Bioresource Technology 102 (2011) 35123520

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

The characteristics of bio-oil produced from the pyrolysis of three marine macroalgae
Yoon Ju Bae a, Changkook Ryu b, Jong-Ki Jeon c, Junhong Park d, Dong Jin Suh e, Young-Woong Suh e, Daejun Chang f, Young-Kwon Park a,g,
a

Graduate School of Energy and Environmental System Engineering, University of Seoul, Seoul 130-743, Republic of Korea School of Mechanical Engineering, Sungkyunkwan University, Suwon 440-746, Republic of Korea Department of Chemical Engineering, Kongju National University, Cheonan 331-717, Republic of Korea d School of Mechanical Engineering, Hanyang University, Seoul 133-791, Republic of Korea e Clean Energy Center, Korea Institute of Science and Technology, 39-1 Hawolgok-Dong, Seoul 136-791, Republic of Korea f Division of Ocean Systems Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea g School of Environmental Engineering, University of Seoul, Seoul 130-743, Republic of Korea
b c

a r t i c l e

i n f o

a b s t r a c t
The pyrolysis of two brown macroalgae (Undaria pinnatida and Laminaria japonica) and one red macroalgae (Porphyra tenera) was investigated for the production of bio-oil within the temperature range of 300600 C. Macroalgae differ from lignocellulosic land biomass in their constitutional compounds and high N, S and ash contents. The maximum production of bio-oil was achieved at 500 C, with yields between 37.5 and 47.4 wt.%. The main compounds in bio-oils vary between macroalgae and are greatly different from those of land biomass, especially in the presence of many nitrogen-containing compounds. Of the gaseous products, CO2 was dominant, while C1C4 hydrocarbons gradually increasing at 400 C and above. The pretreatment of macroalgae by acid washing effectively reduced the ash content. The pyrolysis of macroalgae offers a new opportunity for feedstock production; however, the utilization of bio-oil as a fuel product needs further assessment. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 30 June 2010 Received in revised form 3 November 2010 Accepted 4 November 2010 Available online 12 November 2010 Keywords: Macroalgae Pyrolysis Laminaria japonica Porphyra tenera Undaria pinnatida

1. Introduction Due to their high photosynthesis efciency and production rates (Gao and McKinley, 1994), algae are attractive biomass for the production of chemicals and fuels. Microalgae have so far received more attention than macroalgae for biofuels production, which can be cultured in pond or photobioreactors with supply of nutrients or wastewater. However, macroalgae, especially those cultivated in the shallow seawater, also have good potential as a source for biofuels. Marine macroalgae are currently being cultured on a large-scale in coastal areas of East Asian countries including Korea. For example, the annual production of Laminaria is estimated to 58 kton/year on a dry basis in 2008 in Korea (Ryu et al., 2009). Macroalgae naturally grow absorbing phosphorus and nitrogen compounds, which helps to reduce eutrophication (Ryu et al., 2009) and minimizes the cost and energy input for supply of nutrients, unlike microalgae cultured in fresh water.
Corresponding author at: Graduate School of Energy and Environmental System Engineering, University of Seoul, Seoul 130-743, Republic of Korea. Tel.: +82 2 2210 5623; fax: +82 2 2244 2245. E-mail address: catalica@uos.ac.kr (Y.-K. Park).
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2010.11.023

Biodiesel production based on trans-esterication has been of major interest for algae, but pyrolysis is another option in processing biomass for the production of feedstock and fuel (Huber et al., 2006; Heo et al., 2010a; Park et al., 2007, 2010a). This thermochemical conversion takes place at mild temperatures in an inert atmosphere without use of a catalyst, thus being faster and simpler than the process to produce biodiesel from algae. Pyrolysis decomposes organic structures to various vapor phases and gas compounds, leaving a carbon-rich solid residue (char). The vapor phase compounds are condensed into liquid (bio-oil) downstream of the process. Bio-oil is a useful fuel with better transportation, storage and feeding properties as potential carbonneutral surrogate for petroleum. Char is also a value-added product that can be utilized as fuel or chemical adsorbent with high energy content and reactivity. The yields and properties of pyrolysis products depend mainly on the heating rate, temperature and retort atmosphere. Faster heating rates at a temperature of about 500 C maximize the yield of bio-oil (Mohan et al., 2006), while slower heating rates favor the formation of char. The effects of the process parameters, and the detailed bio-oil characteristics have been extensively studied for land biomass (Lee et al., 2008; Park et al., 2008a,b; Mohan et al., 2006; Demirbas, 2009).

