogas production by anaerobic digestion of organic wastes coming from agricultural practices is one of most promising approach to generate renewable energy, giving as end — product a digested organic biomass with specific characteristics useful for soil fertilization. This last aspect represents an opportunity in relation to the need to close the nutrient cycles within the agricultural and natural ecosystems, particularly in specific systems underwent to a constant resources depletion, as those of Mediterranean area, where the C-sink loss represents one of the main causes of desertification [1], [2]. The composting process was yet identified as one of the promising answers to the need of soil organic matter conservation, such as the addition to the soil of different organic materials of different origins [3], but the anaerobic digestion could represent an effective further step able to guarantee the recycle of nutrients, coupled with an environmental-friendly energy production [4].

Particularly, anaerobic digestion of livestock manures allows us to achieve several purposes: i) renewable energy generation; ii) reduction of nitrate leaching in livestock exploitations, iii) production of an organic biomass as by-product employable as organic fertilizer [5]. Actually, digestates coming from livestock manure give biomasses characterized by biologically stable organic matter and relevant nitrogen content; these traits suppose that these biomasses may be usefully utilized as N-fertilizers and soil organic amendments in agriculture, but also as a component of growing media in pot horticultural cultivation.

It should be remarked that production of greenhouse horticultural crops requires the use of growing media of high quality, with specific physical-chemical characteristics. Being the peat, organic component traditionally used in substrates formulation, a non-renewable resource (its extraction involving many environmental issues), it becomes ever more urgent the need to individuate alternative organic materials with the same functioning, such as composts or products coming from biogestion processes [6]. Nevertheless, the use of

© 2013 Trinchera 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.

biodigestate as amendment, still now not allowed in Italy, should provide the declaration of stability parameters for organic matter, since the utilization of matrices not properly stabilized could lead to the risk of high fermentescibility of organic components and, thus, consequent phytotoxicity phenomena [6],[7]. The stabilization of organic matter actually involves the mineralization of the most labile organic fraction, with the following decrease of C/N ratio; this means physical, chemical and biological changes of the starting material and, thus, the decrease of porosity, increase of pH, CEC, bulk density and salinity, due to a concentration of organic compounds which, generally, are characterized by lower molecular weight respect to the starting ones, more resistant to microbial degradation [8].

The amendment properties of composts and biodigestates could be assessed by different analytical methods, such as the isoelectrophoretic techniques (IEF) [9],[10],[11]. Results obtained after IEF characterization of the extractable fraction in alkaline environment of dried vine vinasse (an anaerobically digested solid residues, constituted by exhausted stems, skins and grape seeds, obtained after distillation of the "grappa", the Italian "acquavite"), showed an increase of the extractable organic components in alkaline environment, with a higher content in less acidic organic fraction, probably due to a "concentration effect" of the more complex organic components not, or only partially, degraded during the anaerobic digestion process.

Other works demonstrated also that the same dried vine vinasse, applied together with other mineral components in growing media, was able to increase nutrient availability [12] and express a sort of biostimulant activity on plant roots [13]. Study performed by optical microscopy demonstrated that digested vine vinasse in combination with clinoptilolite addition, promoted maize roots development, by increasing mucigel production by root tip and thus favoring the following solubilization and uptake of nutrients by plant from the added organic biomass (Figure 1).

image98

Figure 1. Root of Zea mais L., treated with micronized clinoptilolite and digested vine vinasse.

In relation to the N-fertilizer attitude of a biodigestate, it has a particular relevance in the case of the biodigestion of animal manure. The anaerobic process allows to maintain constant the total N amount of the original material, even if the organic N is mainly transformed into ammonia, the mineral form most easily available to the crops. The separation between the liquid and the solid fractions after biodigestion allows to recover the ammonium-N in the fluid fraction and the residual organic matter in the solid fraction, so to emphasize the different characteristics of the two fractions: the first one, usable as a typical N-fertilizers, able to furnish nutrient supply to plant; the second one as organic amendment, able to supply organic matter to soil and then improve its chemical, physical and biological characteristics. A proper composting process applied to the solid fraction of this digestate could lead to a further improvement of the biomass, by promoting its biochemical stability and giving those amendment properties yet described, which constitute the adding value of the final product.

