Category Archives: Advances in Biofuels

Materials and Methods

The seaweed (E. cottonii) used in this work was obtained from Semporna, Sabah. The materials used were Yeast Peptone Dextrose (YPD) broth, S. cerevisiae pow­der, potato dextrose agar powder, distilled water, ethanol 98%, sodium hydroxide (NaOH), sodium chloride (NaCl), sulphuric acid 99% (H2SO4), phenol, sodium sulphate anhydrous (NaSO4H2O).

The equipments used were gas chromatography GC (Agilent, California), UV — vis spectrometer (Jasco UV-vis 650, Germany), conical flasks (250 mL), graduated cylinder (1 L), beakers (250 mL and 500 mL), blue cap bottles (1 L), pipettes (0.1 mL and 1 mL), pipette tips (0.1 mL and 1 mL), micro-centrifuge tubes 1.5 mL, cotton, loop, aluminium foil, sterile petri plates, balance, pH meter, autoclave (HICLAVE HVE-50, Japan), incubator, oven, fridge (5%), Bunsen burner, perma­nent marker pen, paper tape (for labelling), glass spreader, cuvette, oven, parafilm, filter paper 0.2 |rm, filtration unit, spectrophotometer, laminar flow cabinet, and 0.45 |rm Durapore (PVDF) syringe-driven filter.

Before fermentation of the E. cottonii, the broth media and agar medium was prepared and sterilised. Initially 20 g of potato dextrose powder was weighed and mixed with 1,000 mL distilled water in a sterile blue cap bottle. The pH was adjusted to pH 7 using 1 mol/L NaOH. A clean glass rod was flame sterilised to stir the medium. The nutrient agar did not fully dissolve until it was autoclaved at 121% for 20 min (HICLAVE HVE-50, Japan). Following that, the agar medium was allowed to cool to around 45%. Next, 20 mL of agar was carefully poured out into sterile plastic petri dishes. The YPD (yeast peptone dextrose) broth was mixed in the fol­lowing formula: 10 g yeast extract, 20 g peptone and 20 g dextrose (glucose). Following that, the broth was mixed with H2O to make up 1 L. The pH was adjusted to pH 7 using 1 mol/L NaOH and then autoclaved at 121% for 20 min (HICLAVE HVE-50, Japan). This preparation was conducted in an aseptic environment.

Subsequently, the yeast suspension was prepared. Firstly, 5 g of dry yeast powder was dissolved in 100 mL of warm water at 30%. The solution was incubated in a rotary incubator for 30-60 min prior to use. A portion of the culture suspension was used for inoculation and the remainder was kept as stock in glycerol (2:1 v/v glyc­erol and yeast solution at -82%).

The innoculum was prepared by aseptically transferring the yeast suspension into 100 mL of sterilised medium (YPD) and cultured in a rotary incubator. The incubator was set to 200 rpm and 32%. Yeast population (CFU/mL) was monitored periodically every 3 h for 36 h. The spread plate technique was used to obtain the colony forming units per mL, CFU/mL. After 48 h at 30%, yeast growth was moni­tored by measuring the optical density (OD) at 620 nm (OD620) after every 3 h. A calibration curve was constructed based on the population cell number and OD620 measured.

Next, the fresh substrates (E. cottonii) were prepared by cutting the samples into ~0.5 cm x 0.5 cm. The substrate was then mixed with water in 1:4 volume ratios and further size reduced using a blender for about 10 min, producing finely shredded seaweed slurry. It was stored in a refrigerator at 5% for future use.

Following that, the three types of fermentation media (YPD, YP and distilled water) were prepared. The YPD broth powder was prepared aseptically with the following formula: 1% yeast extract 10 g, 2% peptone 20 g and 2% dextrose (glu­cose) 20 g. This formed 50 g of YPD powder, which was mixed with 1,000 mL of distilled water. The YP broth was prepared using the following formula: 10 g of yeast extract and 20 g of peptone were mixed with 1,000 mL distilled water. The pH of the fermentation media were adjusted to pH 7 using 1 mol/L NaOH. Then 1,000 mL of distilled water was also prepared as addition to the E. cottonii as fer­mentation medium. After that, the media were autoclaved at 121% for 20 min to sterilise the medium.

