Category Archives: Microbes and biochemistry of gas fermentation

Lignin in thermosets

The lignins of different resources have been incorporated into various thermoset resins. Amorphous/heterogeneous nature and the complex structural composition of lignin result their behavior as either like a filler or like a reactive macromonomer in epoxy resin systems. Man- souri et al. [181] characterized the alkaline lignin and suggested their possible use for phenol- formaldehyde resin due to the availability of huge OH groups. Peng et al. [182] reported the fabrication of phenol-formaldehyde thermoset resin with lignin fillers and investigated their chemo-rheological properties. They found that the curing rate of the resin system decreased with increasing lignin content. Guigo et al. [183] fabricated the poly(furfuryl alcohol)/lignin compo­site resins and reported their mono phase behavior. This indicates the reactive monomer behavior of lignin in this thermoset system. Thielemans et al. [184] investigated the effect of kraft lignin on unsaturated thermosetting resin, which was a mixture of epoxidized soybean oil and styrene, for the fabrication of natural fibre reinforced thermoset composites. They found the complete solubility of lignin into the resin system and their result on natural fibre composites indicateed the compatibilizing effect of lignin. Nonaka et al. [185] reported the fabrication of a new resin system by aqueous mixing of alkaline kraft lignin with polyethylene glycol diglycidyl ether (PEGDGE), and a curing reagent. They identified the complete compatibility between lignin and PEGDGE though the studies on dynamic mechanical analysis.

Cetane index

Krisnagkura [1986] proposed the equation for the estimation of cetane index (CI) based on the saponification and iodine values, recommending not to be used for oils, only for methyl esters. Namely, it has been previously documented that despite the fact that triglycerides and fatty acid methyl esters have similar saponification and iodine values, like it was ob­tained in this study too, cetane indexes of oils are generally much lower than those of meth­yl ester derivates. Thus, discussion on CI of frying oil will not be made. In this work, the CI value was 38 and this value less than the CI of Egyptian diesel, EN 14214 and D-6751 (55, 51 and 47 respectively). Siler-Marinkovic’ and Tomasevic [1998] also used CI for the characteri­zation of methyl esters produced from crude frying oils, and the estimated values were from 49.7 to 50.9. As an alternative to cetane number, cetane index is also an indicator of ignition quality of the fuel and is related to the time that passes between injection of the fuel into the cylinder and onset of ignition [Knothe, 2005].

Test

Produced

Biodiesel

Egyptian Diesel oil

Biodiesel

(EN14214)

Biodiesel

D-6751

Flash point oC

202

”/> 55

”/> 101

”/> 130

Density g/cm3 @ 15.56 oC

0.9055

0.82-0.87

0.86-0.9

Kinematic Viscosity cSt @ 40 oC

8.38

1.6-7

3.5-5

1.9-6

Kinematic Viscosity cSt @ 100 oC

4.34

Total acid number (mg KOH/g)

0.48

Nil

< 0.5

< 0.8

Cloud point oC

3

— 4

Pour point oC

0

4.5-15

Initial boiling point IBP oC

229

Cetane number

63.8

Min. 55

”/> 51

”/> 47

Calorific value MJ/Kg

38.54

Min. 44.3

32.9

Total S wt%

0.12

Max. 1.2

< 0.01

< 0.05

Ash content wt%

0.002

Max. 0.01

0.02

< 0.02

Carbon residue wt%

0.63

Max.0.1

< 0.03

< 0.05

Copper strip corrosion @ 100oC

1a

1a

Class 1

No. 3 Max.

Water content wt%

0.08

Max. 0.15

< 0.05

0.05

Iodine number mg I2/100 g

60

120

Table 3. Physicochemical properties for produced biodiesel compared to the Egyptian standards of petro-diesel fuel and two international biodiesel standards

Bioconversion

Bioconversion of lignocellulosic biomass to fuels involves three major steps: 1) pretreatment — to effectively broken the biomass structure and release the biomass components i. e. cellu­lose, hemicellulose, and lignin, and therefore increase the digestibility of the biomass; 2) enzymatic hydrolysis — to hydrolyse cellulose and hemicellulose and produce fermentable sugar, such as glucose, xylose etc.; 3) fermentation — to convert the biomass hydrolysate sug­ars to the desired products. OPEFB was intensively investigated as a potential substrate for the production of biofuels, such as ethanol, butanol, and biogas etc. Among the biofuels pro­duced through bioconversion of OPEFB, cellulosic ethanol is the most intensively studied.