What is relevant is that the risk of nitrate leaching in water represents the main limitation to the direct application of not pre-treated livestock manure to soil: effectively, its amendment properties, linked to soil organic matter addition, often go in conflict with the Council Directive 91/676/EEC on the "Water protection from nitrates" [14], especially in vulnerable zones, such as those of Italian northern regions. In this sense, the biodigestion process represents a great opportunity to utilize livestock manure digestates as N fertilizer, potentially allowing to overcome the limit of 170 Kg N ha-1 year-1 superimposed by EU Nitrates Directive, since the high N-efficiency coefficient of these digestates, similar to that of soluble mineral fertilizers [15]. The solid fraction, containing organic matter already partially stabilized, could also permit its application during the winter season, provided the obtained amendment has a constant composition and a fraction of slow release-N, eventually increased by a following composting process [16],[10],[17]. On the other hand, the anaerobic conditions ensure the formation of high amount of ammonium during the organic matter degradation process, without incurring in the subsequent oxidation into nitrate [18],[4]. Being the ammonium the N-form more rapidly assimilated by the crops, this could be a further element in favor of the utilization of biodigestates as components of growing media, effectively conjugating the physical amendment properties with those chemical, connected with fertilization.

In 2007, the Italian ministry of agriculture financed a Research Project on the "Anaerobic digestion of livestock manure and EU Nitrates Directive — Effect due to the anaerobic digestion on N availability in livestock manure for overcoming the limit of 170 Kg N ha-1 year-1 superimposed by imposto EU Nitrates Directive". The main aim of the reported study was to verify the N-fertilizer properties of a digestate coming from a swine livestock manure, taking into account the possibility to utilize this processed agricultural waste of animal origin for limiting the risk of environmental pollution. Hereafter, results related to the effect of the digested and not-digested solid fraction of this bovine livestock manure applied as N-organic fertilizers on lettuce growth in a greenhouse experiment are reported.

Decarboxylation

Bio-oil contains considerable amounts of acids such as acetic, formic, and butyric acid, resulting in low pH values (c. a. pH 2-3). The presence of these acids creates various practical challenges for bio-oil applications. Highly corrosive nature makes bio-oil not suitable for applications with metals and rubber. Further, the presence of acids would increase O/C ratio and make bio-oil more reactive. Accordingly, it is critical to develop chemistries that can deal with carboxylic acids when upgrading bio-oil. Decarboxylation refers to the removal of oxygen in the form of CO2 from a carboxylated compound and can be given in a general equation as follows (eq.(2) ):

RCO2H — RH + CO2 (2)

Insights on effective catalysts for removing oxygen in carboxylic acids can be obtained from studies on decarboxylation of model systems that include stearic, palmetic, benzoic, and heptanoic acids. Equations (3) and (4) depict the thermodynamic favorability of the decarboxylation reactions. The negative values for AG° implies that the decarboxylation reactions of acetic and benzoic acids have a significant activation energy barrier to overcome[44].

CH3CO2H — s

► CH4 + CO2

AGo =

— 68.5 kJ / mol

(3)

C6H5CO2H-

— C6H6 + CO2

II

О

%

— 54.3 kJ / mol

(4)

Biodiesel research is an important area to look for information related to decarboxylation. Fatty acids and fatty acid methyl esters from biodiesel industry have been subjected further deoxygenation with the intension of obtaining higher quality liquid fuels [45, 46]. In one such study, Pd has been identified to be an active metal for decarboxylation of fatty acids present in plant oil. In this study, the ability to convert heptanoic acid to octane was investigated using Pd/SiO2 and Ni/АЬОз catalysts [47-50]. It was reported that 98% acid conversion was obtained with Pd/SiO2 at 330oC but only 64% was reported by Ni/АЬОз [44].

Pd supported on active carbon has also been tested as the catalyst for decarboxylation of stearic acid at 300oC. The results indicated that the reaction was selective toward n — heptadecane [47]. Further, they claimed that conducting the reaction in the presence of hydrogen increased the rate of decarboxylation. А comparative study performed with thermal and catalytic deoxygenation of stearic acid further proved that catalytic deoxygenation is highly selective toward hydrocarbons. In this study, 5%Pd supported on mesoporous silica, SBA-15, MCM-41and zeolyte-Y has been used as the catalyst. It was reported that SBA-15 had a selectivity of 67% for n-pentadecane [48]. The study further revealed that the deoxygenation activity reduces in the order as SBA -15 > MCM-41 > zeolite-Y.