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According to Dawczynski et al. (2007), the organic constituents of macroalgae differ greatly between brown and red algae. The protein content, including various amino acids, is lower (7 16 wt.%dry) in brown algae than in red algae (2147 wt.%dry). The fat content is very low (16 wt.%dry) in marine macroalgae. The carbohydrates in brown algae consist of laminarian and mannitol, together with fucoidan, cellulose and alginates. The typical carbohydrates in red algae include oridean starch, cellulose, xylan and mannan. Macroalgae also have high mineral or ash content (about 38 wt.%dry in Laminaria, 39.3 wt.%dry in Undaria and 20.6 wt.%dry in Porphyra), mainly comprised of K, Na, Ca and Mg

(Reprez, 2002), which is not benecial for the use of macroalgae as a fuel; however, Ross et al. (2009) reported that pretreatment by acid-washing greatly reduced the ash content. In contrast to macroalgae, woody biomass consists of cellulose, hemicellulose and lignin with low ash content (Demirbas, 2009). The above discussion suggests that the pyrolytic behavior and the compounds in the bio-oil produced by pyrolysis signicantly differ from those produced from land biomass; they also vary between algae species. The route of pyrolysis for the production of feedstock and fuel from two types of brown algae (Undaria pinnatida and Laminaria

Fig. 1. Schematic of pyrolysis reactor.

Table 1 Physicochemical properties of the seaweeds. Materials Proximate analysis (wt.%) Water V.M F.C Ash C H Ob N S Undaria 9.50 53.62 11.04 25.84 34.01 4.99 56.95 3.34 0.71 7.68 1.76 1.26 11,190 5694 10,970 68,510 3535 883.8 144.1 33.23 4.62 153 6.35 0.14 0.79 Acid-washed Undaria 4.00 73.88 21.36 0.76 47.48 5.08 42.72 4.11 0.61 17.28 1.28 0.67 21.02 3530 26.77 5026 788.4 9.07 78.78 3.54 <1.00 130 <1.00 0.12 0.27 Laminaria 7.65 53.10 10.97 28.28 30.60 4.89 62.44 1.51 0.56 6.41 1.92 1.53 7726 102,470 5942 26,790 2111 317 59.22 7.65 4.81 60 <1.00 0.04 <0.20 Porphyra 6.41 69.66 13.49 10.44 40.60 4.65 47.4 6.13 1.26 12.29 1.37 0.88 3013 38,710 3369 12,350 6854 31.73 115.0 37.38 17.91 17 15.61 0.07 1.28 Wood (Japanese larch)c 8.8 91.0 0.2 50.8 6.8 42.4 0.1 19.44 1.61 0.63 529.5 348.1 103.3 92.1

Ultimate analysis (wt.%)a

HHV(MJ/kg) H/C atom ratio O/C atom ratio Metal content (ppm)

Ca K Mg Na P Sr Fe Zn Mn Al Cu Se Pb

a b c

On ash free basis. By difference. Park et al.(2008a).

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japonica) and one red algae (Porphyra tenera) were investigated, as the pyrolysis of these seaweeds have not been reported in the literature. The three seaweeds grow naturally in East Asian coastal areas and are extensively cultivated for food and pharmaceutical purposes (Ryu et al., 2009). U. pinnatida typically grows with the rate of about 2 m/year and is well-adapted to large variations in water temperature. L. japonica is an edible alga that grows with the rate of about 34 m/year. Mannitol, algin and iodine are extracted from Laminaria for many industrial and medical purposes. P. tenera is a species of laver or nori with a growth rate of 10 cm/ year. The amount harvested in 2008 in Korea was estimated to 76 kton for Undaria and 44 kton for Porphyra on a dry basis. The price of Undaria and Laminaria ranges from 1050 US$/ton on a dry basis in Korea (Ryu et al., 2009), which is comparable to wood chip (3050 US$/ton in Korea) but is considerably lower than cultured microalgae, e.g., over 185 US$/ton (Huber et al., 2006). In this study, the three macroalgae and acid-washed Undaria were characterized for their fuel properties and pyrolytic behaviors, with a focus on the properties of bio-oils. For the pyrolysis tests, a lab-scale reactor was used, at temperatures ranging from 300600 C. Based on the analytical results for the bio-oils, the use of pyrolysis for the production of feedstock and fuel from macroalgae is discussed.