Two stage dilute acid hydrolysis was applied for OPEFB bioconversion to ethanol, 135.94 g xylose/kg OPEFB and 62.70 g glucose/kg OPEFB were produced in the first stage and 2nd stage, respectively [8]. They were then fermented to ethanol using Mucor indicus and Saccha — romyces cerevisiae, respectively, and the corresponding ethanol yields were 0.45 and 0.46 g ethanol/g sugar.

Alkali is the most often used pretreatment chemical for cellulosic ethanol production from OPEFB. Kassim et al. pretreated OPEFB using 1% NaOH followed by mild acid (0.7% HjSOJ hydrolysis and enzymatic saccharification [26]. A total of 16.4 g/L of glucose and 3.85 g/L of xylose were obtained during enzymatic saccharification. The OPEFB hydrolysate was fermented with Saccharomyces cerevisiae and an ethanol yield of 0.51 g/g yield was obtained, suggesting that OPEFB is a potential substrate for cellulosic ethanol production. Han and his colleagues investigated ethanol production through pilot scale alkali pretreatment and fer­mentation [9]. The best pretreatment condition was 127.64 °C, 22.08 min, and 2.89 mol/L

NaOH. Enzyme loading of 50 FPU/g cellulose resulted in 86.37% glucose conversion in their Changhae Ethanol Multi Explosion (CHEMEX) facility. An ethanol concentration of 48.54 g/L was obtained at 20% (w/v) pretreated biomass loading, along with simultaneous saccha­rification and fermentation (SSF) processes. This is so far the highest reported ethanol titre from OPEFB. Overall, 410.48 g of ethanol were produced from 3 kg of raw OPEFB in a single run, using the CHEMEX 50 L reactor.

Jung and his colleagues tried aqueous ammonia soaking for the pretreatment of OPEFB and its conversion to ethanol [12]. Pretreated OPEFB at 60°C, 12 h, and 21% (w/w) aqueous am­monia, showed 19.5% and 41.4% glucose yields after 96h enzymatic hydrolysis using 15 and 60 FPU of cellulase per gram of OPEFB, respectively. An ethanol concentration of 18.6 g/L and a productivity of 0.11 g/L/h were obtained with the ethanol yield of 0.33 g ethanol/ glucose.

Lau et al. successfully applied ammonia fibre expansion (AFEX) pretreatment for cellulosic ethanol production from OPEFB [14]. The sugar yield was close to 90% after enzyme formu­lation optimization. Post-AFEX size reduction is required to enhance the sugar yield possi­bly due to the high tensile strength (248 MPa) and toughness (2,000 MPa) of palm fibre compared to most cellulosic feedstock. Interestingly, the water extract from AFEX-pretreat — ed OPEFB at 9% solids loading is highly fermentable and up to 65 g/L glucose can be fer­mented to ethanol within 24 h without the supplement of nutrients.

OPEFB was also used for butanol production. Noomtim and Cheirsilp (2011) studied buta­nol production from OPEFB using Clostridium acetobutylicum [27]. Again, the pretreatment by alkali was found to be the most suitable method to prepare OPEFB for enzymatic hydrol­ysis. 1.262 g/L ABE (acetone, butanol and ethanol) was obtained in RCM medium containing 20 g/L sugar obtained from cellulase hydrolysed OPEFB. Ibrahim et al also investigated OPEFB as the potential substrate for ABE production [28]. Higher ABE yield was obtained from treated OPEFB when compared to using a glucose-based medium using Clostridium bu — tyricum EB6. A higher ABE level was obtained at pH 6.0 with a concentration of 3.47 g/L.

The accumulated acid (5 to 13 g/L) had inhibitory effects on cell growth.

