Bioresource Technology 102 (2011) 33883395

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Microwave induced pyrolysis of oil palm biomass

Arshad Adam Salema, Farid Nasir Ani
Department of Thermodynamics and Fluid Mechanics, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, UTM 81310, Skudai, Johor D.T., Malaysia

a r t i c l e

i n f o

a b s t r a c t
The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and bers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature proles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 18 May 2010 Received in revised form 27 September 2010 Accepted 28 September 2010

Keywords: Oil palm biomass Pyrolysis Microwave Microwave absorber Bio-oil

1. Introduction Biomass which was once considered as socio-environmental liabilities is now scrutinized to be contributor of wealth from waste and establishment of carbon credit business. Oil palm biomass such as shell, bers and empty fruit bunches are generated as by-products from oil palm mills in millions of tones per year in Malaysia. This is also true for surrounding regions of Malaysia, such as Thailand and Indonesia. It is enough to consider that there are about 400 oil palm mills operating currently in Malaysia. Normally, this biomass is either used as boiler fuel for generating electricity in mills itself or burnt in uncontrolled condition to obtain ash for oil palm plantation which causes environment damage. According to Kawser and Ani (2000), the mills have generally excess amount of oil palm biomass leftover that demands to obtain value added products from them in a sustainable approach. Sumathi et al. (2008) has recently published a comprehensive review on the oil palm biomass and its types generated from oil palm industries as a source of renewable energy. Transforming this abundant available oil palm biomass into bio-oil and bio-fuels is emerging and futuristic move to be considered in Malaysia to overcome the concern about the environmental protection, energy supply and green house gas emissions. Hence, the bio-oil and bio-fuels are considered to be alternative of crude petroleum oil and as a source of clean energy or to produce value added products. However, the technology needs revolutionize in order to produce
Corresponding author. Tel.: +60 7 5534715; fax: +60 7 5566159.
E-mail address: farid@fkm.utm.my (F.N. Ani). 0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2010.09.115

bio-oil in a technically and economically feasible way, which is environmental friendly and sustainably accepted. One of effective way is the pyrolysis process whereby bio-oil (liquid), char (solid), and ue gas are obtained in the temperature range of 400600 C and in absence of oxygen. Pyrolysis process not only reduces the volume of waste signicantly, but also allows recovering value added-products. Furthermore, pyrolysis is considered as one of the most promising route for thermochemical treatment since it can be used as independent process for bio-fuels and other valuable chemical products or as an initial step for gasication and combustion (Baysar et al., 1988). The fast pyrolysis system has already been developed in our laboratory to obtain bio-oil from various biomasses (Ani et al., 2008) and the techno-economic feasibility of uidized bed pyrolysis was done in our previous work (Islam and Ani, 2000). This process needs continues supply of heat for chemical decomposition in biomass because of its endothermic reactions nature. Conventional heating methods include external heating by conduction, convection or radiation (Chen et al., 2008). This method suffers from certain drawbacks including heat transfer resistance, heat losses to surrounding, utilization of portion of heat supplied to biomass materials, damage to reactor walls due to continuous electrical heating etc. Another drawback is the lack of rapid heating which results in long heating duration which causes undesired or secondary reaction. These secondary reactions are responsible for low product quality due to further cracking of product. Furthermore, the temperature along the reactor in conventional systems is high enough to favor the secondary reactions. Lastly, large biomass particles are not recommended for conventional heated

