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Bioresource Technology 99 (2008) 320326

Activated carbon from olive kernels in a two-stage process: Industrial improvement


A. Zabaniotou *, G. Stavropoulos, V. Skoulou
Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, University Box 455, 54124 Thessaloniki, Greece Received 27 September 2006; received in revised form 6 December 2006; accepted 17 December 2006 Available online 20 February 2007

Abstract Activated carbons have been prepared from olive kernels and their adsorptive characteristics were investigated. A two stage process of pyrolysis-activation has been tested in two scales: (a) laboratory scale pyrolysis and chemical activation with KOH and (b) pilot/bench scale pyrolysis and physical activation with H2OCO2. In the second case, olive kernels were rst pyrolysed at 800 C, during 45 min under an inert atmosphere in an industrial pyrolyser with a throughput of 1 t/h (Compact Power Ltd., Bristol, UK). The resulting chars were subsequently activated with steam and carbon dioxide mixtures at 970 C in a batch pilot monohearth reactor at NESA facility (Louvain-la Neuve, Belgium). The active carbons obtained from both scales were characterized by N2 adsorption at 77 K, methyl-blue adsorption (MB adsorption) at room temperature and SEM analysis. Surface area and MB adsorption were found to increase with the degree of burn-o. The maximum BET surface area was found to be around 10001200 m2/g for active carbons produced at industrial scale with physical activation, and 3049 m2/g for active carbons produced at laboratory with KOH activation. The pores of the produced carbons were composed of micropores at the early stages of activation and both micropores and mesopores at the late stages. Methylene blue removal capacity appeared to be comparable to that of commercial carbons and even higher at high degrees of activation. 2007 Elsevier Ltd. All rights reserved.
Keywords: Activated carbons; Olive kernel; KOH Activation; H2OCO2 Activation

1. Introduction The enormous potential of agricultural residues can be utilized to create sustainable bioproducts, bioenergy and materials. They can play a dual role in greenhouse gas mitigation; both as an energy source to substitute fossil fuels and as a carbon sink. Pyrolysis, an endothermic process, oers an environmentally attractive way of reducing those residues. Unlike incineration, the pyrolysis process does not lead to air emissions. The solid product of pyrolysis, named char, can be activated and produce active carbon, a high value added product. With the parallel use of char as feedstock for material production, the targets set out in the Biomass Action Plan (EU, 2005) and Commission

Corresponding author. Tel.: +30 2310 996274; fax: +30 2310 996209. E-mail address: sonia@cheng.auth.gr (A. Zabaniotou).

Green Paper for A European strategy for sustainable, competitive and secure energy (EU, 2006) could be reached because optimisation of agricultural residues exploitation can be achieved and cost-eective integrated approaches can be, also, developed. Active carbons are of great interest in many economic sectors. In recent years, a lot of research has been reported on activated carbons from agricultural wastes, such as from fruit stones (Lussier et al., 1994; Gergova and Eser, 1996), sugar canes almond shells (Toles et al., 2000a,b; Marcilla et al., 2000a,b), nut shells (Hu and Vansant, 1995b,a) and many others (wheat straw, grape seeds) (Gergova et al., 1992, 1994). Little has been mentioned about olive residues (La, 2001; Zabaniotou et al., 2000; Al-Khalid et al., 1998; Bacaoui et al., 2001; Galiatsatou et al., 2002) although this is a cheap and quite abundant, especially in Mediterranean countries, agricultural waste of no economical value.

