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Energy Sources, Part A: Recovery, Utilization, and Environmental Effects

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Producing Bio-oil from Olive Cake by Fast Pyrolysis

A. Demirbas
a a

Sila Science, Trabzon, Turkey

Available online: 29 Feb 2008

To cite this article: A. Demirbas (2007): Producing Bio-oil from Olive Cake by Fast Pyrolysis, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 30:1, 38-44 To link to this article: http://dx.doi.org/10.1080/00908310600626747

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Energy Sources, Part A, 30:3844, 2008 Copyright Taylor & Francis Group, LLC ISSN: 1556-7036 print/1556-7230 online DOI: 10.1080/00908310600626747

Producing Bio-oil from Olive Cake by Fast Pyrolysis

A. DEMIRBAS1
1

Sila Science, Trabzon, Turkey

Abstract This article reports on physico-chemical properties of olive cakes to evaluate them as a raw material in energy production through thermo-chemical pyrolysis conversion process. The present study focuses on the actions related to the possibilities to utilize in particularly olive cake as an agricultural residue. Olive cake is a very promising material for the production of bio-oil. Liquid, solid, and gaseous products were obtained from olive cake by pyrolysis. If the purpose were to maximize the yield of liquid products resulting from biomass pyrolysis, a low temperature, high heating rate, and short gas residence time process would be required. Flash pyrolysis gives high oil yields. The heating was carried out from 298 K to 1,050 K in the absence of oxygen. The yields of liquid products were obtained from the olive cake by pyrolysis for the runs of different heating rates: 10 K/s, 20 K/s, and 40 K/s. The highest bio-oil yields from the olive cakes were 31.0% at 700 K, 36.0% at 700 K, and 41.0% at 700 K obtained from 10 K/s, 20 K/s, and 40 K/s heating rate runs, respectively. The highest bio-oil yields olive stone shells were 27.0% at 700 K, 31.0% at 700 K, and 34.5% at 750 K obtained from 10 K/s, 20 K/s, and 40 K/s heating rate runs, respectively. Keywords bio-oil, fast pyrolysis, fuels, olive cake, olive kernel

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Introduction
Agricultural residues such as olive kernels, fruit stones and nut shells, are very good precursors for the production of bio-oil, bio-char and bio-gas fuels (Demirbas, 2000a; Aygun et al., 2003). Energy in agriculture is important in terms of crop production and agroprocessing for value adding (Ozkan et al., 2004). Direct combustion is the old way of using biomass. Biomass thermo-chemical conversion technologies such as pyrolysis and gasication are certainly not the most important options at present; combustion is responsible for over 97% of the worlds bio-energy production (Demirbas, 2004a). Amongst thermochemical transformations, pyrolysis has received much attention since the process conditions can be optimized to produce liquids, which may be upgraded to fuels and solid (Zabaniotou et al., 2000). Use for energy recovery is mainly by combustion, while pyrolysis and gasication are being investigated at laboratory and plot scales (Di Blasi et al., 1997). Beside forest residues, a variety of organic materials has been pyrolized successfully in the current pilot plant, such as hazelnut shell, palm residues, rice husks, olive kernels, wheat straw, plastic wastes, automotive shredder residues, dried sludge, and switch grass (Demirbas, 2004b). Olive kernels have been used traditionally for combustion.
Address correspondence to Professor Ayhan Demirbas, P.K. 216, TR-61035 Trabzon, Turkey. E-mail: ayhandemirbas@hotmail.com

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Pyrolysis of biomass generates three different energy products in different quantities: coke, oils, and gases. Liquid, solid, and gaseous products were obtained from olive cake by pyrolysis. These included oil, water-soluble products, char, permanent gases, and C1 C4 hydrocarbon gases. The liquid fraction of the pyrolysis products consists of two phases: an aqueous phase and a non-aqueous phase. The non-aqueous phase is called as pyrolysis oil or bio-oil, and is the product of greatest interest. Because of its size and composition, olive kernel is a very promising material for the production of bio-oil. Depending on the operating conditions, the pyrolysis process can be divided into three subclasses: conventional slow pyrolysis, fast pyrolysis, and ash pyrolysis (Maschio et al., 1992). Fast pyrolysis for production of liquids has developed considerably since the rst experiments in the late 1970s (Bridgwater and Peacocke, 2002). If the purpose were to maximize the yield of liquid products resulting from biomass pyrolysis, a low temperature, high heating rate, short gas residence time process would be required. For a high char production, a low temperature, low heating rate process would be chosen. If the purpose were to maximize the yield of fuel gas resulting from pyrolysis, a high temperature, low heating rate, long gas residence time process would be preferred (Demirbas and Arin, 2002). The chemical composition and caloric value of olive husks have been studied in detail by Demirbas (1998; 2000b; 2002a; 2002b). Table 1 shows the results of structural, proximate and elemental analyses of olive husk samples given in several articles. From Table 1, the higher heating value (HHV) of fresh olive husks (23.2 MJ/kg) is higher than the HHV of processed husks (20.6 MJ/kg). The difference can be explained by the absence of the extracted olive oil, which has estimated HHV of 39.6 MJ/kg. Table 2 shows the average ash composition from olive husk samples. Table 3 shows the elementary analysis results and ash contents of chars from the olive husk samples.