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pyrolysis processes (Bridgwater, 1999). Since this can acutely deteriorate the heating rates, yield and quality of bio-oil and bio-fuel. Keeping in view the above problems, a new technique of utilizing microwaves as an alternative heating source was developed. Microwave has gained interest in recent decades as an efcient source of energy to pyrolysis different wastes such as plastic (Ludlow-Palafox and Chase, 2001), sewage sludge (Domnguez et al., 2008; Menndez et al., 2002), biomass (Yu et al., 2007; Huang et al., 2008, 2010; Guo et al., 2006; Wan et al., 2009), and wood (Miura et al., 2004). In addition to this, microwaves have been effectively used in various elds of waste and environmental engineering (Jones et al., 2002; Appleton et al., 2005). Various advantages of microwaves are also reported in there. The key merit of the microwave pyrolysis as stated by Miura et al. (2004) was the prevention of an undesired secondary reaction that leads to formation of impurities in the product by decreasing the yield of desired compounds. Another advantage is the volumetric heating of microwaves as shown in Fig. 1, which gets the molecules into rotation due to high frequency and thus creates the heat, provided the penetration depth of the microwaves into the materials is sufciently enough. Thus, microwave heating offers distinct heating mechanism unlike the conventional heating whereby the surface heating takes place. Fig. 1 also shows the electromagnetic spectra with microwaves lying in frequency between 300 MHz and 300 GHz. However, two most common frequencies allocated for material heating are 915 and 2450 MHz for industrial, scientic and medical (ISM) applications. Specic research activities on microwave pyrolysis of biomass includes pyrolysis of r pine wood sawdust (Chen et al., 2008), corn stover (Yu et al., 2007), rice straw (Huang et al., 2008, 2010), r sawdust (Guo et al., 2006), biomass (Wan et al., 2009), coffee hulls (Domnguez et al., 2007) and wheat straw (Budarin et al., 2009). Nevertheless, to our knowledge none has attempted microwave pyrolysis of oil palm biomass till date in the literature. Particularly, the effect of microwave absorber (MA) on the temperature proles and yield of bio-oil was found lacking in the literature. Therefore, the present research work holds interest to investigate the performance of oil palm biomass under microwave radiations. Among the researches mentioned above, few used catalyst to carry out the microwaves pyrolysis of biomass but were chemicals. However, in our present work we used char as microwave absorber to initiate the pyrolysis reaction and enhance the heating process. The objective of the present study was to investigate the effect of microwave irradiation on oil palm biomass pyrolysis with and without char as a microwave susceptors. The heating characteristic

was investigated through the temperature proles of the biomass under the microwave irradiation. Moreover, the effect of biomass to microwave absorber ratio on the yield of bio-oil was given particular attention. Further, some characterization of the pyrolysis products was presented in the paper. 2. Methods 2.1. Materials Two types of as received oil palm biomass, oil palm ber (OPF) and oil palm shell (OPS) were obtained from Felda Kulai palm oil mill situated in Johore state of Malaysia. OPS were used as large particles i.e., without any grinding, and size ranging from 0.001 to 0.1 m, while OPF was grinded into smaller size to about 300 600 lm. The width of the OPS was in range of 0.00050.004 m and that of OPF was <0.001 m. In present work, the char obtained from conventional pyrolysis of oil palm shell was used as microwave absorber. The size of microwave absorber char was in the range of 100300 lm. Repeatedly carbon, char, graphite and other related carbonaceous materials were reported to be good microwave absorbers (Domnguez et al., 2008; Menndez et al., 2002; Appleton et al., 2005). Proximate analysis of oil palm biomass at dry condition is as shown in Table 1. As received moisture content of OPS and OPF was found to be about 8 and 10 wt%, respectively. 2.2. Experimental set-up The experiments were carried out in a 1 kW domestic modied microwave system having 2450 MHz frequency. Schematic diagram of experimental set-up for the modied microwave pyrolysis system is as shown in Fig. 2. The microwave power can be selected at different level (100, 180, 300, 450, 600, 850 and 1000 W) and for various exposure times (190 min). Microwave cavity was modied in order to accommodate the uidized bed quartz glass reactor (0.1 m I.D. 0.15 m height). This reactor was facilitated with perforated steel distributor plate of 1 mm holes. Both ends of the uidized bed quartz reactor were closed with glass caps and tighten by clips. This glass caps consisted of suitable openings to facilitate the entrance of nitrogen gas from the bottom and exit of pyrolysis vapors from the top. Measurement of process temperature was done by two K-type metallic thermocouples connected to 8 channels Pico data acquisition system (temperature accuracy of 0.5 C, as many readings as possible per second) acquired from U.K., and further this was linked to personal computer for continuous

Fig. 1. Electromagnetic spectra (Kappe and Stadler, 2005) and microwave heating nature.