Nieves et al. investigated biogas production using OPEFB. OPEFB was pre-treated using NaOH and phosphoric acid [29]. When 8% NaOH (60 min) was used for the pretreatment,

100% improvement in the yield of methane production was observed and 97% of the theo­retical value of methane production was achieved under such pretreatment condition. The results showed that the carbohydrate content of OPEFB could be efficiently converted to methane under the anaerobic digestion process. O-Thong et al. investigated the effect of pre­treatment methods for improved biodegradability and biogas production of oil palm empty fruit bunches (EFB) and its co-digestion with palm oil mill effluent (POME) [30]. The maxi­mum methane potential of OPEFB was 202 mL CH4/g VS-added corresponding to 79.1 m3 CH4/ton OPEFB with 38% biodegradability. Co-digestion of treated OPEFB by NaOH pre­soaking and hydrothermal treatment with POME resulted in 98% improvement in methane yield comparing with co-digesting untreated OPEFB. The maximum methane production of co-digestion treated OPEFB with POME was 82.7 m3 CH4/ton of mixed treated OPEFB and POME (6.8:1), corresponding to methane yield of 392 mL CH4/g VS-added. The study
showed that there was a great potential to co-digestion treated OPEFB with POME for bio­energy production.

image199In summary, OPEFB has been frequently investigated as a substrate for biofuel production through bioconversion. Cellulosic ethanol production was most intensively investigated and the highest ethanol titre of 48.54 g/L was obtained through alkali pretreatment in a pilot scale reactor [9]. Although not much research has been done for ABE and biogas production, the few reports summarized in this paper suggest that OPEFB is also potential substrate for butanol and biogas production. Throughout the reports reviewed, alkali-based pretreatment methods, such as NaOH alone, NaOH followed by acid, and ammonium fibre expansion (AFEX) pretreatment are the most effective in enhancing OPEFB digestibility.

2. Conclusion

In conclusion, OPEFB is the most potential renewable resource for biofuel production in South­east Asia. It can be converted to biofuels through thermo-chemical or biological conversion. Pretreatment of OPEFB is necessary for both routes of conversion and alkali pretreatment is the most effective. A summary of OPEFB conversion technology is shown in Fig. 2.

Oil Palm Empty Fruit Bunch

Подпись: Pretreatment

Подпись: > Chemical

Biological

Physical-chemical

Подпись: Biological ConversionПодпись: Pyrolysis

Подпись: Bio-oi Подпись: Syngas image292 Подпись: Ethano Подпись: Butanol Biogas

Thermo-chemica Conversion

Figure 2. Biofuel production from OPEFB.

Among the studies on OPEFB thermo-chemical conversion, it seems that gasification is the most suitable approach to obtain bioenergy from OPEFB and has potential in commerciali­
zation. Pyrolysis, on the other hand, produced very complex bio-oil with high viscosity and water content, making it challenging for commercialization. However, charcoal from OPEFB pyrolysis can be a potential commercial product. Compared to other palm oil residues, such as oil palm kernel, OPEFB may not be a good candidate for solid fuel production, even after torrefaction pretreatment due to its high water content and low energy capacity.

Biological conversion of OPEFB is another route to obtain biofuels from OPEFB. Cellulosic ethanol production was most intensively studied and around 50 g/L titre was obtained with 20% (w/v) biomass loading through NaOH pretreatment. AFEX also showed potential in OPEFB pretreatment and a glucose yield of 90% was obtained with 9% biomass loading. The water extract of the AFEX pretreated OPEFB was highly fermentable. OPEFB also showed some promising preliminary results in ABE (acetone, butanol and ethanol) and biogas produc­tion; however, further investigation is necessary to enhance OPEFB conversion potentials in these areas.

For both thermo-chemical and biological conversion of OPEFB, pretreatment technology is the key for the process cost. Although alkali pretreatment is effective, scaling-up the process re­quires huge amount of acid to neutralize the base in the pretreatment solution. In addition, be­fore alkali pretreatment, OPEFB should be milled to reduce its size, which is energy­consuming. Steam explosion is effective for a lot of lignocellulosic biomass, however not much research was found on its pretreatment of OPEFB. A cost-effective pretreatment is the key for the successful commercialization of OPEFB conversion technologies for biofuel production.