Table 1 Structural, proximate, and elemental analyses of olive husk samples Fresh olive husk (wt% dry basis) Structural analysis Hemicelluloses Cellulose Lignin Extractives Proximate analysis Ash Fixed carbon Volatile matter Elemental analysis C H O N Higher heating value (MJ/kg) 22.3 23.5 44.9 9.3 3.2 32.8 64.0 52.2 6.5 40.5 0.8 23.2 Processed olive husk (wt% dry and ash free basis) 24.3 25.6 50.1 33.8 66.1 52.8 6.7 39.8 0.7 20.6

Source: Demirbas, 1998, 2000, 2002a, 2002b.

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A. Demirbas Table 2 Average ash composition from olive husk samples (wt% dry basis)

SiO2 29.4

Al2 O3 8.4

Fe2 O3 6.3

CaO 14.5

MgO 4.2

Na2 O 26.2

K2 O 4.3

SO3 0.6

P2 O5 2.5

Others 3.6

Source: Demirbas, 2002b.

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The char produced from the olive husk sample contained 91.3% carbon where the carbonization temperature was 1,150 K. This article reports on physico-chemical properties of olive cakes to evaluate them as a raw material in energy production through thermo-chemical pyrolysis conversion process.

Experimental
The physico-chemical characteristics of olive fruit constituents and olive cakes were analyzed according to standard methods. Moisture and total solid contents were determined by heating the sample at 378 K for 24 h. The olive stone shell and olive cakes were utilized for thermo-chemical conversion process for liquid bio-oil production in pyrolysis unit as per the procedure followed by Demirbas et al. (1996). The main element of this device was a horizontal cylindrical reactor of stainless-steel, 127.0 mm height, 17.0 mm inner diameter, and 25.0 mm outer diameter inserted vertically into an electrically heated tubular furnace and provided with an electrical heating system power source, with changing heating rates. Air dried sample was weight for run 1.00 g and pyrolyzed in the horizontal tube reactor. Heat to tube was supplied from external heater and the power was adjusted to give an appropriate heat up time. The simple thermocouple (NiCrConstantan) was placed directly in the pyrolysis medium. For each run, the heater was started at 298 K and terminated when the desired temperature. The heating was carried out from 298 K to 1,050 K in the absence of oxygen. The pyrolysis products were collected as condensable liquids products, tarry materials, non-condensable gaseous products, and solid residue (char). The experiments were carried out to determine the effect of the pyrolysis temperature and the heating rate

Table 3 Elementary analysis results, ash contents and higher heating values (HHVs) of chars from the olive husk samples 550 K C H O N Ash HHV, MJ/kg 71.2 6.0 16.0 1.0 5.8 29.1 650 K 78.0 4.2 11.1 0.8 5.9 30.1 750 K 86.4 3.0 3.9 0.6 6.1 32.3 850 K 89.0 2.4 1.9 0.4 6.3 32.5 950 K 89.6 2.0 1.5 0.5 6.4 32.7 1,050 K 90.6 1.8 0.9 0.3 6.5 32.8 1,150 K 91.3 1.4 0.6 0.2 6.7 32.8

Source: Demirbas, 2001.

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on pyrolysis yields. The temperature was maintained at 550 K, 600 K, 650 K, 700 K, 750 K, 800 K, 850 K, 900 K, 950 K, 1,000 K, and 1,050 K, while the heating rates were 10 K/s, 20 K/s, and 40 K/s. Following pyrolysis, the liquid products were collected in a series of traps maintained at about 273 K. These liquid products contained an aqueous and a non-aqueous phase, which were separated and weighed. After pyrolysis, the solid char was removed and weighed. The soluble part of the liquid phase which dissolved in dichloromethane was extracted in a rotary evaporator and the quantity of bio-oil was established. Then, the gaseous phase was calculated from the material balance.