3390 Table 1 Proximate analysis of oil palm biomass. Biomass Shell Fiber Volatile matter (wt.%) 78 72.8

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Fixed carbon (wt.%) 20 19.2

Ash content (wt.%) 2 8

recording of data using Picolog Software. Thermocouple T1 was inserted inside the bed region and T2 was held just above the bed surface. The thermocouples were grounded to avoid any discrepancy in temperatures reading or arcing due to microwaves. However, for further reassurance, infrared temperature detector supplied by ColeParmer Inc. 08406 series (temperature accuracy of 1 C), Illinois, U.S.A. was used. It was found that the metal thermocouple and infrared temperature detector readings almost agreed with a difference of 1 or 2 C utmost when done at the end of experiments. 2.3. Method

reconnect back for further experimental runs. Thus total bio-oil, and solid char residue was weighted at the end of the experiments to investigate the yield. The yield of the ue gas was measured by difference. All the experiments were repeated twice to conrm the values obtained. The temperature proles were found to be more or less similar with small variation in case of OPF. The product yield repetition caused variation of about 1 to 2 wt%. Bio-oil was subjected to viscosity measurement using Petrotech equipment available in Petroleum Engineering Department, UTM, and pH value was determined using Eurotech pH tutor (pH accuracy of 0.01). FT-IR spectra of bio-oil were performed using Thermo Corporation FT-IR analyser manufactured in Madison, WI, U.S.A. model Nicolet Avatar 370 DTGS using a smart detector. Image analysis of oil palm shell char was conducted under ZEISS microscope image analyzer (Axiotech model), Germany attached with it was the Sony digital color video camera (SSC DC-338P model). The images were captured with the help of 5, 10, 20, 50 microscope resolution. 3. Results and discussion

For each experiment, the ratio of biomass to microwave absorber was varied (1:0.25, 1:0.5, and 1:1) and charged into the uidized bed quartz reactor. Nitrogen gas at about 20 liter per minute (LPM) ow rate and 99.96% pure was supplied before the initiation of the experiments to ensure an inert environment. During the experimental run nitrogen gas was continuously supplied at ow rate of about 10 LPM to maintain the inert environment as well as to sweep the vapor out of the reactor. The inert gas can also play an important role in avoiding any possible explosion or hazard, thus taking care of safety issue during the experiments. Microwave power (450 W) and the radiation time of 25 min was kept constant for each batch. The vapor generated out of the reactor was condensed into bio-oil (liquid) using water cooled condenser at temperature of about 58 C. Bio-oil remained in the equipments was also determined via weight difference of the equipments before and after the experiments. The remained bio-oil was determined from uidized bed reactor, connecting tube and condensing unit. This all equipments were made up of glass materials and can be easily dismantled in order to weight them individually and

3.1. Temperature proles Fig. 3 depicts the real time temperature proles of oil palm shell (OPS) and oil palm ber (OPF) with and without microwave absorber under microwave power input of 450 W. It can be observed that absence of microwave absorber resulted in a maximum bed temperature (T1) of about 122 and 95 C for OPS and OPF respectively. The maximum surface temperature (T2) was 180 C for OPS and 93 C for OPF. This illustrates that the bed temperature for OPS was lower than its surface temperature while it was vice versa for OPF. From this it seems that the penetration of microwaves depends on the types of materials. Since OPS are hard nut shell also referred to as oil palm stone and OPF are thin, oppy brous materials, the microwaves absorbed by these biomass materials might have depended on its physical characteristics. The interaction between microwaves and the materials properties plays an important role in dening the temperature proles. Apparently, neither the release of volatile matter in form of vapor

10

3 7

6 1 8 2 4 5

9 N2

Fig. 2. Schematic diagram of microwave pyrolysis system: (1) microwave cavity, (2) quartz glass uidized bed reactor, (3) thermocouples, (4) distributor plate, (5) temperature data acquisition system, (6) personal computer, (7) condensing unit, (8) bio-oil collector, (9) rotameter, and (10) ue gas.

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200 180 160 140 120 100 80 60 40 20 0

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Microwave OFF

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Temperature, C

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Microwave ON

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0 2 3 5 7 8 10 12 13 15 17 18 20 22 Time, min

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200 150 100 50

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T1 T2

0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time, min

8 10 12 14 16 18 20 22 24 Time, min

Fig. 3. Effect of biomass to microwave absorber ratio on real time temperature prole of OPS (A-OPS: without microwave absorber, C-OPS: 25% microwave absorber, E-OPS: 50% microwave absorber) and oil palm ber (B-OPF: without microwave absorber, D-OPF: 25% microwave absorber, F-OPF: 50% microwave absorber); microwave power 450 W; T1 bed temperature and T2 bed surface temperature.