Acknowledgement

The. authors are grateful for the financial support to the research on cellulosic ethanol by the Science and Engineering Research Council of the Agency for Science, Technology and Re­search (A*STAR), Singapore.

Author details

Anli Geng

Address all correspondence to: gan2@np. edu. sg

School of Life Sciences and Chemical Technology, Ngee Ann Polytechnic, Singapore

Sustainability through value addition

Due to the uncertainty in long term availability of fossil fuels and their continuous threat to environment through greenhouse gas emission, there is a drive across the globe towards the exploration of various biorefinery systems. Production of biofuel creates impact in utilization of biomass, replacement of possible extend of gasoline, reduction of greenhouse gas emission and the creation of significant amount of coproducts [112]. Biofuel production from biomass tends to strengthen the entire value chain (farming community-biofuel industries-consumers) and claims as the probable sustainable alternate for the conventional fossil fuel systems. Biomass is the sustainable feedstock for biofuel industries and biofuel provides ecological safety towards sustainable transportation, however the emerging concern is about the co/by-products. If they create challenging environmental issues in disposal, sustainability of this technology is challenged. Thus, value addition to these biofuel coproducts plays key role for the sustainabili­ty of biofuel technology in long term perspective [113]. With this understanding, the ultimate aim of biorefinery is focused to satisfy the conceptual "triple bottom line" of sustainability that includes (i) economic development; commercial value for biomasses, biofuels and coproducts, (ii) social development; appearance of new manufacturing sectors as well as creation of rural job opportunities, and (iii) environmental/resource sustainability; greenhouse gas reduction and eco-friendly green products [114]. In order to ensure the sustainability of biofuel technology it is essential to address various issues including (i) "food vs. fuel" due to the usage of edible resource for biofuel production, (ii) resource availability/management; effective utilization of land/water resources, (iii) environmental impact; issues related to land/water quality reten­tion, conversion of grasslands/forests to agricultural fields and the efficient disposal/utiliza — tion of biofuel coproducts and (iv) validated measures: policy making and certification/ standardization [115]. Scale-up activities of biofuel production is essential due to the increas­ing demand for the substitution of fossil fuel. However, it is significantly controlled by vari­ous factors such as effective land usage for the larger biomass generation, water availability for agricultural forming, retention of soil quality, environmental impact of biofuel coproducts and labor market shift towards biorefinery [116117]. The successive transformation of biofuel production from conventional to second generation effectively addresses the issues related to water consumption. Lignocellulosic ethanol industries utilise perennial crops such as miscan — thus and switch grass, which grows on marginal land and consume very less water. The challenge is towards biofuel coproducts. Failure ofhandling these large quantity coproducts will ultimately create serious environmental issues. These emerging technologies related to the effective utilization of biofuel coproducts that holds significant quantity of renewable content significant­ly substitute/ replace petroleum-based products and helps in reduction of greenhouse gas emission.

Bioethanol extraction

Bioethanol is one of the most important renewable fuels due to the economic and environ­mental benefits of its use. The use of bioethanol as an alternative motor fuel has been steadi­ly increasing around the world for the number of reasons. 1) Fossil fuel resources are declining, but biomass has been recognized as a major reasons World renewable energy source. 2) Greenhouse gas emissions is one of the most important challenges in this century because of fossil fuel consumption, biofuels can be a good solution for this problem. 3) Price of petroleum in global market has raising trend. 4) Petroleum reserves are limited and it is monopoly of some oil-importing countries and rest of the world depends on them. 5) Also known petroleum reserves are estimated to be depleted in less than 50 years at the present rate of consumption. At present, in compare to fossil fuels, bioethanol is not produced eco­nomically, but according to scientific predictions, it will be economical about 2030.

image184

Figure 4. The IR spectrum of oil after two step transterification (produced biodiesel) process

Biomass commonly gathers from agricultural, industrial and urban residues. The wastes used for bioethanol production are classified in three groups according to pretreatment process in sugary, starchy and lignocellulosic biomasses. Lignocellulosic biomass, including forestry residue, agricultural residue, yard waste, wood products, animal and human wastes, etc., is a renewable resource that stores energy from sunlight in its chemical bonds. Lignocellulosic biomass typically contains 50%-80% (dry basis) carbohydrates that are poly­mers of 5C and 6C sugar units. Lignocellulosic biomasses such as waste wood are the most promising feedstock for producing bioethanol.