min up to 800 C, in an inert atmosphere (N2 at a ow rate of 20 ml/min). 2.3. Pyrolysis tests and products characterization Pyrolysis tests were carried out in a packed tube reactor, as shown in Fig. 1. A quartz U-tube reactor, with an internal volume of 50 ml, height of 160 mm and diameter of 15 mm, was lled with 68 g of biomass sample and purged with nitrogen at 50 ml/min for 15 min. The reactor was then inserted into the furnace at a prescribed temperature of 300, 400, 500 or 600 C and remained there for 1 h in order for complete pyrolysis to occur. The vapor-phase products produced during pyrolysis were passed through a condenser (RW 1025G, JEIO TECH) at 20 C, using ethanol as the coolant, for collection of the bio-oil. The compounds in the bio-oil were quantied using GCMS (HP 5975C inert), with an ultra alloy-5 (30 m 0.25 mm 0.5 mm) capillary column. The water content in the bio-oil was determined by ASTM E203 using a Karl-Fischer titrator (Metrhom 870 KF Titrino), with HYDRANAL Composite 5 K (Riedel-de Haen) and methanol as the solvent. The ultimate analysis of the bio-oil was carried out using the same method described previously for the biomass samples (Park et al., 2010b,c,d). To assess the composition of gases, the product gases in each pyrolysis experiment were collected into a sampling bag and then analyzed using GC (ACME 6000, Young Lin Instrument Co. Ltd),

2. Methods 2.1. Sample preparation

1.2

Air-dried samples of U. pinnatida, L. japonica and P. tenera were shredded and sieved into three particle size ranges: 450 lm (300 600 lm), 800 lm (6001000 lm) and 1300 lm (10001600 lm). The samples were then dried in an oven at 80 C for 48 h to reduce the moisture content prior to storage in sealed containers. The amount of samples used for each pyrolysis experiment was 810 g. To investigate the effect of pretreatment by acid, a 300 g U. pinnatida sample was treated with 2 M HCl solution. The sample and acid solution were mixed on a hot plate stirrer at 60 C for 6 h. The Cl remaining was checked by dropping 0.1 M of AgNO3 onto the sample. The sample was then washed 34 times in distilled water before undergoing the drying process described above.

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2.2. Fuel characterization of macroalgae A proximate analysis for the samples was performed based on ASTM methods E871, E872-82 and D1102-84. The moisture was evaporated in an oven at 110 C for 4 h. The volatile matter was removed in a furnace with an inert atmosphere at 950 20 C for 7 min. The ash content was then acquired by removing the combustible matter in air at 600 25 C. The C, H, N and S contents of the samples were determined using a Vario-EL III analyzer (Elementar Analysensysteme GmbH), which can burn up to 2 mg of sample at 1150 C, with a sulfanilic acid standard. The oxygen content was calculated by difference. The higher heating value (HHV) of the samples was then estimated by the correlation of Channiwala and Parikh (2002). The metal composition of the samples was analyzed using an ICPOES (JY Ultimate2C, Jobin Yvon) and ICPMS (Elan 6100, Perkin Elmer). The ICPMS used 0.1 ml of sample diluted with 20 g of 2% HNO3 solution. TGA was used to examine the thermal decomposition of the samples, which is essential in identifying the range of temperatures required for the pyrolysis tests (Heo et al., 2010b; Park et al., 2008a, 2009). A TGA Pyris 1 analyzer (Perkin Elmer) was used, with about 8 mg of each sample, at a heating rate of 10 C/

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Fig. 2. TG (a) and DTG (b) curves of the macroalgae.

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with CO, CO2, H2 and CH4 measured via a TCD with a Carboxen 1000 column (15 ft 1/8 inch), while the hydrocarbons were measured via a FID HP-plot Al2O3/KCl column (50 m 0.322 m 8.00 lm). All the experiments, including the pyrolysis tests and products characterization, were carried out in triplicate, with the mean values taken for each experiment. 3. Results and discussion 3.1. Fuel properties of macroalgae Table 1 shows the properties of the fuel from the seaweeds tested. The seaweeds contained higher ash content and possessed higher amounts of N and S compared to typical land biomass, Japanese Larch (Park et al., 2008a), also shown in Table 1. This led to signicantly lower HHVs of the macroalgae than the land biomass. Laminaria had the highest ash content at 28.8%, but Porphyra had the highest N and S contents at over 6% and 1%, respectively. The hydrogen and oxygen contents in Undaria and Laminaria were higher than those for marine biomass reported in Ross et al.s study (Ross et al., 2008), which showed typical H/C and O/C ratios in the ranges of 1.01.4 and 0.50.8, respectively. The ash content of the acid treated Undaria dramatically decreased to 0.76% and the oxygen content to 42.72%, which led to a substantial increase in the HHV. The metal composition of the seaweeds is also shown in Table 1. Undaria was rich in Na, while K was dominant in Laminaria and