In an analogous study, pure palmitic acid, stearic acid, and a mixture of 59% of palmitic and 40% of stearic acid was deoxygenated over 4 % Pd/C catalyst at 300 oC and 5% H2 in argon at 17 bar of pressure. The conversion of the catalyst was reported to be over 94% after 180 min of the reaction time with a selectivity of 99% [51]. The kinetic behavior of decarboxylation of ethyl stearate over Pd / C has been investigated with the aim to verify the reaction mechanism. As shown in figure (9), decarboxylation of ethyl stearate proceeded through fatty acid decarboxylation to the desired и-heptadecane. The produced paraffin simultaneously dehydrogenated to unsaturated olefins and aromatics. A kinetic model has been developed based on the proposed reaction network in figure (9) using Langmuir — Hinshelwood mechanism with the assumptions that the surface reaction is rate limiting and the adsorption reaction is rapid compared to surface reaction [52]. The rate equation for the proposed reaction scheme can be represented in a simplified form as shown in eq.(5). According to the rate information, step 6 in figure (9) can be considered as the rate limiting step with the rate constant of 1.45×10-12/min. Both decarboxylation steps which were represented in step 4 and 5 is shown to be the fastest steps in the scheme.

ki •C (5)

Ti-7—————

1+ Z Ki • Ci

(ri: reaction rate, ki: lumped reaction rate, Ci: concentration, Ki: equilibrium constant )

image135

Aromatic C17 compunds

Figure 9. Decarboxylation of elthyl stearate ( Information was adapted from Snare et al.[52])

HZSM-5 can be considered as a versatile catalyst that has the ability to do both dehydration and decarboxylation. For example, decarboxylation of methyl esters to hydrocarbon fuels has been studied using methyl octonoate (MO) on HZSM-5 [53]. The catalyst showed strong signs of MO adsorption on to the catalyst surface. This reaction produced significant amounts of C1-C7 hydrocarbon compounds and aromatics. Formation of octonic acid as a primary product indicates that acidic hydrolysis reaction has taken place. However, it was noted that these primary products further undergo conversion into aromatic compounds. The proposed reaction scheme for the MO conversion is presented in figure (10).

image136

Direct Cyclization

Figure 10. A possible reaction pathway for the deoxygenation of methyl octonoate ( Information was adapted from Danuthai et al. [53] ).

Rather than complete removal, partial removal of oxygen to aldehydes or ketones would also be useful during upgrading since the latter product(s) can go through HDO pathway relatively easily. Various studies have been conducted in this regard and many have used benzoic acid as the model compound [54-58]. In such a study, different weak base catalysts such as MnO2, CeO2, MgO, ZnO, Fe2O3, K2O supported on SiO2, AhO3, TiO2 have been tested for upgrading the acid-rich phase of bio-oil through ketonic condensation. The study further evaluated the effect of the presence of water on ketonic condensation of three model components, phenol, p-methoxyphenol, and furfural (typically seen in bio-oil). They reported that CeO2 on Al2O3 and TiO2 had better catalytic activity and tolerance to water. Although the presence of water and phenol did not have a significant impact on the ketonic condensation of acetic acid, the presence of furfural exhibited a strong inhibitory effect on the reaction [54].

Recent studies reported that the best catalysts for the conversion of carboxylic acids to aldehyde /alcohol(s) were Al2O3, SiO2, TiO2 or MgO supported transition/noble metals such as Pt, Pd, Cu, or Ru. For example, in deoxygenation of methyl stearate and methyl octanoate over alumina-supported Pt [59], 1% Pt/y-AhO3 reported to be highly active and selective toward deoxygenation. They reported that 1% Pt/TiO2 displayed a higher Q hydrocarbon selectivity than 1% Pt/AhO3. This was attributed to the presence of larger oxygen vacancies on the TiO2 support [59]. Results of a similar screening study for the decarboxylation of stearic acid are depicted in the figure (11). It is apparent that Pd, Pt on activated carbon and 5% Ru on MgO resulted in the highest conversion of stearic acids to hydrocarbons.

image137

Figure 11. Conversion of stearic acid on different catalysts ( Information was adapted from Snare et al. [45].)

Contribution to household income and food security

Indicative economic assessments included the use of gross sales for the raw material (farm gate) and ethanol. Annualized sugarcane net sales were compared to household annual expenditures to allow assessment of cane contribution to household income. Integration of commodity prices gives insight on the potential contribution of bio-fuels to household poverty alleviation and overall development of rural areas.