nor the pyrolysis took place at this stage, although water evaporation was noticed. This also proves the poor microwave absorber characteristics of these biomasses. The increase in temperature at this stage was due to presence of moisture in the biomass. Since water is good microwave absorber (Zhang and Datta, 2003) due to its dielectric property and polar nature (Kappe and Stadler, 2005) it can generate the heat within the biomass. Hence, once the microwave encounters the biomass, the moisture absorbs the microwaves and creates a dielectric polarization whereby the water molecules try to align themselves according to the radiation, which nally leads to friction within the molecules generating energy in the form of heat. This heat is sensed as increase in temperature. The instant microwave is turned ON there was sudden increase in temperature because the water molecules comes to super heated point the moment it absorbs the microwaves. However, once the water is evaporated from the biomass, other constituents such as volatile matters (see Table 1) present in the biomass do not absorb the microwaves readily. Therefore, the temperature was observed to stabilize after initial rise (see Fig. 3A and B). This trend was also observed at 100, 180, 300, and 450 W microwave powers. Increase in microwave power beyond 450 W do not show any progress in temperature proles and was almost similar. Nevertheless, for OPF at higher microwave power say for 850 and 1000 W, mild vapor were generated and the temperature was

somewhat higher (T1 was 120 C) than 450 W. But there was no condensation of these vapors into bio-oil. This might be due to heating of low temperature volatile components present in the OPF. The addition of microwave absorber (char) with oil palm biomass not only increased the temperature as shown in Fig. 3CF but also initiated the pyrolysis process by generating the vapors. The commencement of microwaves and generation of vapors were instantaneous. It appears that microwave absorbers (MAs) played a crucial role in rapid transfer of heat to the biomass materials. The maximum bed temperature, T1 recorded for 1:0.25 and 1:0.5 (OPS to microwave absorber) ratio was about 200 and 237 C respectively. This temperature was well below the reported (Islam and Ani, 2000) temperature to initiate the pyrolysis i.e., around 450 C. This result provided some interesting fact about low temperature pyrolysis which otherwise was believed to rarely take place at such temperature. Several possible reasons can be extracted at this stage. Firstly, the measurement of temperature during microwave heating plays a role. This is because the core or centre of the biomass particles is at higher temperature compared to surface due to penetration nature of microwaves into the materials. Thus, according to Guo and Lua (2000), in microwave heating the sample internal temperature is ten or hundred degrees higher than that of surface temperature. Secondly the hot spots in

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multi-mode domestic microwave system can delude the temperature prole. Another reason might be the low temperature pyrolysis of biomass in microwaves as reported by Budarin et al. (2009). In their research work bio-oil was produced from wheat straw at pyrolysis temperature as low as 120 C in a microwave and in a very short time. They also reported that the release of volatile at low temperature depends on the type of biomass and additives used. This clearly shows that certain biomass can be devolatilized even at lower temperature under microwave irradiation. The temperature proles in case of OPF were much higher compared to OPS. The maximum bed temperature recorded for 1:0.25 and 1:0.5 (OPF to microwave absorber) ratios was about 1340 and 1460 C respectively. This was around 550 and 500% increase compared to OPS respectively. This could be due to physio-chemical characteristics of the biomass used, since the OPF are much lighter and thinner in diameter or thickness compared to OPS which are hard and thick. It can be observed from Table 1 that if the volatile matter of both the oil palm biomass is considered to be similar i.e., around 72 wt%, the only factor to vary their temperature proles was the physical characteristics of the oil palm biomass. This is because it could be hypothesized that the temperature prole should have been nearly similar if volatile matter would have played a role. But the microwave heating of this physically dissimilar oil palm biomass transpired that the temperature followed different proles. It should also be noted that the OPS was used as received without any grinding and pre-treatment as mentioned earlier compared to OPF which were grinded to smaller size. The discussion regarding the sinusoidal nature of the temperature proles will be mentioned later. Thus, it was evident from the temperature proles that char as a microwave absorber played a crucial role in increasing the heating rate of the biomass materials under microwave irradiation. Carbonaceous char was used to achieve high temperature for sewage sludge pyrolysis (Menndez et al., 2002). A maximum temperature of about 900 C was achieved in just 2 min with addition of 5 wt% carbon char with sewage sludge compared to only 200 C without any char. In our study, it just took about 0.1 second to reach 1000 C (see Fig. 3D-OPF) which was a signicant response in temperature. This rapid heating if not possible is difcult to achieve in conventional heating methods. Other study (El har et al., 2000) used carbon grains of about 0.5 wt% and mixed with oil shale sample to pyrolyse under microwave radiation in order to allow uniform temperature or heating. Coupling of poor microwave absorber materials or low dielectric loss materials with highly microwave absorbing materials having high dielectric loss, results in selective heating characteristics of microwaves which is difcult in conventional heating. Thus, system of different permittivities can be heated selectively which consequently leads to less overall process energy (Conner and Tompsett, 2008). The synergistic effect produced by coupling the biomass materials with microwave absorber was encouraging. Another interesting investigation was the heating nature of the bed region which depended on the type of biomass material used. Fig. 3 clearly shows the difference in bed, T1 and surface temperature, T2. In case of OPS with microwave absorber, the bed temperature was higher than surface temperature at initial stage, but after a short time they crossed each other and eventually surface temperature started gaining. However, in case of OPF with microwave absorber, the difference between bed and surface temperature was more prominent with higher bed temperature. This proves that microwaves did penetrate the OPF to large extent compared to OPS. Mostly the pyrolysis of OPS was observed on the top of the bed region and hence, the surface bed temperature of OPS happened to be higher with and without microwave absorber. Hence, the temperature proles for the bed region can be helpful to predict the penetration of the microwaves. So far this particular investigation was missing in the literature. The importance of this study