Porphyra. Ca, Mg and P were also common in the seaweeds. Such high concentrations of alkali and alkali earth metals in untreated seaweeds may act as catalysts during pyrolysis by accelerating the cracking of tar vapors. If the seaweeds are burned or gasied, the alkali metals may lead to severe operational problems by lowering the ash melting points (Ross et al., 2008). When acid treated, the Undaria sample showed signicant reductions in Na, Mg and Ca, while K was resistant to washing. Fig. 2 shows the TGA and differential thermogram (DTG) for the seaweeds. Following the evaporation of moisture at around 100 C, mass loss actively occurred in the range of 180500 C, with a peak in the DTG at 280300 C, while a gradual decrease continued above 500 C. Such trends may be attributed to the decomposition of carbohydrates (180270 C) and proteins (320450 C), followed by the gradual loss of volatile metals and the decomposition of carbonate (Ross et al., 2008). The reduction of the inorganic contents due to acid washing decreased the onset of pyrolysis for Undaria by about 40 C. The remaining mass (char and ash) was also reduced from 44% to 26% at 700 C, which was mainly due to the loss of ash content. 3.2. Pyrolysis products of macroalgae The product yields from pyrolysis for an average particle size of 0.8 mm, in the temperature range of 300600 C, are shown in Fig. 3. The solid residue (char) decreased with increasing temperature, which was comparable to the TGA results shown in Fig. 2. The vapor-phase products comprised of condensable compounds and

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Fig. 3. Product yields of macroalgae for different pyrolysis temperatures: (a) Undaria, (b) acid-washed Undaria, (c) Laminaria and (d) Porphyra.

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light-weighted gases, which were separated by the oil collectors. The bio-oil yields peaked at 500 C for all four samples, with a maximum of 47.4 wt.% (Porphyra). The acid-washed Undaria produced 45.8 wt.% bio-oil at 500 C (Fig. 3b), which was 6.3 wt.% more than that of the untreated sample, (Fig. 3a), due to the removal of ash content. Laminaria produced the lowest bio-oil content at 37.5 wt.%. When considering the ash content in macroalgae, the peak temperature and the maximum oil yield were similar to those via the slow pyrolysis of land biomass (Phan et al., 2008), but lower than those via fast pyrolysis (6075 wt.% for woody biomass) (Mohan et al., 2006). The bio-oil yields decreased at 600 C, especially

for untreated Undaria and Laminaria. This was believed to be the result of secondary tar reactions in the vapor phase since the liquid yields decreased while the gas yields correspondingly increased at 600 C. In the pyrolysis of land biomass, the secondary tar reactions have been shown to become signicant at high temperatures, forming more aromatic oil compounds, but releasing gases, such as CO and H2 (Morf et al., 2002; Gilbert et al., 2009; Heo et al., 2010c). The gaseous products, which consisted largely of CO2, gradually increased with increasing temperature, as shown in Fig. 4. In the early stage of pyrolysis, at 300 C, CO2 accounted for 85.8

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Fig. 4. Effect of reaction temperature on gas composition: (a) Undaria, (b) acid-washed Undaria, (c) Laminaria and (d) Porphyra.

Table 2 Properties of bio-oils produced from pyrolysis of seaweed at 500 C. Phases Materials Elemental composition (wt.%dry) C H Oa N S Aqueous phase Undaria 10.1 11.5 72 6.2 0.2 9.56 39.0 Laminaria 20.6 10.0 65.1 4.3 0.6 12.24 44.7 Porphyra 16.3 7.0 69 7.6 0.6 6.75 27.1 Organic phase Undaria 56.5 5.7 29.8 7.2 0.8 23.33 Laminaria 73.5 7.9 12.9 5.7 0.2 33.57 Porphyra 65.7 7.4 17.3 9.6 0.2 29.74 57.0 7.0 34.2 1.8 22.2c 62.07 8.76 19.43 9.74 30d Bio-oil from Japanese larchc Bio-oil from C. protothecoidesd

HHVb (MJ/kg) Water content (wt.%)

a b c d

By difference. HHV of oils in this study was estimated by using the correlation of Channiwala and Parikh(2002), excluding the water content. Park et al. (2008a). Miao et al. (2004).