0960-8524/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2006.12.020

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Activated carbons can be produced either by physical or chemical routes. The former involves two steps: carbonization of the raw material followed by controlled gasication in a stream of oxidizing agent such as steam, CO2, or air. The chemical route consists of impregnating the carbonaceous precursor with a chemical reagent and heating (Marsh et al., 1984; Yamashita and Ouchi, 1982; MolinaSabio et al., 1995). Furthermore, olive tree cultivation presents a signicant agricultural activity in Greece and traditionally plays an important role to countrys agriculture and food export activities. Greece owns the third place, among all other Mediterranean countries, in olive oil production and covers almost 15% of worldwide olive oil production (Vourdoubas, 1999, 2004). As a result, agricultural and industrial activities emerging from this characteristic cultivation generate huge amounts of solid residues (olive kernel) and liquids (olive mill wastewaters), that are produced seasonally from olive oil and olive kernel oil factories and could constitute a serious environmental problem due to their phytotoxic nature. Especially, as its concerns the solid waste (olive kernel), the predominant energy exploitation method in Greece is conventional combustion, but this process contributes negatively to atmospheric pollution by releasing gaseous and particle emissions to the atmosphere. Moreover, pyrolysis/gasication related to direct combustion aligns well with Kyoto protocol commitments (zero CO2 emissions), reduces waste volumes, contributes towards the conservation of fossil fuel resources and generally moves towards the clean and green energy production targets of European Union. Greece owns the third place in the world over olive oil production activity, following Italy and Spain, respectively. As a result, a modest olive kernel production in Greece reaches 300,000400,000 t/year (Vamvuka and Tsoutsos, 2002). Additionally, from estimations that approximately from 100 kg of olives produced 20 kg olive oil, 35 kg olive kernel, almost 5 kg of olive leaves and cuttings and 40 kg of olive mill wastewaters (Vourdoubas, 2004), turns out that a considerable huge amount of solid (olive kernel and olive wood) and liquid (olive mill wastewaters) waste should be managed with environmental accepted way. The present work focuses on a two-stage pyrolysis-activation process as a possible way for recycling of the organic matter in order to produce activated carbon and deals with requirements for industrial application. The study is a part of a research eort addressed to the full utilization of agricultural wastes for the production of materials with high absorbing capacity and high added value, such as active carbons. The experimental work described in the present paper is part of a series of experimental investigations: (a) experimental and analytical work on pyrolysis and activation of the raw material and characterisation of the produced carbons in laboratory scale, in order to study the processes and to provide data for pilot test procedures, (b) experimental work of pyrolysis using material samples in pilot scale and activation in bench

scale, (c) evaluation of ndings and comparison of results with commercial active carbons and (d) identication of decisive parameters in scale up consideration and extrapolation of laboratory-scale experimental results to establish criteria for reactor design and process development. 2. Experimental 2.1. Biomass characteristics In the experiments performed, samples of olive kernels, originating from Greece were used. The elemental analysis of biomass was carried out using a LECO COR Analyser CHN-800. Table 1 presents characteristics of olive kernel and char, on dry basis. Oxygen was calculated on wt.% basis after elimination of C, H, N and S percentages. Determination of ash and moisture was performed according to ASTM Standards (D-1102-84 for ash in wood and D-2016-74 for moisture). 2.2. Pyrolysis in laboratory scale reactor Pyrolysis of olive kernel samples was carried out in a laboratory captive sample reactor that could be identied as a wire mesh microreactor. The experimental facility is presented in Fig. 1. The experiments were carried out in a temperature range of 270600 C, with heating rates of 100300 C/s and gas/vapour residence times of approx. 0.51.0 s at atmospheric pressure, under He ow. The technique enables the achievement of high heating rates as a prerequisite for short reaction periods. 2.3. Pyrolysis in industrial scale unit Pyrolysis of olive kernel has also been performed in the Compact Power Ltd. at Bristol, UK Compact Power Ltd. has developed a new advanced thermal conversion technology for a wide range of wastes using the process of pyrolysis, gasication and high temperature oxidation. The plant is designed as a closed system in which all waste materials are converted into simple gases and used to fuel conventional steam power cycles. Pyrolysis was carried at 800 C for 45 min in an inert atmosphere, in the Avonmonths industrial pyrolyser, with a capacity of 1 t/h. The pyrolysis reactor has been presented in another paper (Zabaniotou et al., 2004).