3. Results

3.1. Suitability

The agro-ecological settings favor the growing of sugarcane with a potential 10,212,757 ha (49.6%) at a marginal level of production with 2,558,698 ha (12.4%) land area potentially not suitable for cane production. Although the current production is far below the potential production "in [12]", the related cane production is 908,935,330 and 60,769,069 tons respectively. It is also evident that there is possibility of increasing production through expansion of land area under sugarcane.

1. Suitability of sugarcane production and conflict visualization between food crops and gazetted areas in Uganda

image163

Figure 3. Sugar cane suitability ratings (i) and conflict visualization between food crops and gazetted areas

The marginal productivity of cane in Uganda is a function of Rainfall amount and the atmospheric temperature. Nevertheless the average optimum yields (89 ton / ha) at marginal level of productivity are comparable to yields of 85 ton / ha in a commercialized production in Brazil "in [13] ".

Expanding acrage under sugarcane is likely to increase pressure on gazetted biodiversity rich areas including wetlands with consequent potential loss of bio-diversity.

Sugarcane and maize (food crop) have similar ecological requirements, presenting a situation of high potential land-use conflict as 49.6 % of arable land can be grown with both sugarcane and food crops (figure 3 i). Figure 3 ii), shows 14 % of the land where sugarcane has potential conflict with gazetted areas of which 4.3 % has potential conflict with forest reserves.

Sugarcane, given its energy balance advantage, is likely to be beneficial if promoted as bio­fuel feedstock as this is likely to increase sugarcane prices to the benefit of the small scale farmer.

Biomass Production in Northern Great Plains of USA — Agronomic Perspective

Qingwu Xue, Guojie Wang and Paul E. Nyren

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/52917

1. Introduction

The development of biofuel is an important measure to meet America’s energy challenges in the future. In the 2007 Energy Independence and Security Act, the U. S. government mandates that 136 billion liters of biofuel will be produced by 2022, of which 60 billion liters will be cellulosic ethanol derived from biomass [1-3]. Currently, ethanol is one of the biofuels that has been developed extensively. In the U. S., initial efforts for ethanol production were focused on fermentation of sugars from grains (especially maize). However, there have been criticisms for ethanol production from maize because of low energy efficiency, high input cost and adverse environmental impacts [4-5]. Biofuels from biomass feedstocks are more attractive because biomass is a domestic, secure and abundant feedstock. There are at least three major benefits for using biofuels. The very first benefit is national energy security. To reduce the reliance of imported oil for transportation, alternative energy options must be developed. Economically, a biofuel industry would create jobs and ensure growing energy supplies to support national and global prosperity. Environmentally, producing and using more biofules will reduce CO2 emission and slow down the pace of global warming and climate change.

There are several sources of biomass feedstocks in forest and agricultural lands. The agricultural resources for biomass include annual crop residues, perennial crops, and miscellaneous process residues and manure [2, 3, 6]. Among the agricultural sources, the dedicated biofuel crops based on perennial species have been considered to the future of the biofuel industry and are the focus of intense research [2, 3, 6-8]. In addition, perennial biofuel crops also can provide other environmental and ecological benefits such as improving soil health, providing wild life habitat, increasing carbon sequestration, reducing soil erosion and enhancing water conservation [2, 9]. A key factor for meeting the government’s goal is the development of biomass feedstocks with high yield as well as ideal quality for conversion to liquid fuels and valuable chemicals [2-3, 6-8,10].

Подпись:© 2013 Xue 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.

The Northern Great Plains (NGP) of USA has been identified as an important area for biomass production. In particular, North Dakota is ranked first in potential for producing perennial grasses and other dedicated biofuel crops among the 50 states [10]. With about 1.2 million ha of CRP (Conservation Reserve Program) land and over 2.8 million ha of marginal land that are not suitable for cropping, the state has great potential for liquid biofuel production from biomass crops such as perennial grasses [11]. Before the great potential for biofuel production can be realized, questions still remain for developing management practices and their economic and environmental benefits for biofuel crops, such as appropriate species in certain areas, biomass yield potential and quality, harvesting scheduling (e. g., annual vs. biennial harvest), and effects on soil health and carbon sequestration.

In this paper, we review the current research progress for developing perennial biofuel crops in the NGP, primarily based on long-term field studies. We start to briefly discuss the species selections for biofuel crops in the USA and Europe. Then, we focus on development of crop management strategies for high yield as well as ideal quality. Finally, some possible environmental and ecological benefits from perennial biofuel crops are briefly discussed.