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95.1 vol.% of the gases. On the generation of other gases from the thermal decomposition, the proportion of CO2 reduced to between 64.6 and 74.9 vol.% at 500 C. The yield of CO remained relatively consistent at about 4.314.0 vol.%, while the C1C4 hydrocarbons rapidly increased to above 30 vol.% with increasing temperature. H2 also appeared at above 500 C, but only as a minor component. No signicant difference in the gas composition was observed between the untreated and acid-washed Undaria. The sole dominance of CO2 in the gases also differentiates the pyrolysis of macroalgae from that of land biomass, where the CO2 and CO are generally equally dominant (Yang et al.,2007; Phan et al., 2008). For the Undaria samples with particle sizes ranging between 0.30.6 mm and 1.01.6 mm, identical product yield trends were acquired, as described above. Although not shown here, the biooil yields were only 12 wt.% lower than those in Fig. 3, because the particle size range had no signicant effect on the heat transfer or pyrolysis characteristics with the current reactor conguration.

pared to the microalgae, C. protothecoides, (Miao et al., 2004), the HHV is lower due to the high oxygen content in the aqueous phase.

Table 4 Compounds identied in the organic phase of Laminaria (area%). No. Compound Pyrolysis temperature(C) 300 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Benzene 2-Pentanone Furan, 2,5-dimethylPhenol 1H-Pyrrole, 1-methylToluene 1H-Pyrrole 1-Hexene 2(1H)-Pyridinone, 6-methylPyridine, 4-methylFuran, 2,5-dihydro2-Pentene, (E)1,3-Cyclohexadiene, 5,6-dimethyl-,ciso-Xylene 2-Furanmethanol 1-Pentyne Styrene Ethanone, 1-(2-furanyl)2-Cyclopenten-1-one, 3,4-dimethylCyclopropanecarboxylic acid Bicyclo[4.1.0]heptane, 1-methyl2-Cyclopenten-1-one, 2,3,4-trimethyl (Phenol, 2-methoxy-) 3,4-Heptadiene (E)-Hex-2-en-4-yn-1-ol 1-Cyclohexene-1-methanol Phenol, 3-methylPhenol, 3,5-dimethyl1H-Indene, 3-methyl2-Propenylthiobenzene Dianhydromannitol Cyclohexane, 1,2-propadienyl1-(3-Methylphenyl)buta-1,3-diene Indole Isosorbide 6-Cyclobut-1-enylspiro[2.4]hept-4Spiro Benzene, 2-propenylPentadecane (4Z)-5-Chloro-3,4-dimethyl-2,4heptadiene Bicyclo[3.1.1]heptane, 2,6,6-trime thyl 0.15 1.25 0.13 0.39 0.49 12.94 0.31 27.28 5.09 1 400 0.39 0.25 0.23 0.74 0.9 0.17 0.1 0.19 0.91 0.59 11.77 0.74 0.76 0.85 0.66 0.65 1.44 0.48 12.31 1.24 0.88 2.95 0.14 0.28 0.9 1.03 500 0.44 0.48 0.4 0.35 1.69 2.64 2.89 3.76 0.32 0.24 1.19 3.78 0.84 1.36 0.33 3.21 1.79 9.25 2.05 0.15 1.52 2.17 0.63 1.07 0.6 0.5 3.47 1.07 0.42 0.14 0.42 1.06 0.71 600 0.76 0.19 0.32 1.43 2.85 3.3 2.16 0.87 0.31 1.83 1.84 7.76 0.46 0.97 2.5 0.75 2.65 1.29 0.59 2.17 1.41 0.19 0.13 0.43 1.71 0.73

3.3. Elemental composition and HHV of the bio-oil The collected bio-oil formed into two strata; aqueous and heavy organic phases. Each phase was separated using a centrifugal separator, operated at 300 rpm for 5 min, with elemental and compound compositions characterized. The mass fraction of the organic phase was 55.7% for Undaria, 54.6% for acid-washed Undaria, 43.6% for Laminaria and 59.9% for Porphyra. Table 2 lists the properties of the two phases together with the data for land biomass and microalgae for comparison. The aqueous phase contained a large amount of water (2745 wt.%). Due to the presence of oxygenated compounds, the oxygen content in the aqueous phase was over 65% even after the water had been removed using a Karl-Fisher titrator. The carbon content in the aqueous phase was very low (about 1020%). In contrast, the organic phase contained a very high carbon content (56.565.7 wt.%). The oxygen content in the organic phase was about 1330 wt.%, which was much lower than that of woody biomass (Phan et al., 2008), which led to considerably high HHVs within the organic phase (23.3 MJ/kg for Undara, 33.6 MJ/kg for Laminaria and 29.7 MJ/kg for Porphyra), as estimated by the correlation of Channiwala and Parikh (2002). When combining the two phases excluding the water content, overall HHV of the bio-oils became 19.2 MJ/kg for Undaria, 25.4 MJ/kg for Laminaria and 22.6 MJ/kg for Porphyra, similar to that of the land biomass (Japanese Larch: Park et al., 2008a). However, com-

