PERGAMON

Carbon 39 (2001) 14151420

Chemical and physical activation of olive-mill waste water to produce activated carbons
a , M. Victoria Lopez-Ramon b, Carlos Moreno-Castilla a , *, Francisco Carrasco-Marn Miguel A. Alvarez-Merino b
b

, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain Departamento de Qumica Inorganica , 23071 Jaen , Spain , Facultad de Ciencias Experimentales, Universidad de Jaen Departamento de Qumica Inorganica y Organica Received 17 July 1999; accepted 13 October 2000

Abstract Olive-mill waste water is produced in large quantities during the manufacture process of the olive oil in mills. This by-product has been used as raw material to produce activated carbons by both chemical and physical activation methods. In the rst case, KOH and H 3 PO 4 were used as activating agent, and in the second case, CO 2 at 8408C for different periods of time. Results obtained indicate that the chemical activation with KOH at 8008C, in an inert atmosphere, yielded activated carbons with the highest surface area and more developed micro, meso and macroporosity. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: A. Activated carbon; B. Chemical treatment; D. Surface areas; Textures

1. Introduction Activated carbons can be produced from a large variety of raw materials, basically by two methods: Physical or chemical activation or a combination of both of them. The physical activation method involves carbonization of the raw material and the subsequent activation at high temperature in a carbon dioxide or steam atmosphere. The chemical activation method involves the carbonization of the raw material previously impregnated with a chemical agent. Different chemical agents, known for a long time [1], can be used in the chemical activation process, and out of all of them the activation with KOH [110] and H 3 PO 4 [1119] are two of the more used methods. One of the research objectives of this laboratory is to explore the possibility of using different agricultural wastes as raw materials to produce activated carbons for different uses, such as adsorbents in liquid and gas phases, catalysts and support for catalysts. So far, we have used olive stones and almond shells to produce different activated carbons by physical activation either with CO 2 or
*Corresponding author. Tel.: 1 34-958-248-526; fax: 1 34958-248-526. E-mail address: cmoreno@ugr.es (C. Moreno-Castilla).

steam and, the application of the activated carbons so obtained in the above uses was investigated [2024]. the The most abundant agricultural waste of Andaluca, southern Spanish region, comes from olive trees. Thus, in the year 1998 were produced around 3.5310 6 tons (metric) of olives. During the manufacture process of the olive oil in the mills about 20% of oil, 30% of waste solids and 50% of waste water are obtained. The waste solid is composed of a mixture of olive pulp and olive stone, and we have used, as commented above, this last solid to obtain activated carbons. The waste water is composed essentially of the own water of the olives, together with the water used in their washing and processing, and its average composition is around 80% water, 18% organic matter and 2% mineral matter [25]. The composition of the organic portion of the olive-mill waste water is quite complex, containing: Greases, proteins, carbohydrates, organic acids, polyalcohols, pectines, tanines, glucosides and polyphenols. The mineral matter is composed essentially of carbonates, phosphates, sodium and potassium as the major ions. The water content of this waste liquid can be reduced in a 7075% and reused in the process, obtaining in this way a concentrated olive-mill waste water. The residue could be treated appropriately to obtain

0008-6223 / 01 / $ see front matter 2001 Elsevier Science Ltd. All rights reserved. PII: S0008-6223( 00 )00268-2

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Table 1 Ash content and ultimate analysis of activated carbons obtained by chemical activation with KOH Sample g KOH / g sample A 0 0.5 / 1 1/1 2/1 Ash (%) 17.7 7.7 0.6 0.4 0.4 Ultimate analysis (% daf) C 74.7 88.0 90.7 91.5 92.4 H 6.7 0.5 0.2 0.2 0.2 N 1.3 1.3 0.6 0.4 0.0 Oa 17.3 10.2 8.5 7.9 7.4

A A-0 A-0.5 A-1 A-2

a

By difference.

activated carbons, and so far, there is not any study about its use as raw material to prepare them. For this reason, the objective of this work is to explore the possibility of using this waste liquid to obtain activated carbons by both chemical activation, with KOH and H 3 PO 4 , and physical activation with CO 2 . The production of these materials could be of great interest because of the olive-mill waste can cause environmental contamination problems in the areas where the olive mills are placed.