Bioconversion of lignocellulosic biomass to ethanol is significantly hindered by the structur­al and chemical complexity of biomass, which makes these materials a challenge to be used as feedstock for cellulosic ethanol production. Cellulose and hemicellulose, when hydro­lyzed into their component sugars, can be converted into ethanol through well-established fermentation technologies. However, sugars necessary for fermentation are trapped inside the crosslinking structure of the lignocellulose.

Conventional methods for bioethanol production from lignocellulosic biomasses take three steps: pretreatment (commonly acid or enzyme hydrolyses), fermentation, distillation. Pretreat­ment is the chemical reaction that converts the complex polysaccharides to simple sugar. pretreatment of biomass is always necessary to remove and/or modify the surrounding ma­trix of lignin and hemicellulose prior to the enzymatic hydrolysis of the polysaccharides (cellulose and hemicellulose) in the biomass. Pretreatment refers to a process that converts lignocellulosic biomass from its native form. In general, pretreatment methods can be classi­fied into three categories, including physical, chemical, and biological pretreatment. In this step, biomass structure is broken to fermentable sugars. This project focused on chemically and biologically pretreatment. For example: this project shows the effect of sulfuric acid, hy­drochloric acid and acetic acid with different concentration by different conditions also shows the effect of cellulase enzyme by different techniques. Then fermentation step in which there are a series of chemical or enzymatic reactions that converted sugar into etha­nol. The fermentation reaction is caused by yeast or bacteria, which feed on the sugar such as Saccharomyces cerevisae. After that, distillation step in which the pure ethanol is separated from the mixture using distiller which boil the mixture by heater and evaporate the mixture to be condensate at the top of the apparatus to produce the ethanol from joined tube.

image185

The way to manufacture bioethanol is basically the same as that of liquor. Generally, saccha — rinity material such as sugar and starchy material such as rice and corn are saccharified (Figure 5-7), fermented and distilled till absolute ethanol whose alcoholicity is over 99.5%. It is technically possible to manufacture ethanol from cellulosic material such as rice straw or wood remains.

Ligninin rubber blends

Although the history of lignin/rubber blend started in 1949, a very little work has been performed till date [186]. The role of lignin in rubber is identified as reinforcing filler and stabilizer or antioxidant. Kumaran et al. [186] performed an extensive research on the utiliza­tion of lignins in rubber compounding and identified the improvement of many properties.

They reported that the addition of lignin into rubber improved their tear, abrasion and flexural crack resistances. Kosfkova et al. [167] investigated the reinforcement effect of sulfur-free lignin with styrene butadiene rubber (SBR). They identified that the lignin blending with SBR influenced their vulcanizing behavior and enhanced the various physicomechanical properties significantly. In addition to that, Wang et al. [187] investigated the fabrication of latex/modified lignin blend and identified their effective water barrier properties. Processing condition of the lignin/rubber is critical for the achievement of better properties. Tibenham et al. [188] reported the hot-milling of lignin/rubber precursors with hexamethylenetetramine, which yields a vulcanizate. They also found that the modulus, tensile strength, and hardness properties were in the same order as the rubber reinforced with carbon blacks.

Fatty acid composition

As can be observed from Table 5, regardless of the fatty acid profiles were observed in the biodiesel produced from frying oil, consisting mainly of methyl esters of oleic (C 18:1), pal­mitic (C 16:0), and stearic (C 18:0) acids (30.60, 3.0 and 66.40 % respectively) and 2.8 % un­known fatty acid. these results are in agreement with the results obtained by Predojvic (2008) who reported that, fatty acid profiles were observed in the biodiesels produced from sun flower oil consisting mainly of methyl esters of oleic (C 18:1), palmitic (C 16:0), linoleic (C 18:2) and stearic (C 18:0) acids.