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Table 3 Compounds identied from the organic phase of untreated and acid-washed Undaria (area%). Peak no. Pyrolysis temperature(C) Compound 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Toluene 2-Butenenitrile 4-Methyl-3-penten-2-one 2-Methyl-pyridine Ethylbenzene 1-Methyl-piperazine Styrene 1-Ethyl-2-methyl-benzene 2,4-Nonadiyne Indane Phenol 4-Methyl-phenol 2,2,6,6-Tetramethyl-4-piperidinone 2(1H)-Pyridinone Indole Pentadecane Neophytadiene 2,6,6-Trimethyl-bicyclo[3.1.1]heptane 300 Untreated 0.27 1.09 1.76 5.8 2.61 0.6 6.48 2.22 5.68 7.97 Acid-washed 0.91 0.37 1.7 0.22 0.18 0.83 1.12 25.31 3.67 18.88 400 Untreated 0.28 0.97 11.6 3.61 3.72 3.02 7.31 0.88 3.07 0.3 4.28 Acid-washed 0.52 0.59 5.25 0.3 4.78 0.23 1.88 2.42 24.58 4.34 1.00 6.58 500 Untreated 1.12 1.07 5.44 0.25 1.09 1.73 1.91 0.58 3.73 3.86 5.33 0.26 2.56 0.46 4.04 1.98 Acid-washed 1.39 0.83 4.62 0.89 0.74 5.04 0.66 0.33 1.64 3.81 22.51 3.95 0.96 0.82 3.77 2.80 600 Untreated 0.49 1.60 3.79 1.22 0.53 0.73 2.28 2.94 0.57 1.37 2.94 3.84 4.64 2.19 0.44 2.99 1.17 Acid-washed 2.00 0.94 2.92 0.96 0.65 1.54 0.66 0.73 0.3 1.99 3.67 21.47 3.29 0.90 0.86 3.57 2.34

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Y.J. Bae et al. / Bioresource Technology 102 (2011) 35123520 Table 5 Compounds identied in the organic phase of Porphyra (area%). No. Compound Reaction temperature (C) 300 1 2 Furan, 2,5-dimethylToluene Pyridine 1H-Pyrrole 3-Penten-2-one, 4-methylPyridine, 2-methyl2-Pentanone, 4-hydroxy-4-methyl1H-Pyrrole, 2-methylEthylbenzene 2-Pentanone, 4-amino-4-methylStyrene Ethanone, 1-(2-furanyl)Butyrolactone Pyridine, 3,5-dimethyl1H-Pyrrole, 3-ethyl-2,4,5-trimethylPhenol N-(3-Oxobutyl)-2-methylazetidine 4-Piperidinone, 2,2,6,6-tetramethylPhenol, 4-methylBenzeneacetonitrile Naphthalene Phenol, 2,4-dimethyl2-Pyridinecarboxaldehyde 1-Cyclohexene-1-methanol Indole 7-Oxabicyclo[4.1.0]heptane, 2methyleneNaphthalene, 1,2,3,4-tetrahydro-1,1,6trimethyl1-Dodecene 1-Tetradecanol Pentadecane 2-Chloro-3-hydrazinopyrazine 8-Heptadecene Heptadecane 2-(2-Nitrovinyl)furan Benzenamine, N-1-cyclohexen-1-yl-Nmethyl1H,3H-Pyrano[3,4-c]pyran-5carboxaldehyde, 4,4a,5,6-tetrahydro6-methyl-1-oxo-, [4as(4a.alpha.,5.alpha.,6.beta.)]4-[5-Methyl-2-(1methylethylidene)cyclohexyl]-3cyclohexen-1-one 2-Propenal, 3-(dimethylamino)-3-(1piperidinyl)4-Nonene, 5-butylNeophytadiene (2E)-3,7,11,15-Tetramethyl-2hexadecene Heptadecanenitrile Pentadecanenitrile 1H,3H-Pyrano[3,4-c]pyran-5carboxaldehyde, 4,4a,5,6-tetrahydro6-methyl-1-oxo-, [4as(4a.alpha.,5.alpha.,6.beta.)]9-Hexadecenoic acid Sulfonium, dimethyl 0.7 0.17 1.95 0.23 0.65 6.62 1.75 0.33 0.56 5.52 8.45 1.03 0.17 0.29 0.32 0.67 1.25 0.38 400 0.16 1.88 0.45 0.25 2.01 0.45 1.59 0.25 0.35 11.07 0.66 0.35 1.29 0.22 1.36 2.67 9.39 3.05 0.45 0.18 0.18 0.1 0.35 0.08 0.26 1.06 0.42 1.21 0.31 0.44 0.12 500 0.14 2.22 0.84 2.79 0.81 2 0.74 10.17 0.99 0.61 1.1 0.35 1.51 1.78 2.97 12.23 3.03 0.68 0.38 0.6 0.2 0.25 0.28 0.76 0.92 0.44 1.16 0.27 0.25 0.09 600 0.1 2.15 2.11 1.04 1.25 0.87 0.34 7.13 0.74 0.52 0.94 0.46 2.25 2.39 11.47 3.55 0.88 0.46 0.48 0.29 0.77 0.51 0.3 0.69 0.77 0.7 1.22 0.29 0.12 0.34 0.32