Table 1 Analysis of olive kernel and their pyrolysis char Element N C H S O Raw material (% w/w, dry basis) 1.95 49.74 6.06 0.18 39.07 Char (% w/w, dry basis) 1.35 75.68 0.79 0.00 12.18

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9. Filter of HC 17. H2O tube 18. Volumetric cylinder 6. Manometer 7. Connector 5. Flange SS316 8. Jointure

Water

15. 3way electrovalve 16. Valve 14. 2way electro valve


V3V 3 2 1 3 2 Ve3V 1

13. Filter silica gel

1. Electrode 4. Flange of bronze 21. Thermocouple on I off

3. Membrane 2. Reactor plexiglas

10. He supply

11. Flowmeter

U He

Water

Electricity 12. Water Cooling

on off on 19. Set and temperature control off 20. Button of alimentation of the electronic valve

Fig. 1. Schematic representation of laboratory pyrolysis unit.

2.4. Chemical activation of char in laboratory scale For the char activation, a tubular xed-bed reactor was used with 2-in. nominal diameter made of a 316 stainless steel. Batches of 2 g of sample were employed in each experiment as shown in Fig. 2. The absence of sulphur and the low ash content of the char are positive factors and make olive kernel a good starting material for the production of active carbons. The char was mixed with KOH,
PI VENT PI PI CO PI TI FM SP PI TI N
2

in a ratio C/KOH of 1:4, as suggested in literature to be the optimum one (Hayashi et al., 2002). Activated carbons with various extents of burn-o were prepared at activation temperatures of 800 and 900 C and reaction times of 1, 2, 3 or 4 h. Carbonized products were cooled and washed by boiling with HCl for 1 h for residual KOH removal. The acid washed samples were further washed with distilled water several times until neutral pH. The nal carbon products were dried at 110 C for 24 h, for moisture removal. 2.5. Physical activation of char, in bench scale reactor Physical activation is the mild oxidation of the material with steam, carbon dioxide or air at high temperatures (8001000 C). Activation procedure results in the creation of a pore system responsible for the adsorbing capacity of the carbon. Pellets of olive kernels have been used. The oxidising agent tested in this study was H2OCO2 mixture. The char obtained from olive kernel pyrolysis, in a pilot scale reactor, was activated in an activation kiln at NESA Company at Louvain la Neuve. NESA furnace has also used for tires char activation (Zabaniotou et al., 2004). Natural gas was burned in the combustion chamber; the hot combustion gases were ducted to the top of the reaction chamber where they came into contact with the tested material and the temperature of the gases in the reaction

TI

BM WTGM VENT SP SAMPLE BAGS : Sample Port : Pressure Indicator : Temperature Indicator : Bubble Meter : Flow Meter

PI PI

BM FM

WTGM : Wet Test Gas Meter

Fig. 2. Schematic representation of laboratory activation gasication activation apparatus.

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Amount adsorbed, scm /g

chamber was measured with a thermocouple. In the reaction chamber steam was injected. The fact that the combustion gases came in contact with the biomass, had as a result the steam/CO2 activation. 2.6. Active carbon BET surface area measurements The nitrogen adsorption isotherms of the resulting carbons, used for calculating their BrunauerEmmettTeller (BET) surface areas and total pore volumes, were obtained by using a Micrometerics Co., USA apparatus. The surface areas of activated carbons were measured with FLOWSORB 2300 by determining the quantity of a gas that adsorbs as a single layer of molecules, a so called monomolecular layer, on a sample. Methylene blue (MB) was employed as the adsorbate in liquid-phase adsorption experiments. Adsorption experiments were conducted by mixing the carbon sample with a certain amount of the MB solution and distilled water in a glass-stoppered ask. The ask was then put in a shaker and shaked for 24 h. Upon equilibration, all adsorption samples were removed and used for the determination of residual MB. The concentrations of the adsorbate in the adsorption samples were determined spectrophotometrically at a wavelength of 660 nm, using an UV/visible spectrophotometer (Thermospectronic Helios E). The equilibrium adsorption capacities (Qe) at dierent MB concentrations were determined according to the mass balance on the adsorbate Qe C i C e V =m; 1

1400 1200
3

1000 800 600 400


800-1h 800-2h 900-1h 900-4h 800-3h 900-2h

200 0 0.000

800-4h 900-3h

0.200

0.400

0.600

0.800

1.000

P/P0

Fig. 3. N2 Adsorption isotherms of carbons prepared from olive seed waste activated with KOH.