2. Experimental The olive-mill waste water was rst evaporated at 608C till it was converted in a cake. Subsequently, it was cut in small pieces and dried in a vacuum oven at 1108C. The weight loss during this drying process was 70% which corresponds, approximately, to the water content of the original material. The solid so obtained had an ash content of 9.7% and its ultimate analysis (daf) was: 55.5% C, 7.5% H, 1.1% N, 0.7% S and 35.2% O (by difference). Carbonization of the above solid was carried out in a furnace at 3508C for 1 h under air ow (300 cm 3 min 2 1 ) before proceeding to its chemical activation. The sample so obtained was ground and sieved to obtain a particle size between 1 and 1.4 mm, and it will be referred to in the text as sample A. This sample A was chemically activated by both KOH and H 3 PO 4 . Treatment with KOH was similar to that described elsewhere [9]. For this purpose, sample A was mixed with

a concentrated solution of KOH in the adequate proportions to obtain three slurries, which had different KOH / sample A mass ratio as shown in Table 1. The slurries were dried at 608C and treated in N 2 ow at 3008C for 3 h. Finally, they were carbonized at 8008C for 2 h (108C min 2 1 ) under the same N 2 ow, 300 cm 3 min 2 1 . Subsequently, all samples were washed with a 0.1 N solution of HCl (1 g carbon / 25 cm 3 of solution) and with distilled water till an absence of chloride ions in the washing water. A blank sample was also prepared by carbonizing sample A in the same conditions as before, but without containing KOH. After the carbonization, the blank sample was also washed with the HCl solution and distilled water. This sample will be referred to in the text as A-0. The ash content and ultimate analysis of all samples are shown in Table 1. Treatment with H 3 PO 4 was similar to that described elsewhere [19]. Thus, sample A was mixed with a 75% phosphoric acid aqueous solution, with a H 3 PO 4 / sample A mass ratio equal to 2.4. The slurry was dried rst at 608C and nally at 1108C. The dried mixture was activated at 5008C for 1 h (108C min 2 1 ) under different ows (300 cm 3 min 2 1 ) of nitrogen, carbon dioxide, air and steam. Samples so obtained will be referred to in the text as: AP-N, AP-C, AP-A and AP-S, respectively. Activation with steam was similar to that described elsewhere [26]. Blank samples were also prepared by heating sample A at 5008C for 1 h under air and N 2 ow (samples AA and AN, respectively). All samples obtained were washed with HCl solution and distilled water as commented above. The weight loss, ash content and ultimate analysis of all these samples are compiled in Table 2. Sample A-0 was physically activated with CO 2 (300 cm 3 min 2 1 ) at 8408C and for different periods of time to obtain different degrees of activation. All activated carbons were characterized by N 2 and CO 2 adsorption at 77 and 273 K in a conventional volumetric system. The BET equation was applied to the N 2 adsorption isotherm, to obtain the surface area, and the DR equation to the CO 2 adsorption data. From this last equation, the micropore volume, W0 , the characteristic adsorption energy, E0 , and the mean micropore width, L0 , were obtained. L0 was calculated by applying the equation

Table 2 Ash content and ultimate analysis of activated carbons obtained by chemical activation with H 3 PO 4 under different atmospheres Sample Atmosphere Ash (%) 7.5 7.3 29.0 12.6 10.0 7.1 Ultimate analysis (% daf) C 82.4 79.6 93.2 88.8 86.9 87.4 H 2.6 2.5 2.4 2.3 2.3 2.5 N 1.7 1.8 1.8 1.4 1.3 1.4 Oa 13.3 16.1 2.6 7.5 9.5 8.7

AA (blank) AN (blank) AP-A AP-N AP-C AP-S

a

Air N2 Air N2 CO 2 H2O

By difference.

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3.5 L0 5 2(13.03 2 1.53 3 10 2 5 E 0 ) / E0 [27]. Mercury porosimetry was carried out up to a pressure of 4076 kg cm 2 2 by using a porosimeter Quantachrome, model Autoscan 60. This technique allowed to obtain the particle density, r, the pore volume corresponding to pores with a diameter between 3.7 and 50 nm, V2 , which will be referred to as mesopore volume, although in fact the mesopore volume is between 2 and 50 nm [28], and the volume of pores with a diameter larger than 50 nm, V3 , referred to as macropore volume. Water density of selected samples was obtained by picnometry. The ultimate analysis was performed with an analyzer Fisons-Carlo Erba 1108CHNS equipment. The pH of the point of zero charge, pH PZC , was obtained as described elsewhere [29].