Parameters

Feedstock

Produced biodiesel

Acid value mg KOH/g

5.1

0.48

Iodine value mg ^/g

62.0

60.0

Saponification value mg KOH/g

199.5

207.0

Table 4. Some chemical properties of waste cooking oil (WCO) used as feedstock for methyl esters preparation and produced biodiesel

Fatty acid ester

Carbon number chain

Wt%

Molecular formula

Palmetic

16

3.00

C16H 32O2

Stearic

18

66.40

C18H36°2

Oleic

18

30.60

C18H34O2

Table 5. Composition of biodiesel obtained by transesterification of WCO using GC

1.6. Bioethanol

1.6.1. Property of ethanol Melting point: -114.15 Boiling point: 78.3 Molecular formula: C2H5OH Molecular weight: 46.07 Specific gravity: 0.789 Toxicity: Get intoxicated

1.7. Biomethane

1.7.1. Gas properties

1.7.1.1. Molecular weight

• Molecular weight : 16.043 g/mol

1.7.1.2. Solid phase

• Melting point : -182.5 °C

• Latent heat of fusion (1,013 bar, at triple point) : 58.68 kJ/kg

1.7.1.3. Liquid phase

• Liquid density (1.013 bar at boiling point) : 422.62 kg/m3

• Liquid/gas equivalent (1.013 bar and 15 °C (59 °F)) : 630 vol/vol

• Boiling point (1.013 bar) : -161.6 °C

• Latent heat of vaporization (1.013 bar at boiling point) : 510 kJ/kg

Coproducts of Biofuel Industries in Value-Added Biomaterials Uses: A Move Towards a Sustainable Bioeconomy

S. Vivekanandhan, N. Zarrinbakhsh, M. Misra and A. K. Mohanty

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/55382

1. Introduction

World population is expected to grow nearly 9 billion in 2040 and eventually increases the global energy demand by 30% compared to current conception [1]. The issues related to increasing trend of crude oil cost, depleting source of fossil fuels and emerging threat on greenhouse gas emissions are leading the global energy sector to undergo a fundamental transformation towards renewable energy sources [12]. As the result, a main focus is motivated on renewable energy technologies that are based on solar, wind and biofuels. In transportation point of view, biofuels receive extensive attention due to their versatility in storage and refilling. Both bioethanol and biodiesel come together as biofuel currently produced from renewable resources through two different pathways. In some countries like Brazil, biofuels are produced and marketed at competitive cost compared to petroleum-based fuels employing existing technology [34]. They also carry following advantages comparing to petro fuels; (i) create significantly less pollu­tants (SOx and NOx), which also mitigates CO2 emission, (ii) biodegradable nature lead to the less environmental leak risk and (iii) provides better lubricant effect, which enhances the engine life [5]. In addition, these emerging biofuel technologies will be expected to create more economic benefits to agriculture sectors and new rural job opportunities. Moreover, biofuels are attrac­tive options for future energy demand since they can be produced domestically by many countries while the respective retail and consumer infrastructure needs minimum modifica­tion; so does the existing engine and fueling technology [6].

However, biofuel foresees a challenging journey to benefit from its highest potentials and to guarantee a viable future. Primarily, it needs policy support and commercialization. At the

same time, research and development is crucial to conquer the challenges and bring sustain­ability to biorefinery facilities [7]. Major motivation for biofuels usage arises from the execution of biofuel policies by many countries, which mandates the incorporation of bio-counterpart into traditional fuels. United Kingdom introduced the Renewable Transport Fuels Obligation (RTFO) and encouraged the oil suppliers to incorporate biofuel into transport fuel between 2.5 and 5% during 2008-2010. RTFO’s ultimate aim is to increase this 5% upto 10% by 2020, which will reflect in the demand of minimum 5 million tonnes [8]. Renewable fuel blending mandates in Canada was implemented through Canadian Environmental Protection Act, which recom­mends 5% ethanol with gasoline (in 2010) and 2% biodiesel with diesel (in 2012) [9]. In South Africa, the National Biofuels Industrial Strategy was introduced by the government in 2007, which recommends the implementation of 2% biofuels into liquid road transport fuels by 2013 [10]. Currently India’s ~80% crude oil demand is satisfied by foreign suppliers, which is projected to rise 90% in 2025. In order to reduce this foreign dependency, India has announced the target of ethanol blending with gasoline 20% by 2017 [11]. In biofuel production, China has clear production goals to meet emerging demand in near future. China’s integrated biofuel polices (rural welfare, improved energy security, reduced fossil fuel dependence, and CO2 emissions) aimed to meet ~ 15% of the total transportation fuel demand by 2020 [12]. In Malaysia, the National Biofuel Policy initially planned to proceed with 5% biodiesel blend with 95% petroleum diesel, which is similar to Europe’s B5, which has been started from 2009. This will be implemented through short, medium and long term strategies aiming to reduce their petroleum imports [13]. In addition to that, many countries have already designed various incentive programs for the effective promotion of biofuel production including bioethanol and biodiesel. This implements 5-20% biofuel supplement into traditional fuels [14].