Then a carbohydrate extraction step was introduced (Table 13.3). Eight samples of seaweed (100 g seaweed each) in slurry form were mixed with 250 mL of dis­tilled water. Seven flasks were heated on a hot plate at 100% for 2 h to extract the polysaccharide (Lin et al. 2000). The last flask was left at room temperature without carbohydrate extraction. Subsequently, aliquots of 2 mL extracted solution were filtered using filter paper, followed by reducing sugar concentration analysis.

After the extraction step, the seaweed slurry was put through acid hydrolysis. Firstly, the extracted seaweed was cooled to 80%. Six flasks were then added with 70% sulphuric acid to a final concentration of 0.4 M. The other two flasks were added with 70% sulphuric acid to a final concentration of 0.1 M. One of these flasks at 0.1 M and five flasks at 0.4 M were heated at 100% for 3 h. The remaining flasks, one at 0.4 M and one at 0.1 M, were incubated at 30% for 3 h. The hydrolysate was neutralised with sodium hydroxide 5 M.

A reducing sugar concentration analysis was conducted to analyse the contents of sugar in samples without carbohydrate extraction, after carbohydrate extraction, without acid hydrolysis and after acid hydrolysis. The reducing sugar concentra­tions were analysed using the phenol-sulphuric acid method. Glucose was used as the standard for this analysis. A reducing sugar standard curve was generated as

Table 13.3 Experiment set-up for fermentation of seaweed (Eucheuma cottonii)

Experiment no.

Carbohydrate extraction at 100% for 2 h

Acid hydrolysis (conducted for 3 h) Sulphuric acid Temperature concentration (°C)

Fermentation media

1

Yes

0.4 M

100

Yeast Peptone Dextrose (YPD) broth

2

Yes

0.4 M

100

Yeast Peptone Dextrose (YPD) broth

3

Yes

0.4 M

100

Yeast Extract Peptone (YP) broth

4

Yes

0.4 M

100

Water

5

No

0.4 M

100

Yeast Peptone Dextrose (YPD) broth

6

Yes

0.4 M

30

Yeast Peptone Dextrose (YPD) broth

7

Yes

0.1 M

100

Yeast Peptone Dextrose (YPD) broth

8

Yes

0.1 M

30

Yeast Peptone Dextrose (YPD) broth

follows: firstly, 2 mL of different concentrations of standard glucose solution (0-0.5 mg/mL) were prepared and 1 mL of the phenol reagent was added to each standard solution. Secondly, 5 mL of sulphuric acid was added, and UV absorbance was read at 495 nm using Jasco UV-vis 650. All the samples were then tested with this method for reducing sugar concentration. The concentrations of reducing sugar in the samples were estimated by comparison with the standard curve.

Following acid hydrolysis, the samples were fermented. The fermentation was initiated via inoculation of yeast culture added at 20% v/v of the fermentation vol­ume. The yeast inoculums should be harvested at the exponential phase. Flasks were sealed with parafilm and placed in a rotary incubator at 200 rpm and 30%. The fermentation process lasted for 72 h. Samples for analysis were taken at the end of fermentation.

Subsequently, the fermentation broth was distilled using a distillation unit Buchi K-350. Each distillation batch contained 50 mL of sample. The final volume of distillate was measured and recorded. Next the distillate samples were stored in 5-8% prior to gas chromatography (GC) analysis.

The alcohol content of the distilled samples was estimated using the relationship between specific gravity and percent of alcohol. According to Amerine and Ough (1974), the percentage of ethanol present in a mixture of water and ethanol (distil­late) can be obtained from the specific gravity of the distillate as a function of per­cent ethanol (volume/volume). From the specific gravity of the distillate which contains mainly ethanol and water, the volume percentage of ethanol in the distillate can be determined from Eq. (13.2).