3500 3000

Surface area, m2/g

2500 2000 1500 1000 500 0 0 20 40 60 80

where Ci is the initial concentration, Ce is the equilibrium concentration, V is the volume of the liquid phase, and m is the mass of the activated carbon sample. 3. Results and discussion 3.1. Lab scale results N2 Adsorption isotherms of olive kernel derived activated carbons produced in laboratory scale with chemical activation can be seen in Fig. 3. Based on those isotherms BET surface areas were found to be increasing with activation time and temperature from a minimum value of 1339 C at 1 h and 800 C to a maximum of 3049 m2/g, at 4 h and 900 C (Stavropoulos and Zabaniotou, 2005). On the other hand, BET area shows an increase with an increase of the burn-o, regardless of the activation temperature (Fig. 4). This indicates that the burn-o of the activated carbon has the most signicant eect on the increase of the surface area. Indeed, the surface area depends on the carbon mass, removed during the activation, creating pores to the material. The general trend is that as activation proceeds all kinds of porosity are increasing. At the nal conditions of 900 C and 4 h, an activated carbon is obtained possessing the entire spectrum of pore sizes (super) micropores prevailing,

Burn-off,wt %
Fig. 4. Relationship between BET surface area of active carbons issued from olive kernels and burn o.

Table 2. Based on the trend of the experimental results, it can be anticipated that extension of the activation process

Table 2 The burn-o, BET surface area, external surface area, pore volume and pore size distribution of the produced activated carbons Activation type Burn-o (wt.%) SBET (m2/g) Content of micro- and mesopores Micropore (%) 56 50 70 59 54 53 50 78 Mesopore (%) 44 50 30 41 46 47 50 22

800 C/1 h 800 C/2 h 800 C/3 h 800 C/4 h 900 C/1 h 900 C/2 h 900 C/3 h 900 C/4 h

24 28 51 58 35 41 53 68

1170 1179 1842 1582 1480 1370 1728 2159

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will give a more mesoporous carbon with augmented percentage of ultramicroporosity. The enormous BET surface areas created by a distinct KOH activation mechanism could be explained by the fact that KOH is dehydrated to K2O, which reacts with CO2 produced by the water-shift reaction, to give K2CO3. Inter300 250

200 150 100 50 0 0 20 40 60 80

Burn-off, wt %

calation of metallic potassium, which is also formed above 700 C, appeared to be responsible for the drastic expansion of the carbon material and hence the creation of a large specic surface area and high pore volume (Rouquerol et al., 1999). Methylene blue (MB) served as a model compound for adsorption of medium size organic compounds from aqueous solutions. The Langmuir adsorption model is a typical model for monolayer adsorption and was adapted to model isotherms and calculate the MB adsorption capacities of the produced carbons. The MB adsorption experiments of the KOH activated carbons gave values between 190 and 263 mg/l. The adsorption isotherms of MB onto the carbons activated at 800 and 900 C have been reported elsewhere (Stavropoulos and Zabaniotou, 2005). The BET surface area of activated carbons depends on the burn-o as shown in Fig. 5. Compared to the F300 commercial carbon (with MB capacity 240 mg/l), the values obtained in this study are similar and even higher. Based on gas and liquid phase adsorption results, prepared carbons can be used as substitutes of existing products. 3.2. Pilot/bench scale results Table 3 shows the activation characteristics of biomass pyrolysis char in NESA bench scale reactor. The BET surface area of olive kernel derived activated carbons produced at pilot scale with physical activation found to be as high as 10001200 m2/g. This fact makes interesting the exploitation of those agricultural residues by pyrolysis and steam activation for active carbons production, especially for Mediterranean countries, such as Greece.