Such blending mandates of biofuels adopted by the E. U. and U. S. created a dispute of increased food prices. Besides, the contribution of corn bioethanol in addressing the global warming issues is very modest while having a small positive net energy balance; i. e. the energy return on investment (EROI) of corn bioethanol is low (=1.2-1.6) compared to oil (=9) [6]. The emerging challenges for 1st generation of biofuel industries that utilizes corn and soybean as a major feed stock for biofuel production motivated the search for non-food and more efficient energy feedstocks like jatropha, lignocellulosic biomass and algae. Among them, cellulosic matter will be the major feedstock for second generation biofuel, since it exhibits much higher yield per hectare in comparison with sugar or starch crops [6]. As a result, cellulosic biomass can potentially yield higher land fuel (135 GJ/ha) than corn kernel (85 GJ/ha) and soy (18 GJ/ha) [15]. Moreover, significantly higher carbon sequestration is another advantage of the use of cellulosic biomass in biofuel production compared to the first generation biofuel crops [6].

This biomass-biofuel conversion can be performed under three major classes and they are (i) conversion of renewable polysaccharides into sugar molecules and their effective fermentation into ethanol, (ii) syngas production and their bio/chemical conversion into alcohols and (iii) production of bio-oil though fast-pyrolysis and their upgrade into transportation fuels. Considering the lignocellulosic feedstock as the biofuel precursor, it is crucial to create the necessary infrastructure in many levels from biomass to biofuel production; agriculture — technology-policy. The new utilization of biomass would largely affect the agriculture sector and necessitates effective actions to ease the adaptation process. Biofuel production uses land which keeps it from food production and environmental preservation. Other issues might be

considered; soil erosion may worsen by expanding the biomass production, reduction of environmental land affects biodiversity and more pesticides and fertilizers may be used. Thus, the sustainability of biofuel is not achieved solely by a positive net energy balance [6]. In spite of all raised issues, it is important to bear in mind that biofuel still offers its advantages even if it has a small contribution compared to fossil fuels. In this regard, the two main challenges in biomass production can be (a) developing crops with suitable physical and chemical traits for biofuel production and (b) increasing biomass yields (double or more) [7]. How to put these two different strands into an integrated production strategy is important and brings new research topics into the whole agriculture picture. The outcome of such productivity-enhanc­ing innovations, research and development motivated by biofuel can be such that by 2050, the whole world population could be supplied enough diet while less cropland is used than today [6]. The respective biorefinery operation also needs improvements so that sugars can be produced from cellulosic biomass and fermented economically feasible and able to compete with production from corn and sugar. These include improvement in lignocellulosic pretreat­ment, reduction in enzyme (cellulase) cost, both cellulase production and ethanol fermentation by using modified microorganisms [7].

In general, the growth of biofuel industry consists of (i) increased production capacity and (ii) successful transformation of industrial technology from discrete batch method (small-scale) into continuous flow method (larger-scale) [16]. In most of the small scale manufacturing, the industries do not have the practice of collecting coproducts, thus they run with increased operating costs. Hence, larger-scale industries are keen in capturing their coproducts in order to reuse them in the production process, which results in the reduction of operating cost significantly. Thus, value-added processing may serve as a viable alternative that not only reduces the impact on the environment, but also generates additional revenue source for biofuel plants [17]. Sustainable bioeconomy road map that integrates renewable resources, biofuel production/ utilization and the value-addition to the respective coproducts is shown schematically in Figure 1. In recent years, biofuel coproducts have been utilised for the fabrication of various chemicals for diversified applications and used as the filler/reinforce — ment for polymer blends as well as composites. The emerging opportunities for the biofuel coproducts in biomaterials (polymers/ composites) applications make successive transforma­tion of coproducts to renewable feedstock with economic benefits. Capitalizing this transfor­mation enhances the economic viability and also the sustainability of biofuel industries. Thus, this chapter summarizes the various aspects in biomaterial applications of the biofuel copro­ducts and their role in sustainable bioeconomy.