%Ethanol = (7,982.69 x SG2) — (16,602.41 x SG) + 8,619.74. (13.2)

Table 13.4 GC setting

Detector

Thermal conductivity detector (TCD)

Column

Capillary column, 30 mL x 0.25 ID x 0.25 pm film thickness

Carrier gas

Helium gas (99.995% purity)

Injection technique

Automatic injection

Initial oven temperature

40%

Temperature ramp

10%/min

Final oven temperature

100%

Runtime

3.10 min

Injection volume

1.0 pL

Type of inlet mode

Split

Split ratio

200:1

Flow rate of the mobile phase

0.7 mL/min

Further analysis using gas chromatography GC (Model 6890N, Agilent Technologies, CA) equipped with thermal conductivity detector and HP-5MS column, 0.25 mm x 30 m x 0.25 pm ID (Agilent, CA) was conducted to verify the presence of ethanol in the sample. Prior to the GC analysis, sodium sulphate anhy­drous (NaSO4H2O) was added to the distilled sample in order to remove the water in it. The NaSO4H2O was added slowly to the sample until there was no solid for­mation upon further addition. Then the samples were syringed through a 0.45 pm Durapore (PVDF) syringe-driven filter unit into 1.5 mL glass vials, sealed with a crimp cap and stored at 5-8% prior to the GC analysis. In order to get a clear and sharp peak for ethanol, trial and error was done to find the suitable setting for GC (Adams et al. 2009). Table 13.4 shows the setting of GC.

Investment Opportunities at Palm Oil Industrial Cluster (POIC) Lahad Datu with Special Reference to Biofuels

Teck Wai Pang and Ming Tong Lee

Abstract Agriculture has long been a mainstay of the economy of Sabah with relatively little contribution from industrial activity. At 1.4 million hectares, Sabah is the largest oil palm growing state in Malaysia. With the abundant oil palm raw materials for value adding, the Sabah State Government established the Palm Oil Industrial Cluster (POIC) Lahad Datu in 2005 as the catalyst in spearheading the state industrial drive through provision of appropriate physical infrastructure and policies. POIC thus serves as the center for integration of investment in upstream and downstream industries. The development of other industrial clusters such as logistics and oil and gas will follow in stages. The National Biomass Strategy 2020 mentioned in this chapter aims not only to generate a gross national income (GNI) of RM30 billion to the national economy by 2020 but also to meet the nation’s renewable energy target, reduce emission, and create about 66,000 jobs by 2020.

Keywords Palm oil • Lahad Datu • POIC • Biomass strategy

2.1 Introduction

Endowed with favorable climate and rich soils, agriculture has always been the mainstay of economy of the State of Sabah. However, there is relatively little con­tribution of industrial activity to the state economy.

The rapid development of the oil palm planting industry in recent decades has made Sabah the largest oil palm growing state in Malaysia with 1.4 million hectares of oil palm planting area and a production of 5.84 million tonnes of crude palm oil, representing about 30% of national total in 2011 (MPOB 2012). Seeing the potential advantage of the abundant oil palm raw materials for value-adding downstream

T. W. Pang (*) • M. T. Lee

POIC Sabah Sdn Bhd, Kota kinabalu 88400, Sabah, Malaysia e-mail: ptw@poic. com. my

R. Pogaku and R. Hj. Sarbatly (eds.), Advances in Biofuels,

DOI 10.1007/978-1-4614-6249-1_2, © Springer Science+Business Media New York 2013 industrial activities, the State Government of Sabah established the Palm Oil Industrial Cluster Lahad Datu (POIC Lahad Datu) as the catalyst in spearheading the state industrial efforts to drive the economy of the state.

The announcement of the Malaysian National Biomass Strategy 2020 in November 2011 signified the government’s determination to turn the available large quantity of agricultural waste, namely, oil palm biomass residue, into new sources of energy and material resources for high-value-added uses such as bioenergy, bio­based chemicals, and biofuels (Agensi Inovasi Malaysia 2011). This strategic move provides additional avenues of investment opportunity at POIC Lahad Datu.