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3. Results and discussion

3.1. Chemical activation with KOH

Chemical activation of sample A with KOH brought about, with regard to the blank sample (A-0), a large decrease in the ash content and an increase in the carbon content, which increased from sample A-0.5 to A-2. The N and O content gradually decreased with the increase in the KOH / sample A mass ratio between 0 and 2 (see Table 1). The effects of KOH on carbonization of carbonaceous materials have been studied by several authors. Thus, Marsh et al. [5] in studying the formation of active carbons from petroleum cokes, metallurgical coke and charcoals from wood, after their reaction with KOH in the temperature range 5509008C, indicated that the oxygen of the alkali can remove cross-linking and stabilizing carbon atoms in crystallites. K metal obtained at reaction temperatures may intercalate and force apart the separate lamellae of the crystallite. Removal of potassium salts, by washing, and carbon atoms from the internal volume of the carbon, by activation reaction, create the microporosity of the activated in the new structure. Later, Otowa et al. [7,8] conrmed this mechanism and indicated that high temperature and high KOH / carbon ratio produced large pores in the carbon structure, due to the presence of K 2 O, derived from KOH, expanded the carbon atomic layers. When the temperature exceeded

7008C, a considerable amount of K was formed by the reduction of K 2 O with carbon. Since the inner carbon atoms were consumed, pores were formed in the structure. Surface area, pore texture and pH PZC of the activated carbons obtained by the KOH treatment are shown in Table 3. Carbonization of sample A at 8008C in N 2 to obtain sample A-0 increases the nitrogen surface area. But with regard to this blank sample, the chemical activation of A with KOH brought about a very large increase in nitrogen surface area and pore volumes, even for the lowest KOH / sample A ratio. An increase in this ratio brought about an increase in all textural parameters. As a consequence of the KOH chemical activation, there was an increase in the micropore width, L0 , and a decrease in the particle density, r. The pH PZC of the activated carbons obtained indicates that they are slightly acidic or almost neutral. It is noteworthy the surface characteristics of activated carbon A-2, with very high nitrogen surface area and very large values of micro and macropore volumes. This last type of pores underwent the highest increase in volume with the increase in the KOH / sample A ratio, which is in agreement with the observation of Otowa et al. [7,8]. Finally, the pore volume accessible to water, VH 2 O , increased with the activation, and its value was equal to the addition of W0 , V2 and V3 , which indicates both a good accessibility of water to all the pore texture of carbons and that they did not swell into water.

3.2. Chemical activation with H3 PO4

It has been described [13,14] that in the phosphoric acid activation method, temperatures around 4508C produce the maximum development of porosity, even though the carbonization of the material can be incomplete, because the effect of H 3 PO 4 is to produce chemical changes and structural alterations at temperatures lower than in the thermal treatment without impregnation. Phosphoric acid functions in two ways [17]: As an acidic catalyst in promoting bond cleavage reactions and formation of crosslinks; and by being able to combine with organic species to form phosphate linkages, such as phosphate and polyphosphate esters, that can serve to connect and crosslink biopolymer fragments.

Table 3 Surface characteristics of activated carbons obtained by chemical activation with KOH Sample A A-0 A-0.5 A-1 A-2 SN 2 m 2 g 21 ,2 345 1500 1635 1768 E0 kJ mol 2 1 25.1 18.9 18.6 18.3 L0 nm 0.94 1.33 1.35 1.38 W0 cm 3 g 2 1 0.28 0.54 0.55 0.57 V2 cm 3 g 2 1 0.01 0.01 0.12 0.16 0.18 V3 cm 3 g 2 1 0.13 0.05 0.19 0.36 0.62 VH 2 O cm 3 g 2 1 0.31 0.87 1.10

r g cm 2 3
0.96 1.18 0.68 0.56 0.45

pH PZC 10.9 7.4 6.0 6.1 6.5

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Table 4 Surface characteristics of activated carbons obtained by chemical activation with H 3 PO 4 Sample AP-A AP-N AP-C AP-S
a

SN 2 m 2 g 21 179(12)a 336(10) 373 393

E0 kJ mol 2 1 24.4 23.4 23.6 22.5

L0 nm 0.98 1.03 1.02 1.09

W0 Cm 3 g 2 1 0.12 0.15 0.16 0.15

V2 cm 3 g 2 1 0.00 0.05 0.04 0.05

V3 cm 3 g 2 1 0.03 0.06 0.05 0.07

r g cm 2 3
1.30 0.97 1.03 0.90

pH PZC 2.4 2.5 2.6 2.6

In parenthesis are given the nitrogen surface area of the blanks AA and AN, respectively.