In both oil phases, the nitrogen contents were very high, ranging from 4.3 (the aqueous phase from Laminaria) to 9.6 wt.% (the organic phase of Porphyra). Compared to the nitrogen contents of the original biomass (3.3% for Undaria, 1.5% for Laminaria and 6.1% for Porphyra), as shown in Table 1, the results suggest that nitrogen was largely concentrated in the bio-oil in the form of nitrogen-containing organic compounds. Bio-oil from microalgae (Miao et al., 2004) also shows a high content of nitrogen, unlike that from land biomass, as also listed in Table 2. Details of the compound composition in the bio-oils of macroalgae will be discussed in the next section. When the bio-oil is used as fuel, the high nitrogen content may lead to the increased formation of fuel NOx during combustion; therefore, further assessment of the combustion properties of the bio-oil will be required. 3.4. Compound compositions of the bio-oil For the GCMS analysis, the heavy organic phase was diluted with acetone at a ratio of 1:5, while the aqueous phase was analyzed without any pretreatment. From the GCMS proles of the untreated and acid-washed Undaria at 500 C, 17 peaks were identied, as listed in Table 3. Increased numbers of compounds, such as 2-methyl-pyridine, styrene and pentadecane, were found in the bio-oils at 500 and 600 C than at lower temperatures. Of these, 6 compounds contained one or two nitrogen atoms: 2-butenenitrile (C4H5N), 2-methyl-pyridine (C6H7N), 1-methyl-piperazine (C5H12N2), 2,2,6,6-tetramethyl-4-piperidinone (C9H17NO), 2(1H)pyridinone (C4H7NO) and indole (C8H7N). Ross et al. (2008) also reported an increased amount of nitrogen-containing compounds and linear chain alcohols in the bio-oil from other macroalgae compared to those from land biomass. In the bio-oil from the acid-washed Undaria, the compounds identied were similar, with the exception of 2,4 nonadiyne, but signicant increases in the relative portions of 2,2,6,6-tetramethyl-4-piperidinone and 2(1H)-pyridinone were observed. This could have been the result of the reduced catalytic effects of minerals on tar cracking, but a detailed explanation will require further investigation. Tables 4 and 5 list the compounds identied in the organic phase of the bio-oils from Laminaria and Porphyra, respectively, and the diversity of the compounds present in both bio-oils was greater compared to those from Undaria. The compounds common to all the bio-oils included toluene, pyridine, ethylbenzene, styrene, phenols, indole, pentadecane and neophytadiene. Some nitrogen-containing compounds (2-butenenitrile; 1-methyl-piperazine; 2,4-nonadiyne and 2(1H)-pyridinone) present in the bio-oil from Undaria were not found in those of Laminaria and Porphyra, although more nitrogen-containing compounds were identied. Certain compounds were also found to be unique to macroalgae. Especially for Laminaria, dianhydromannitol was the dominant compound, which would be from the dehydration of the abundant amount mannitol in the seaweed. Mannitol is a sugar alcohol in brown algae (Abdel-Fattah and Hussein, 1970), which has many uses in the chemical and food industries (Ghoreishi and Gholami Shahrestani, 2009). The organic phase from Porphyra was rich in 4-amino-4-methyl-2-pentanone and 2,2,6,6-tetramethyl-4-piperidinone, the latter of which is used in pharmaceuticals. Aromatic hydrocarbons, such as phenol, benzene, toluene, o-xylene and styrene, were found at 400 C and above. A well known fact related to land biomass is that the tar compounds from the lignocellulosic materials gradually turn into polycyclic aromatic hydrocarbons (PAHs) due to secondary tar reactions (Morf et al., 2002). Unlike land biomass; however, with the exception of naphthalene, no PAHs were found in Porphyra at 600 C. The rare presence of PAHs in the bio-oils of macroalgae is favorable due to the low reactivities during their combustion.