This chapter gives an overview of POIC Lahad Datu and its link to biofuel devel­opment. It also highlights the Malaysian National Biomass Strategy 2020, the investment opportunities in biofuels, and how POIC could participate in the busi­ness development of the biofuel sector.

OPW from the Crude Palm Oil Refining Unit

5.2.4.1 Palm Fatty Acid Distillate

Palm fatty acid distillate (PFAD) is a highly odoriferous by-product (comprising mainly glycerol esters) obtained from the refining of CPO whose main processes include phosphoric acid treatment, bleaching earth treatment, deacidification and deodorisation of CPO (Ab Gapor 2010). At room temperature, its state is solid but becomes liquid on heating at elevated temperatures. Deacidification removes the free fatty acids, whilst deodorisation removes the odour by steam distillation under high vacuum. The distilled fatty acid is known as PFAD. In Malaysia, about 0.63 and 0.71 million tonnes of PFAD were produced in 2006 and 2008, respectively (Ab Gapor 2010).

PFAD has a moisture content of 0.03-0.24%, 80-90% free fatty acid in the form of palmitic acid, 1.1-2.3% unsaponifiable matter, density of 0.8640-0.8880 kg/l, iodine value of 46.3-57.6 I2/100 g and saponifiable value of 200.3-249.4 mg KOH/g PFAD (Bonnie and Mohtar 2009). Other constituents of PFAD include glycerides (14.4%), squalene (0.8%), vitamin E (0.5%), sterols (0.4%) and other extractives (2.2%) (Bonnie and Mohtar 2009; Hamirin 1983).

Figure 5.1 summarises the generation of OPW from the production of 5 tonnes of FFB and a tonne of CPO.

image039

Fig. 5.1 Schematic diagram of OPW generation in the palm oil industry

Ionic Solids

)onic solids are materials that are mostly produced through the combination of organic cations and anions from heteropolyacids. Cations from ILs are suitable for these catalysts because there are different types of cations available and the physi­cochemical properties can be altered by using different ILs. Keggin-type polyoxo — metalates (POMs) are favored for synthesizing these hybrid catalysts because of their good solubility in polar reaction media, which makes their recovery becomes easier (Leng et al. 2011b) . Figure 9.4 represents different use of ionic solids in chemical synthesis. Aside from its heterogeneity, the catalysts also possess high thermal stability and maintained the catalytic activity even after being recycled (Dai et al. 2010; Zhu et al. 2011).

Ionic solid catalysts can be obtained by integrating cations of ILs with anions of HPAs. Rajkumar and Ranga Rao (2008a) investigated the properties of a solid hybrid material containing [BMIM] cations and Keggin anions of phosphotungstic acid (H3PW12O40). The IL ([BMIM][Br]) was first synthesized, followed by the pro­duction of the hybrid material. It was found that it dissolves in organic solvent (DMSO), but not in water. Characterization showed that the pairing of Keggin anion and imidazolium cation leads to the formation of organic-inorganic hybrid molecu­lar solid, and most of water molecules are replaced by three imidazolium cations. Other than that, the weight loss in thermogravimetric analysis (TGA) shows the decomposition temperature was around 400°C, which proved that it is ther­mally stable even at high temperature.

image073

Fig. 9.4 Application of ionic solids in chemical processes

An almost similar pattern was observed when imidazolium ions were paired with silicotungstic acid (Rajkumar and Ranga Rao 2008b) and phosphomolybdic acid (Ranga Rao et al. 2009) for preparation of hybrid molecular materials. Both materi­als were insoluble in water. The former showed major weight loss at 400-580°C for TGA test, while the latter decomposed at 300-500°C.