revealed that the biomass materials such as OPS obstruct the microwaves to penetrate into the bed due to their physical characteristics and hence can lower the pyrolysis efciency. Moreover, the rate of heating, reaction chemistry and temperature proles might also depend on the mode of the microwave applied. It was reported by Lewis et al. (1992) that the steady temperature prole is obtained by continuous or single mode microwave generation, while different effects might be produced by pulsed or multimode microwaves. Since in our present work a modied domestic microwave system was used, the operation of these microwaves was in a pulsed or multimode. The temperature prole obtained from this type of multimode operation microwaves has to be taken carefully because of intense heating at particular spots. According to our knowledge, the char formation during pyrolysis also plays an important role under microwave radiation. Thus, microwave pyrolysis of OPF can produce char much faster due to its low density and size. Conversely, formation of char in OPS might be slower due to large particle size and hard surface. It is evident that quicker the formation of char from biomass will enhance more microwaves to be readily absorbed by newly formed char and consequently higher temperature and progress in reaction can be attained. This phenomenon was also reported in several literatures (Huang et al., 2008; Robinson et al., 2007). The sinusoidal nature of the temperature proles in Fig. 3 shows the cyclic ON/OFF working nature of the magnetron (microwave generator). Basically, all domestic microwave ovens work on this type of cyclic ON/OFF mode. This means that the temperature shoots to higher value when the microwave is in ON mode and drops to a certain level when the microwave is in OFF mode. It should be noted that the ON time of microwave is small and it was about 20 seconds per minute in present microwave system. Hence, there is a variable power output in multimode domestic microwaves which might impedes the exact temperature of the material. The microwave pyrolysis of OPF showed higher sinusoidal nature of temperature proles compared to OPS. Yet again, this shows that the temperature prole greatly depends on the types of biomass material undergoing decomposition in microwave system. Assuming the chemical properties to be similar, the physical characteristics such as shape, size and nature of the biomass materials play an important role in providing the temperature prole. Based on this, OPS showed much stable and steady temperature prole than OPF. A sinusoid nature of temperature was observed too in case of OPS but with microwave absorber (see Fig. 3C and E), whereas without microwave absorber a very steady temperature prole was observed (see Fig. 3A). However, for OPF the sinusoid nature of the temperature prole was less pronounced without microwave absorber than with microwave absorber (see Fig. 3B, D, and F). It can be concluded that biomass materials like OPS can perform better under multimode microwave than OPF. It can be deduced that the magnetron operation (single and multi mode), type of biomass and its physical characteristics, play an important role in dening the temperature prole under microwave radiation. Finally, conventional pyrolysis require preparation of feedstock such as grinding, removal of moisture, etc. in order to enhance the heat and mass transfer to achieve high bio-oil yield. The particle size is usually in microns which needs energy to grind. In addition, to remove moisture the biomass is dried in electrical oven or similar equipments which also consume energy. A unique nding in our present research work was that the OPS biomass was used as received without grinding or removal of any moisture or other pretreatments. These cases can be taken in conventional pyrolysis but with the expense of heating rate, reaction mechanism and yield of the products. But microwave pyrolysis could work better with large particle size and moisture or water is a very good microwave absorber. Thus, according to our knowledge, the cost of grinding

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and removal of moisture can be avoided by keeping high heating rate and better product yield in microwave induced pyrolysis. Similar conclusion was also drawn by Krieger-Brockett (1994). Energy savings with rapid heating and instantaneous pyrolysis of biomass under microwave irradiation contributes signicantly in reduction of process energy and time.