Value-added biomaterials from biofuel coproducts

3.1. Distillers’ grains

3.1.1. As biofiller in producing polymeric biocomposites

The low cost of distillers’ grains (DDG and DDGS) is a key incentive for researchers to utilize them as biobased fillers in manufacturing polymer composites. Also, addition of DDG(S) to the polymer matrix can result in improved stiffness as long as proper treatments and proc-

essing aspects are taken into account. It is less than ten years that DDGS-containing biocom­posites has been reported in the literature. In this regard, the very first produced DDGS — containing composites exhibited low mechanical properties so that the utilization of DDG(S) as a biofiller in composite materials seemed to be not worthy in the beginning. However, recent works project a better future for DDG(S)-based biocomposites.

How to produce bio-ethanol

• Materials Sugarcane stems 5kg Dry yeast, 15g

• Items

Brix meter, 5L flask, Dimroth condenser, Liebig condenser, Stick, Beaker Cloth filter

1. Fermentation method

2. Mill juice out of Sugarcane stems. (about 3L of juice)

3. The juice is filtered out impurities.

4. Measurement Brix of juice.

5. Dry yeast is added to juice, the rate of 6g/L.

6. It keeps in the flask which sealed except the vent.

7. A cover is opened one day and once, then juice and dry yeast mixes so that air may en­ter with stick.

8. It continues until Brix becomes fixed.

9. Distillation method (Fig. 8)

10. Fermented juice is filtered out sediment.

11. It heats to boiling point in distiller.

12. Dimroth condenser is kept warm (about 70 degree) with hot water which is made to cir­culate by a pump.

13. Allihn condenser cools with tap water (about 20 degree).

14. Bio-ethanol which falls from the point of a allihn condenser is caught with beaker on ice.

1.4.1. Qualitative analysis for ethanol

Iodoform test on cold is special test for ethanol as the following: I ml ethanol layer mix with iodide and sodium hydroxide after that, the presence of yellow crystal and iodoform odor produced, this meaning presence of ethanol.

Saccharinitv

Material

sugarcane, sugar
beet, etc.

 

Ethanol alcoholicitv after fermentation

 

compression

 

Over 99. 5%

 

image253
image254

Fermen

-tation

 

abso ute

 

image255

saccharifi’

cation

 

image256

grinding

 

distillation

 

ethanol

 

enzyme

 

yeast

 

Cellulosic

material

 

image257

grinding

 

saccharification

 

wood remains,
lumber residues,
thinned wood, etc

 

hydrolyzation by

 

sulfuric acid

 

Figure 6. Production of absolute ethanol from Saccharinity, Starch and Cellulosic materials

 

image258

image187

image260

thprmnmPtFr

 

image261

C Did nutir eat

 

litblg cqnQfП1ЭГ

 

fraeticnatiii|E

"column

 

eald water in

 

image262

dii till feta

 

іпй — Ьишйійі tf irttUJii

 

HEAT

 

Figure 8. The distillation process for ethanol production.

 

3.2.4. Quantitative ethanol determination З.2.4.1. Direct injected GC method

Beverage sample solution (0.5 mL) was dispensed into an l-mL caped sample vial, and then 5 mL of 1% internal standard solution (equivalent to 50 mg) was added. After mixing, 0.1 pL of the sample solution was injected directly into a GC or GC/MS (Figure 9) with syringe (Anonymous. 1992; Collins et al., 1997).

 

gas chromatograph

 

mass spectrometer

 

injector

 

He inlet

 

image263

detector

 

column

 

evacuated chamber

 

heated oven

 

image188image189