Different ionic solids can be used for catalyzing chemical synthesis. One of the applications of ionic solid catalysts was the epoxidation of alkenes with H2O2 (Leng et al. 2011b). POM-based ionic hybrid catalysts were prepared, which resulted in a semi-amorphous solid composed of nanospheres and insoluble in almost all the commonly used solvents. They hold the advantages of convenient, steady reuse, high conversion and selectivity, simple preparation, and flexible composition. The combination of amino-functionalized cations and Keggin-POM anions showed high conversion and 100% selectivity. In addition to that, the catalysts were insoluble in the reaction, highlighting the convenient step of catalysts recovery by filtration.

Leng et al. (2011a) conducted the hydroxylation of benzene with H2O2 using heteropolyanion-based ionic hybrid solid. The catalyst was the result of combining cation from divalent IL and Keggin-structured heteropolyanion. The evaluation of the catalyst proved that its activity was the highest among other catalysts for the hydroxylation process and insoluble with other reactants. Slight deactivation of the catalyst was observed during the catalytic reusability test and was caused by leach­ing of the catalyst in the early two runs.

Ionic solids also have been proven to be able to catalyze the esterification reac­tion. Leng et al. (2009) prepared ionic solid catalysts by integrating three different organic cations containing propane sulfonate (PS) from IL and anions from H3PW12O40 for esterification of carboxylic acids. [MIMPS]3PW12O40 was successful for ester production of various carboxylic acids and alcohols. An interesting point to be noted here is that the catalyst completely dissolves in the medium to form a homogeneous mixture at the beginning of the reaction, and the catalyst precipitated at the end of the process. The progress of the esterification using citric acid is

image074

Fig. 9.5 Photographs of the esterification of citric acid with n-butanol over [MIMPS]3PW12O40. (a) [MIMPS]3PW12O40 (light brown solid at bottom), citric acid (white solid in the middle), and alcohol (liquid in the upper level before mixing); (b) homogeneous mixture during the reaction; (c) heterogeneous mixture near completion of the reaction; (d) at the end of the reaction, the catalyst has precipitated (Leng et al. 2009)

photographed in Fig. 9.5. The other two catalysts, [TEAPS]3PW12O40 and [PyPS]3PW12O40 have lower catalytic activities than [MIMPS]3PW12O40.

The absence of PS functional group from the organic cations of ILs resulted in much lower ester yield than those with PS functional group. Also, different inor­ganic anions containing the same MIMPS cation, such as SiW12O4O and PMo12O40, lead to different ester yield. The yield from the esterification of citric acid reduced from 95.4% in the first run to 84.5% in the fourth run during catalyst recycling, while the selectivity maintained at 98%.

The transesterification of Jatropha oil was conducted using catalysts based on pyridinium cation of ionic liquids (Li et al. 2010). The inclusion of [BSPy] cation with three HPAs produced [BSPy]3PW12O40, [BSPy]3PMo12O40, and [BSPy]3SiW12O40 catalysts. FAME yield for these three catalysts was around 80%, and the conversion was more than 90%. However, the reaction temperature was a little bit higher than for ILs (i. e., 120°C). Furthermore, these catalysts were less active than those [BSPy]-based ILs, probably as a result of different phase with the reactant mixtures. Biodiesel productivity was higher for ILs because they are considered as homoge­neous catalyst, thus avoiding mass transfer limitation. FAME yield was highest when using [BSPy][CF3SO3] as the catalyst (92%), obtained in 5 h reaction time at the temperature of 100°C.

Enzymatic Trans esterification

Enzymes particularly lipases have been put forward in transesterification reaction mainly to overcome the drawbacks of chemical catalysts. The benefits of using

Table 12.5 Reported studies on enzymatic transesterification of Jatropha oil

Source of lipase

Immobilization method

Duration

(h)

Yield

(%)

References

Pseudomonas cepacia

Celite

8

98

Shah and Gupta (2007)

Novozyme 435

Macroporous acrylic resin

12

91.3

Modi et al. (2006)

Novozyme 435

Macroporous acrylic resin

36

86.1

Su et al. (2007)

Pseudomonas fluorescens

Entrapment sodium alginate

48

72

Devanesan et al. (2007)