Field loss

The yield losses of different herbaceous biomass feedstocks while standing in the field will impact the harvest systems and the windows of opportunities to gather the feedstocks into storage. The inventory losses will be impacted by herbaceous biomass feedstocks, package configurations and integrity, storage facilities and time in storage. Loss of dry matter is also an important parameter in biomass collection and transportation.

Biomass loses dry matter due to its high moisture or dryness. Leaves and other fragile parts of the plant are broken and lost in the wind or mixed with soil. Some of the losses occur during storage due to fermentation and breakdown of carbohydrates to carbon dioxide and other volatiles. Unfortunately the exact account of switchgrass losses in the field or during storage is not available. Sanderson et al. [21] reported dry matter loss in baling and storage of switchgrass and stated that the overall losses were less than for legume hay. They estimated that switchgrass bales stored outside without protection resulted in a dry matter loss of 13% of the original bale dry weight. They also estimated that dry matter loss of 1-5% during baling depending on the moisture content. Kumar and Sokhansanj estimated field and storage losses for straw and stover [22]. Other studies have also estimated the dry matter loss of biomass during storage, collection and transport [23-26]. Turhollow [27] estimated the losses from switchgrass to be similar to losses in alfalfa. The study estimated 8% losses for a mower-conditioner, 3% for a rake, 10% for a round baler, and 0.1% for a round bale wagon. He estimated average loss of 15% over 6 months of storage. A recent study showed that the dry matter loss in switchgrass collection (including storage) is less than 2% for different collection methods.

Moisture causes damage (microorganism growth) and subsequent dry matter losses in stored switchgrass bales. Several studies have shown that dry matter losses in switchgrass bales are greater for bales stored outside as compared to bales stored inside [18,22,28]. Moreover, dry matter losses are far greater for covered rectangular bales than uncovered round bales [18]. Large uncovered round bales had a better economic return than covered rectangular bales, when considering the cost due to mass loss during storage [18]. However, another study highlighted their successful use of rectangular bales [29]; the cost of covered storage was more than offset by the reduction in hauling cost for the square bales.

. Improvement of ozonation on biodegradability of organic matters

Подпись: water ozonation Figure 8. Degradation effects of different layers in BAC bed with ozone pretreatment

Relevant researches indicate that ozonation can change the molecule weight distribution, structures and the biodegradability of the organics in water. To thoroughly understand the role organics degradation and ozonation played in the whole process, degradation of the organics without dosage of ozone shall be taken for comparison. Variation of DOC, BDOC, BDOC/DOC on each layer of BAC bed with ozone or without ozone are both reviewed, the result is shown in Fig. 8 and 9.

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Figure 9. Degradation effects of different layer in BAC bed without ozone pretreatment

As shown in the figure, no matter the ozone is added or not, the tendencies of organics degradation in BAC bed are similar. With the addition of ozone, the properties of organics after ozonation will change, and the amount of BDOC increased. Viewed from aspect of general efficiency of removal, with the addition of ozone, the removal rate of DOC is 31 %, while 18 % removal rate without ozone.

According to further analysis of the data in Fig. 9, results show that, degradation efficiency of DOC without ozone is 18.4 %, DOC of outflow from the BAC bed is 5.92 mg/L and the removal quantity of DOC is 1.351 mg/L, in which the removal quantity of BDOC is 0.676 mg/L. In this case, the removal of NBDOC takes a proportion of 49 % in the total removal of DOC. Bio-degradation mainly removes BDOC in organics, while adsorption mainly removes NDOC and part of BDOC. That is to say, for BAC process absorption takes a proportion of 49 % during the entire removal process without dosage of ozone. Similarly, to analyze the data shown in Fig. 8, the variation of adsorption and bio-degradation effects during the organic degradation process whether added with ozone or not are shown in Table 2.

BAC/DOC Degradation

With Ozone Pretreatment

Without Ozone Pretreatment

Adsorption

35 %

>49 %

Biodegradation

65 %

<51 %

Table 2. Effect of ozonation on adsorption and biodegradation during BAC process

According to Fig. 3, on the aspect of the adsorption and bio-degradation in DOC removal process, ozonation can enhance the bio-degradation effect greatly, while exert a negative effect on adsorption of activated carbon.