3.2. Effect of microwave absorber on the product yield The yield of microwave pyrolysis products such as bio-oil, char and gas at different biomass to microwave absorber ratio is depicted in Fig. 4. Maximum bio-oil yield was obtained at 1:0.5 biomass to microwave absorber ratio for both oil palm biomass. It should be noted that this bio-oil yield was including the water content. Correspondingly, lowest char yield was obtained at the same ratio. It was assumed that as the amount of microwave absorber is small, biomass could not get enough heat to pyrolysis. Therefore, most of biomass was not pyrolysed. Conversely, higher amount of microwave absorber might have lead to localized heating of char material alone. Yet the exact reason for this has to be investigated and understood since the heating characteristics of microwave is very fast. Uniform temperature measurement is also a difcult task in microwave systems. However, microwave irradiation for oil palm biomass for 25 min was not enough for complete pyrolysis. Basically, the yield of bio-oil is considered to be proportional to the condensable volatile matter released during pyrolysis process. From Table 1, both oil palm biomass are found to be highly volatile materials. The reported initial degradation temperature for OPS at which the volatile matters are released was approximately 230 C by TGA analysis (Ani and Gibbs, 1992). But the devolatization process for OPS was completed well below 450 C. In present research work, the maximum temperature attained by OPS at 1:0.5 ratio was about 237 C, which might be considered as the initial degradation temperature for the release of volatile matters. Therefore, at this temperature low boiling volatile components might have condensed into bio-oil, either leaving behind volatile matters in char or entrained with ue gas because of short residence time in the condensers. For OPF, even though the high temperature pyrolysis was observed, but short residence time of condensable volatile matter in the condenser might have limited the yield of bio-oil. Moreover, high pyrolysis temperature favors the formation of ue gas compared to liquid product. Recently Budarin et al. (2009), studied that the yield of bio-oil was inuenced signicantly by adding additives such as sulphuric acid, hydrochloric acid and ammonia to the wheat straw biomass before microwave pyrolysis. Related study of microwave absorption media inuence on pyrolysis of r sawdust was done by

Guo et al. (2006). The results of this study showed optimal ratio at which maximum bio-oil yield was obtained i.e., 3:1 for glycerol to biomass and 2:1 for ionic liquid to biomass respectively under microwave irradiation. Nonetheless, a detail understanding about the role of microwave absorber on the yield of bio-oil was found to be at infant stage. Another recent study (Pingale and Shukla, 2008) also demonstrated the effect of catalyst ratio on the depolymerization of poly ethylene terephthalate waste bottles. Hence, it was found that microwave absorbers or catalyst do affect the yield of pyrolysis liquid and other products. 4. Pyrolysis Product Characterization 4.1. Bio-oil Physically the obtained bio-oil from microwave pyrolysis of OPS and OPF was golden brownish in color. The pH was found to be in range of 2.73.0. This indicated that bio-oil was acidic in nature due to presence of acid compounds. The viscosity of bio-oil was found to be 0.0164 and 0.0125 cm2/s at 25 and 40 C respectively. The viscosity of bio-oil decreases with increase in temperature much faster compared to petroleum crude oil (Bridgwater, 2004). In present study the viscosity of bio-oil decreased by 25% when temperature was increased from 25 to 40 C. Another reason for low viscosity was the presence of water in the bio-oil. The FT-IR spectra (not shown here) for as OPS and OPF bio-oil produced via microwave pyrolysis revealed various probable chemical compounds. It illustrated some difference in the peak patterns with some additional peaks observed in OPF bio-oil which might be due to difference in lignocellulosic matter content in the oil palm biomass. Since OPS contain high lignin compared to OPF, it favors the formation of phenolic compounds during pyrolysis. Further, high pyrolysis temperature in case of OPF might also have affected

Table 2 FT-IR analysis for functional group present in OPS and OPF bio-oil. Wave numbers, (cm1) 32003600 30002800 17801640 16801580 15501490 14751350 9501300 900650 Functional group OH CH C@O C@C NO CH CO OH OH Class of compounds Polymeric, water impurities, phenols Alkanes Ketones, aldehydes, carboxylic acids Alkenes Nitrogenous compounds Alkanes Primary, secondary and tertiary alcohols, phenol, esters, ethers Aromatic

100

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0 1:0.25 1:0.5 1:1 Biomass to microwave absorber ratio

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60

40

40

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Fig. 4. Effect of biomass to microwave absorber ratio on the (a) OPS and (b) OPF product yield (microwave power 450 W and time 25 min).