Rhizopus oryzae

Biomass support particles

60

80

Tamalampudi et al. (2008)

Enterobacter aerogenes

Activated silica with ethanolamine and cross-linked by glutaraldehyde

48

94

Kumari et al. (2009)

Chromobacterium

viscosum

Celite-545

8

92

Shah et al. (2004b)

Novozyme 435

Macroporous acrylic resin

36

95.9

Su et al. (2009)

lipases as “potential biocatalyst” include easy recovery of biodiesel and glycerol, complete conversion of FFA to methyl/ethyl ester without pretreatment, ease of enzyme recovery, low temperature and energy inputs, mild reaction conditions, thermal stability at low temperature, operational stability, can accept wide variety of substrates and alcohols, and reaction in a solvent and solvent-free systems (Casimir et al. 2007). On the other hand, the main hurdle of using enzymes as bio­catalyst is its high cost. This can be overcome to a certain extent through immobilization.

It is crucial to identify a lipase with maximum conversion rate and which is read­ily available in the market. For this, various lipases have been screened for biodiesel production, and the lipase from Pseudomonas cepacia (Burkholderia cepacia) has shown good results (Otero et al. 2005; Shah and Gupta 2007). Several researches have been reported with lipase on transesterification of Jatropha oil and are shown in Table 12.5. A high conversion rate can be seen from the table, but the longer reac­tion time is one of the hurdles in its commercialization.

In order to be more economical when using lipases as biocatalysts, researchers are involved in the development of a robust immobilized enzyme for biodiesel pro­duction. Different combinations of basic immobilization techniques (adsorption, cross-linking, entrapment, encapsulation) are being tried in various ways for this reason. Out of these, entrapment and encapsulation in natural polymers like sodium alginate and k-carrageenan are gaining importance due to environmental friendly and low toxicity features (Jegannathan et al. 2009).

Advantages Over Conventional Devices

Membrane contactors have been proven capable of overcoming and lessening the boundaries and limitations of conventional devices for liquid-liquid and gas-liquid separation process. The early application of membrane contactors was meant mostly for the gas-liquid separation process because this separation is difficult to conduct using conventional devices, such as packed columns, packed beds, and equipment for offshore applications.

The application of membrane contactors in separation or absorption units has a size advantage over conventional contactors used for CO2 removal (Feron and Jansen 1995). They are suitable for the removal of CO2 from the exhausts of gas turbines and from flue gas (Pedersen and Dannstrom 1997; Mavroudi et al. 2003) because of their ability to increase the available gas-liquid contact area and provide a very high interfacial area, thereby increasing gas removal efficiency. Membrane contactors also have been used extensively in other applications, such as the predic­tion of the enhancement of ozone fluxes (Phattaranawik et al. 2005) and the deoxy­genation of water in boilers (Shao et al. 2008).

The applications of membrane contactors have an advantage over independency flow rate of two different phases; thus, they can be operated without disturbance,
which contrasts with conventional devices. In terms of their design, membrane contactor modules have a straightforward design that allows operation over a wide range of capacities and only requires the addition of membrane modules when needed to increase the yield of final, desired product. There are no moving parts in a mem­brane module, so it can achieve better efficiency than conventional contactors.

The use of a hollow-fibre, gas-liquid contactor resulted in more than five times larger volumetric mass transfer of CO2 absorption compared to a conventional packed bed (Nishikawa et al. 1995) . It was reported that membrane contactor achieved a CO) absorption rate that was 2.7 times higher than a packed column (Yeon et al. 2005). A pilot-scale membrane contactor showed that it can be used to recover CO) from flue gas (Yeon et al. 2005). It also can be used to capture acid gases from gas streams (Mansourizadeh and Ismail 2009). A membrane contactor that has a comparable mass transfer area to that of a packed column performs better than the structured packing (Vogt et al. 2011). The separation of two different gases simultaneously also can be conducted effectively (Lv et al. 2012).