3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

18 19 20 21 22 23 24

0.11

0.89

0.14

0.37 1.36 0.43 1.48

0.37 1.16 0.36 1.63 0.08

0.18 1.16 0.35 0.8 0.18

0.19 1.26 0.17 0.76 0.26

25 26 27

1.59 0.16

0.34

Table 6 shows the compounds identied in the aqueous phase of the bio-oils produced from the four macroalgae samples at 500 C. The aqueous phase contained many water-soluble oxygenated acid, alcohol and ketone compounds. Other than acetic acid; however, the compound compositions between the macroalgae were very different. Dianhydromannitol was the dominant compound in the aqueous phase of bio-oil from Laminaria, as it was in the organic phase. The aqueous phase from Porphyra largely contained dihydro-2(3H)-furanone, which is used in agrochemical, food and pharmaceuticals. Additionally, the aqueous phase of the

Y.J. Bae et al. / Bioresource Technology 102 (2011) 35123520 Table 6 Compounds identied in the aqueous phase of the bio-oil from 500 C (area%). RT (s) 2.34 2.76 2.91 3.56 4.03 4.36 5.83 6.14 7.03 7.37 7.57 7.79 8.23 8.82 8.96 9.26 10.31 11.94 12.07 12.63 12.88 13.09 13.30 15.41 15.50 15.58 16.63 17.33 17.42 18.55 19.96 21.08 21.52 22.01 22.42 23.31 23.58 24.13 24.33 26.66 29.08 29.77 30.96 32.11 33.08 34.45 35.32 36.69 37.67 37.70 39.07 Compounds Butanal, 3-methyl3-Hexanone Furan, 2,5-dimethylDisulde, dimethyl Toluene Acetic acid Pyridine, 2-methyl1,2-Ethanediol Ethylbenzene o-Xylene Pyridine, 3-methyl2-Furanmethanol Styrene Acetamide 2-Cyclopenten-1-one, 2-methyl1,4-Dimethylcyclohexene 2(3H)-Furanone, dihydro1-Decene Benzene, 1-ethyl-3-methyl2,3,5-trimethyl pyrazine Acetic acid, phenyl ester Benzene, 1,2,4-trimethylBenzene, 2-propenyl1-Undecene 6H-Purin-6-one, 1,7-dihydroPent-2-ynal Phenol, 4-methyl2-Pyrrolidinone 2-Butyl-1,2-oxaborolane 1-Dodecene 2(1H)-Pyridinone Dianhydromannitol 1-Decene Pyridine-2-carboxamide 1H-Imidazole, 2,4,5-trimethyl4-Pyridinol 3,4,5-Trimethylpyrazole 3-Pyridinol ()-(1R,5S)-exo-2(R)-Methylbicyclo[3.2.1]octan-3-one 1-Pentadecene 2H-Pyran-2-one, 3,6-dihydro-5-methylImidazole, 2-triuoromethyl-5-methyl-4-nitroLevoglucosan 6-Tridecene, 7-methyl6-Tridecene, 7-methyl-uric acid Neophytadiene (Z)-6,6-Dimethylcyclooct-4-en-1-one Isophytol 3,9-Diazatricyclo[7.3.0.0(3,7)]dodecan-2,8-dione 5,10-Diethoxy-2,3,7,8-tetrahydro-1H,6H-dipyrrolo[1,2-a;10 ,20 -d]pyrazine 2-Butenoic acid, 3-amino-, ethyl ester Undaria 0.01 7.82 4.98 2.52 0.5 0.15 0.33 0.06 0.13 Acid-washed Undaria 0.02 0.02 0.31 2.24 9.66 0.59 0.94 0.62 0.21 0.94 1.11 0.57 0.27 0.27 0.06 0.52 0.63 0.21 1.52 1.47 0.4 9.16 0.32 1.71 0.86 0.86 3.39 0.62 1.05 2.89 2.44 0.33 1.28 0.18 Laminaria 0.03 0.09 0.56 0.17 0.85 0.12 1.36 18.32 2.47 0.91 0.12 Porphyra 0.2 4.03 5.42 0.3 0.12 1.44 0.32 0.48 1.47

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bio-oil from acid-washed Undaria had a greater diversity of compounds than that of the untreated Undaria.

Acknowledgement This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 20090072328).

4. Conclusions The macroalgae had a high nitrogen (1.56.13 wt.%) and ash (10.4428.28 wt.%) contents. The pretreatment by acid-washing was able to remove most of the ash content. In the pyrolysis tests, the bio-oil yield reached a maximum, within the range of 37.5 47.4 wt.%, at 500 C. The compounds identied suggest that pyrolysis can be used to produce bio-oils for various uses, such as chemical feedstock, through further treatment. However, the use of pyrolysis for the production of a fuel does not look as attractive as that from the use of land biomass due to the high nitrogen content in the oil.

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