Results and Discussion

Crude olive cake contains the olive stone shell crushed into fragments, stone kernel, the skin and the crushed pulp, about 25% water and a remaining quantity of oil making them subject to rapid spoilage. Processed olive cake differs from crude olive cake mainly by lower oil content and smaller water content because it has been dehydrated during the oil extraction process. The quantity extracted oil gained from the fresh olive kernels depends on the extraction method, extraction uid, and the history of the fresh kernels. The quantity and chemical composition of the bio-oil gained from the olive cake depends on the history of the fresh cake, heating rate, pyrolysis temperature, resistant time, and particle size. The main components of ripe olive fruit are given in Table 4. The average dry matter content of olive is 3348% by weight. A ripe olive composes of four parts: epicarp, edible mesocarp, endocarp (stone shell), and olive stone kernel. The olive fruit is ovoid shape and weighs from 315 g. The epicarp (or skin) is covered with wax and turns from light green to black as the fruit ripens. The mesocarp (or esh) has low sugar content (25%) and high oil content (1332%) that varies according to the variety and ripeness of the fruit. The endocarp (or stone) of the olive is hard and made of brous lignin. It is ovoid shape and it encloses a seed (olive kernel) that accounts for 23% of fruit weight and contains 24% oil. The olive stone shell is particularly rich in lignin and poor in cell content. The crude ber content in stone shell is high. The cell wall constituents of olive stone shell can be compared to that of cereal straws having an apparently high degree of lignication. Table 5 shows the yields of condensed liquid, tar, char and gas from the olive cake samples for 10 K/s heating rate at different pyrolysis temperatures. The yields of total biooils (condensed liquid C tar) are 34.4% and 31.8% at 650 K and 750 K, respectively. The most interesting temperature range for the production of the pyrolysis products is between

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Table 4 Main components of ripe olive fruit Component Epicarp Mesocarp Endocarp (Olive stone) Olive stone shell Olive stone kernel Fresh olive, wt% 0.51 8488 1216 914 23 Processed olive, wt% 0.51 7885 1522 1319 23 Processed olive, wt% basis on dry matter 12 2644 5674 4768 69

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A. Demirbas Table 5 Yields of condensed liquid, tar, char and gas from the olive cake samples at different pyrolysis temperatures (wt%). Heating rate: 10 K/s 550 K 650 K 26.5 7.9 39.5 26.1 750 K 25.1 6.7 36.6 31.6 850 K 20.6 5.7 33.3 40.4 950 K 14.9 3.3 31.8 50.0 1,050 K 14.5 1.9 31.6 51.8

Condensed liquid Tar Char Gas

25.4 8.7 45.5 20.4

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625 and 725 K. The char yield decreases as the temperature increases. The production of the liquid products has a maximum at temperatures between 625 and 725 K. At higher temperatures, the rather large molecules present in the liquid and residual solid are broken down to produce smaller molecules which enrich the gaseous fraction (Maschio et al., 1992). Pyrolysis actually begins between 535 and 775 K. The reactions are exothermic, and unless heat is dissipated, the temperature will rise rapidly. The primary products are beginning to react with each other before they can escape the reaction zone (Goldstein, 1991). If the temperature continues to rise above 775 K, a layer of char will be formed that is the site of vigorous secondary reactions. Pyrolysis is completed at temperatures of 675 to 925 K (Chum, 1991). Figure 1 shows the plots of the yields of liquid products from the olive cake by pyrolysis for the runs of different heating rates: 10 K/s, 20 K/s, and 40 K/s. From Figure 1, the highest bio-oil yields were 28.9% at 700 K, 32.9% at 700 K, and 36.8% at 750 K obtained from 10 K/s, 20 K/s, and 40 K/s heating rate runs, respectively. Figure 2 shows the plots of the yields of liquid products from the olive stone shell by pyrolysis. From Figure 2, the highest bio-oil yields were 31.0% at 700 K, 36.0% at

Figure 1. Plots of the yields of liquid products from the olive cake by pyrolysis.

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Figure 2. Plots of the yields of liquid products from the olive stone shell by pyrolysis.

Figure 3. Plots of the yields of liquid products from mesocarp of the olive fruit by pyrolysis. The oil extracted by diethyl ether from the sample before the pyrolysis.