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Cracks

Conventional Heating
Pores

Microwave Heating
Fig. 5. Surface image analysis of OPS chars after conventional heating and microwave heating.

the formation of chemicals in the bio-oil. The possible functional groups and its compounds are shown in Table 2. The presence of signicant peaks between 1640 and 1700 cm1 could be due to C@O stretching vibrations indicating compounds such as ketones, phenols, carboxylic acids or alcohols. Another indication of alcohols including phenols can be found in the range of 3200 3400 cm1 as OH stretching. However, broad OH stretching vibration between 3200 and 3600 cm1 may be due to water impurities also. This peak was much more pronounced in OPS than OPF bio-oil. It can be predicted that OPS bio-oil is rich in phenolic components compared to OPF bio-oil. The peaks between 1300 and 950 cm1 showing the CO and OH stretching vibrations may be due to the presence primary, secondary and tertiary alcohols, phenols, ethers and esters. This fast screen technique of FT-IR was used to observe the extent and presence of hydroxyl group to conrm the phenolic compounds. The extended peak for OPS at 3200 and 3400 cm1 wavelength can assure the high content of phenolic compound compared to miniature peak for OPF at same wavelength. 4.2. Char As received i.e., large size OPS was pyrolysed in conventional electrical furnace using an inert nitrogen gas. The purpose of this experiment was to pyrolyse the OPS to obtain the required char. The pyrolysis was carried out at temperature of about 450 C. The char obtained from this method was compared with that of microwave pyrolysis of same size OPS. The difference in surface image analysis is as shown in Fig. 5. A clear distinction in the surface structure of the both the char was observed. Large and deep cracks were found in conventional pyrolysed OPS char as shown in Fig. 5. On the other hand, pores were observed in microwave pyrolysed char with absence of any cracks. Microwave creates volumetric heating compared to conventional heating. Unlike the conventional heating where the heat is transferred from the outer surface of the material to the inner part, the microwave heat is generated in entire volume of surface (Popescu et al., 2008) and more particular from the core of the materials towards the surface of the materials (see Fig. 1). Hence, in conventional pyrolysis of OPS the outer surface is at higher temperature than inner core. By the time the inner surface gets the heat, the outer surface undergoes overheating and creates the cracks or

ssures. This diminishes the quality and makes the char more fragile. Conversely, the microwaves try to penetrate and might have generated the heat in the inner core of the OPS as reported by Miura et al. (2004) during microwave pyrolysis of wood block. Therefore, the temperature prole during microwave pyrolysis of OPS showed lower surface temperature. Guo and Lua (2000) has also reported the characteristics of activated carbon and its surface properties prepared from OPS via microwave heating. They found that minimum microwave power required to prepare activated carbon or determining the maximum loss of volatile matter was about 450 W which agreed with the our present study.

5. Conclusions Microwave heating technique was highly effective in pyrolysing the oil palm biomass (ber and shell), specically the large size OPS which otherwise if not possible but would had been difcult. Eco-friendly chars as microwave absorber assisted in increasing the pyrolysis temperature within short period of time. The yield of pyrolysis products were found to greatly inuence by microwave absorber. Bio-oil contains important chemical compounds such as phenols, ketone, aldehyde and carboxylic acids. Conventionally pyrolysed char could not be used for further applications since there persist large and deep cracks due to overheating of surface, which make them fragile and lost of porous nature. Overall, the low temperature microwave pyrolysis of OPS gave signicant contribution in energy efcient route to bio-oil production. Moreover, use of ecofriendly microwave absorber can assist the microwave to operate at low power input, thus reducing the need for high power microwave pyrolysis.

Acknowledgements The authors are grateful to Ministry of Higher Education, Malaysia and UTM for Fundamental Research Grant. In addition, the authors thank the staff of Faculty of Science, UTM for their help in obtaining the FT-IR results. The rst author would also like to extend thanks to Mr. Maizan Sulaiman from Manufacturing Department, Faculty of Mechanical Engineering for helping in Image analysis.

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