Although membrane contactors have several advantages over conventional con­tactors, they are subject to fouling, especially in operations that involve biological processes, such as the operation of supplying CO2 to microalgae cultures, and this could shorten their life span. Such fouling can be reduced or avoided by determin­ing the wettability of the hydrophobic membrane materials. The degree of hydro — phobicity of the surface of the membrane increases the performance of the membrane (Nishikawa et al. 1995). The wettability depends to a great extent on the surface tension of the liquid, which can be quantified by breakthrough pressure (Kumar et al. 2002). Wetting can be avoided by applying a slightly higher over pressure on the gas side (Dindore et al. 2004). In the absorption of gases, the use of a chemical stabilization layer on the liquid side of the membrane could prevent wetting (Nymeijer et al. 2004). Partial wetting of the membrane pores reduces the mass transfer of gases (Lv et al. 2012). Thus, it is important to operate the membrane within its pressure wettability.

Liquid Fuel

Industrialised countries used hardwood biomass to manufacture several chemi­cals and products since late 1930s. One example is the Ford Plant, in which the hardwood biomass is converted to esters for automotive (Nelson 1930). Plant — based esters can be classified as the green solvents. For an example, glycerol carbonate is used as nonreactive diluents in epoxy or polyurethane systems and 2 ethylhexyl lactate can be used as degreaser and as green solvent in agrochemical formulation. Biomass can be converted to liquid through pyrolysis. Recent advancement in pyrolysis allows shorter heating time, i. e. <2 s at intermediate temperature of 400-600°C in oxygen-free condition. The produced liquid is known as bio-oil and is dark in colour, with energy density of 20 GJ/m3 and trans — ferrable using exiting oil tankers. It is used as boilers fuels and in specialty chemi­cals flavouring and colouring. Bio-oil can be upgraded using H2 or in catalytic environment it can be converted to BTX, MTBE and compatible transportation fuel (Klass 1998).

For ethanol production via fermentation, three types of biomass are employed. They are originated from sugar, starchy and lignocellulosic crops. For sugar crops, pretreatment is unnecessary, but for other crops the cell walls must be disrupted to expose the sugar polymers. The processes involved in ethanol production are pre­treatment, hydrolysis and fermentation and product separation through distillation. Contrarily, for direct biomass liquefaction, the biomass is not subjected to heat directly (Klass 1998). Direct liquefaction of biomass is in development stage and, namely, biomass-water slurry process, biomass-recycle oil slurries and hydroiodic acid. In recycled oil slurries, it requires sodium carbonate and CO gas at 250-450°C with 10-30 MPa pressure for conversion to liquid fuel with heating value of 33-34 MJ/kg. For the other process hyroiodic fluid is introduced at 127°C to form hydro­carbon at 60-70% yield. Hew et al. (2010) studied conversion of EFB into liquid product. The EFB-derived pyrolysis oil (bio-oil) is converted to liquid fuel, follow­ing Taguchi method. From the analysis, the optimum operating condition for the heterogeneous catalytic cracking process is at 400°C, 15 min of reaction time using 30 g of catalyst weight.

In 1900, Rudolf Diesel demonstrated a direct injection diesel engine fuelled with peanut oil. Ester-type biodiesel is produced catalytically from methanol or ethanol transesterification of triglycerides to methyl or ethyl esters. Its yield and purity depend on ratio of alcohol and triglycerides, catalyst type, temperature and purity of triglyceride. Modhar et al. (2010) investigated the blending of crude palm/crude rubber seed oil and their conversion to biodiesel. Optimum reaction conditions were determined and the conversion of methyl esters exceeded 98%. Biodiesel can be produced from low cost nonedible oils and fats. However most of these sources are of high free fatty acid content which requires two stage processes. The acid treat­ment step is usually followed by base transesterification since the later can yield higher conversions of methyl esters at shorter reaction time.