700 K, and 41.0% at 700 K obtained from 10 K/s, 20 K/s, and 40 K/s heating rate runs, respectively. Figure 3 shows the plots of the yields of liquid products from the olive fruit mesocarp (edible outer part of olive fruit) by pyrolysis. The oil extracted by diethyl ether from the sample before the pyrolysis. From Figure 3, the highest bio-oil yields were 27.0% at 700 K, 31.0% at 700 K, and 34.5% at 750 K obtained from 10 K/s, 20 K/s, and 40 K/s heating rate runs, respectively.

Conclusion
Fast pyrolysis is a technology that can be used to convert diverse wood based and agricultural residues into a liquid called pyrolysis-oil or bio-oil. Liquid (tar), solid (char)

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A. Demirbas

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and gaseous products were obtained from olive cake by pyrolysis. Flash pyrolysis gives high oil yields. The liquid fraction of the pyrolysis products consists of two phases: an aqueous phase containing a wide variety of organo-oxygen compounds of low molecular weight and a non-aqueous phase containing insoluble organics (mainly aromatics) of high molecular weight. This phase is called as bio-oil or tar and is the product of greatest interest. The ratios of acetic acid, methanol, and acetone of aqueous phase were higher than those of non-aqueous phase. If the purpose were to maximize the yield of liquid products resulting from biomass pyrolysis, a low temperature, high heating rate, short gas residence time process would be required. For a high char production, a low temperature, low heating rate process would be chosen. If the purpose were to maximize the yield of fuel gas resulting from pyrolysis, a high temperature, low heating rate, long gas residence time process would be preferred.

References
Aygun, A., Yenisoy-Karakas, S., and Duman, I. 2003. Production of granular activated carbon from fruit stones and nutshells and evaluation of their physical chemical, and adsorption properties. Microp. Mesop. Materials 66:189195. Bridgwater, A. V., and Peacocke, G. V. C. 2002. Fast pyrolysis processes for biomass. Renew. Sustain. Energy Rev. 4:173. Chum, H. L. 1991. Polymers from Biobased Materials. New Jersey, USA: Noyes Data Corporation. Demirbas, A. 1998. Yields of oil products from thermochemical biomass conversion process. Energy Convers. Mgmt. 39:685690. Demirbas, A. 2000a. Biomass resources for energy and chemical industry. Energy Edu. Sci. Technol. 5:2145. Demirbas, A. 2000b. Liquefaction of olive husk by supercritical uid extraction. Energy Convers. Mgmt. 41:18751883. Demirbas, A. 2001. Carbonization ranking of selected biomass for charcoal, liquid and gaseous products. Energy Convers. Mgmt. 42:12291238. Demirbas, A. 2002a. Fuel analyses of selected oilseed shells and supercritical uid extraction in alkali medium. Energy Convers. Mgmt. 43:19771984. Demirbas, A. 2002b. Fuel characteristics of olive husk and walnut, hazelnut, sunower and almond shells. Energy Sources 24:213219. Demirbas, A. 2004a. Combustion characteristics of different biomass fuels. Progress Energy Combust. Sci. 30:219230. Demirbas, A. 2004b. Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons. J. Anal. Appl. Pyrolysis 72:97102. Demirbas, A., Akdeniz, F., Erdogan, Y., and Pamuk, V. 1996. Kinetic for fast pyrolysis of hazelnut shell. Fuel Science and Technology Intl. 14:405417. Demirbas, A., and Arin, G. 2002. An overview of biomass pyrolysis. Energy Sources 5:471482. Di Blasi, C., Tanzi, V., and Lanzetta, M. 1997. A study on the production of agricultural residues in Italy. Biomass Bioenergy 12:321331. Goldstein, I. S. 1981. Organic Chemical from Biomass. Boca Raton, Florida, USA: CRC Press, Inc., p. 64. Maschio, G., Koufopanos, C., and Lucchesi, A. 1992. Pyrolysis, a promising route for biomass utilization. Bioresource Technol. 42:219231. Ozkan, B., Akcaoz, H., and Fert, C. 2004. Energy input-output analysis in Turkish agriculture. Renew. Energy 29:3951. Zabaniotou, A. A., Kalogiannis, G., Kappas, E., and Karabelas, A. J. 2000. Olive residues (cuttings and kernels) rapid pyrolysis product yields and kinetics. Biomass Bioenergy 18:411420.