Fig. 5. Relationship between methylene blue (MB) adsorption of active carbons issued from olive kernels and burn-o. Table 3 Activation characteristics of biomass pyrolysis char in a bench scale reactor Type of biomass Vapour activation Activation temperature Activation time BET (average) Olive kernel Physical, batch; PH2O: 3540% 940 C 3h 1155 m2/g

MB adsorption, mg/g

Fig. 6. SEM analysis of activated carbon from olive kernel.

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A scanning electronic microscopic study is shown in Fig. 6 corresponding to activated carbon produced at bench scale at 3 h. SEM images clearly show that carbon physical structure consists of a system of adjacent cavities that resembles a well organized macropore (>500 A) network with an average diameter of about 5 lm. This texture is benecial for any adsorption process because large sized pores serve as feeder pores to lower dimension ones, i.e., meso- and micropores. Similar pore structure has been observed by other authors (Martnez et al., 2006; Fukuyama et al., 2001) who concluded that the development of the pore system in carbons depends on starting material structure and activation process. 4. Conclusions Severe atmospheric pollution, due to fossil fuel consumption rates, indicates the strong necessity for establishing sustainable alternatives of energy production that will, also, enclose environmental friendly processes. Moving to that direction, characteristic agricultural residues for Mediterranean countries as olive kernel seem to be an attractive form of renewable energy source and can also constitute a source of high added value materials production. Greece, due to its extensive olive tree agriculture activity and olive oil production tradition, is able to take advantage of the solid residue issued from olive oil production activity (named olive kernels) by exploiting it for active carbon production. The best valorization method would be selected, not only from environmental and technological point of view, but also, tacking into consideration needs connected to several socioeconomic factors. In the present study, activated carbons were produced from olive kernel by chemical activation, using KOH as the activating agent, in laboratory scale and by physical activation in bench scale. In both cases, it was employed a two-stage process involving pyrolysis of the precursor material followed by char activation. The main conclusions of the study are The maximum BET surface area was found to be around 10001200 m2/g, for active carbons produced at industrial scale with physical activation, and 3049 m2/g for active carbons produced at laboratory with KOH activation. The BET surface area of olive kernel carbons, produced with steam activation, increases with the time of activation showing a maximum at time 2.5 h. The BET surface increases also with the burn-o of the activation process. Methylene blue removal capacity appeared to be comparable to that of commercial carbons and even higher at high degrees of activation. The innovative aspect of the present study is the fact that both pyrolysis and activation had performed at laboratory and industrial scale (scale up) and, therefore, the

results give a more realistic approach of feasibility of the process. The use of catalyst improves the surface areas making active carbons acceptable substitutes of commercial products. The use of KOH in the laboratory study increased the BET and gave a value of 3049 m2/g. An evaluation of the global viability of the process should involve the substitution value in purchasing commercial activated carbon. The experimental results discussed so far provide a more detailed understanding of the BET surface and pores creation in olive kernel activation process and lead to guidelines for application and extrapolation of laboratory-scale results in reactor design and scale-up considerations. From these ndings criteria for reactor design and scale up in process development can be derived. A signicant improvement in BET surface of active carbons can be attained with KOH activation. From the experimental results, it can be concluded that a combination of a rotary kiln with KOH activation could be a promising process in pyrolytic recycling of agricultural residues for active carbon production. This is a rst approach in determining an optimum production process. A product manufacturing cost analysis (work in progress) should be required to ensure the full techno-economic viability of the proposed scheme. In conclusion, it has been demonstrated that the production of about 105,000 t of active carbon could technically be feasible, at industrial scale, by activating the pyrolytic char issued from approximately 300,000 t of olives kernels that produced annually in Greece. Acknowledgements The part of research performed in Greece (Aristotle University of Thessaloniki), has funded by the European Social Fund and Greek Ministry of Education and Religious Aairs, under the frames of the program EPEAEK-Pythagoras II. Special acknowledgements are expressed to Prof. A. Fontana, Dr. G. Jung, Prof. MariePaule Delplanche and Patric Madou (Universite Libre de Bruxelles, Ecole de Commerce Solvay Centre de Recherche Emile Bernheim), for hosting the corresponding author in order to perform research and also to Mr. Oudenne from NESA who carried out the char activation in pilot scale. References
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