Simultaneous Production of CPO and Utilisation of OPW for Value-Added Bio-Products

The amount of OPWs that are used for mulching and nutrient recycling are more than necessary. Large quantities of OPFs, OPLs, OPTs and OPRs which are underutilised can be effectively used in applications such as bio-fertiliser pro­duction, food and feed production as well as biomass power plant to generate

image040Fig. 5.2 Simultaneous production of FFB and utilisation of OPW for various value-added bio­products incorporating animal husbandry electricity. Figure 5.2 summarises the simultaneous production of FFB and utili­sation of OPF, OPL, OPR and OPT for power generation and feed production around the palm plantation.

The concept of integrating animal husbandry into palm oil plantations is found to be feasible as demonstrated by Jalaludin 1996. Usually, pesticides and weedi — cides from inorganic (chemical) sources are used to control weed growth and insect attacks in the palm oil plantation. These are environmentally unsafe and cost ineffective and can be totally eliminated when livestock production is incor­porated in palm oil plantation whereby forages in the inter-rows grazed off by the livestock. Also, the dung from the animals could be used as organic fertiliser in the plantation hence reducing the cost of FFB production and soil nutrient dete­rioration. Excess dung could be processed in the bio-fertiliser production unit for subsequent sale. Figure 5.3 shows the schematic diagram of the conversion of OPW in the palm oil mill into value-added bio-products.

image041

Fig. 5.3 Schematic diagrams of the simultaneous production of CPO and conversion of OPW into value-added bio-products

5.2 Conclusion

OPW can be utilised efficiently into green wealth by simultaneously transforming some of the wastes into energy to be utilised by the various value-added bio-product production units within the palm oil industry. Converting OPW into bio-products could evolve a lot of creative technologies and industries which would further jobs and improve the life of people in the palm oil-producing countries. Industries such as food, phytochemical, furniture, polymer and composite materials, activated car­bon, soap and cosmetics and power plants could be set up as integration into the palm oil plantation and palm oil mill for the benefit of mankind.

Acknowledgments The authors would like to thank Universiti Sains Malaysia (Research University Grant No. 854002 and USM Fellowship) for the financial support given.

Enzymatic Catalyzed Pathway

An enzymatic transesterification pathway is a biocatalytic reaction using biocatalyst (i. e., lipase enzyme) for biodiesel production (Fig. 10.3). This biochemical approach is able to resolve downstream processing problem that posed by chemical
transesterification (homogeneous and heterogeneous catalyzed reaction). The bio­diesel and glycerol purification steps in chemical reaction will generate huge amount of waste water that eventually increase biodiesel production cost. In contrast, bio­processing of oil via enzymatic reaction for biodiesel production is being simpler, milder reaction condition, lower energy process, less corrosive, and able to simulta­neously catalyze transesterification and esterification in a single-step process with the presence of high FFA oil. However, the enzyme-catalyzed reaction is not sug­gested to be commercially developed due to its higher cost of lipase with its feasibility aspect, and the duration for reaction is still unfavorable compared to chemical reaction.

Optimization of Biodiesel Production from J. curcas Oil

Optimizations of process parameters for biodiesel production have been studied in detail by many researchers. This is mainly because these process parameters have shown important contribution towards attaining maximum biodiesel conversion. The biodiesel process parameters studied here include oil-to-ethanol molar ratio, water content, enzyme loading, reaction temperature, mixing intensity, and finally reaction time. Enzymatic transesterification of crude Jatropha oil was carried out in a 50-ml baffled conical flask (Corning, USA) in an orbital shaker incubator (Heidolp, Germany). This setup was used as a stirred tank batch reactor for the rest of the experiments. The following standard set of reaction conditions were used as the baseline in the optimization studies. The initial conditions were 10 g Jatropha oil, 2 g ethanol (ethanol-to-oil ratio 1:4), 1 g water, 100 mg free lipase or 5.2 g immobi­lized lipase, 35°C, 200 rpm (rotations per minute), and 24-h reaction time. For example, when the effect of oil-to-ethanol ratio was assessed, the remaining reac­tion conditions were unchanged: that is, 10 g oil, 1 g water, 5.2 g immobilized lipase, 35°C, 200 rpm (rotations per minute), and 24-h reaction time.