Thus, the most important difference between the activation mechanism with KOH and H 3 PO 4 is that, whereas the rst mechanism remove and avoid the crosslinking, stabilizing the carbon atoms in crystallites, the second mechanism involves an excessive crosslinking by both acid catalysis and through the phosphate linkages. The treatment atmosphere, in the H 3 PO 4 activation method, appears to be an important parameter controlling the surface area and pore texture of the resulting material [15,19]. Thus, when the precursor was peach stones [15] the activation in a N 2 atmosphere produced a higher development of microporosity than in an air atmosphere. When wood was used as precursor [19], the microporosity and surface area were more developed using either air or N2. Characteristics of activated carbons obtained after phosphoric acid activation of sample A are shown in Tables 2 and 4. The activated carbons obtained by this method had an ash content that depended on the atmosphere of the treatment. Thus, the treatment in air (AP-A) yielded the highest ash content and the treatment in steam (AP-S) the lowest one, which in this case, was similar to that of the blank samples. Furthermore, the ash content of these activated carbons was much higher than those prepared from the KOH method. High ash content in carbons is undesirable because mechanical strength and adsorptive capacity are reduced. The high ash content of these carbons can be due to several reasons such as: (i) The inorganic constituent of the raw material can combine with phosphoric acid giving insoluble phosphates, which furthermore, can be trapped inside the carbon matrix due to the crosslinking that produces the treatment with H 3 PO 4 , and (ii) phosphate and polyphosphate species are incorporated to the carbon

matrix, through COP bonds, connecting and crosslinking different organic species. The lowest ash content of sample AP-S can be due to [19] steam inhibited the formation of condensed phosphates and eliminated the phosphate groups previously attached to the carbon. Nitrogen surface areas (Table 4) of the blanks, AA and AN, were much lower than those of the corresponding activated carbons AP-A and AP-N. Therefore, the H 3 PO 4 activation increased the surface area of the samples, although in much lower extent than the activation with KOH. Surface area of the activated carbons obtained seems to depend on their ash content, with the higher the ash content the lower the nitrogen surface area. Thus, sample AP-A and AP-S had the lowest and the highest SN 2 value, respectively All samples had very low meso and macropore volumes and a somewhat higher micropore volume. All these surface characteristics make that the particle density of these samples be higher than in the case of the KOH treatment. Finally, pH PZC values of these carbons indicate that their surface was more acidic than those obtained by the KOH method.

3.3. Physical activation with CO2

Sample A-0 was activated with CO 2 at 8408C up to different percentages of burn-off (BO). Results obtained are compiled in Table 5. Nitrogen surface area increased with the degree of activation, however the microporosity determined with CO 2 , W0 , increased for activated carbons with degree of activation up to 27% BO and decreased thereafter. This indicates that up to this activation new micropores were created in the carbon matrix, and after

Table 5 Effect of activation of sample A0 in CO 2 at 8508C for different periods of time Sample A0-11 A0-27 A0-57 A0-27(HCl) BO % 11 27 57 Ash % 11.3 13.5 17.8 4.0 SN 2 m 2 g 21 584 793 1038 868 E0 kJ mol 2 1 24.1 22.9 21.7 21.7 L0 nm 0.99 1.06 1.13 1.13 W0 cm 3 g 2 1 0.25 0.26 0.22 0.29 V2 cm 3 g 2 1 0.01 0.01 0.12 V3 cm 3 g 2 1 0.10 0.13 0.17

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that they were widened, which also made to increase the mesopore volume V2 . The widening of the micropores is also shown by the decrease in E0 and the increase in L0 . These activated carbons showed surface area and porosity less developed than those obtained by the KOH method. Finally, sample A0-27 was washed with a 0.1 N solution of HCl to reduce its ash content, obtaining sample A027(HCl). This sample had higher nitrogen surface area and micropore volume and also wider microporosity, which is a consequence of the ash removal by the acid treatment. This indicates that the mineral matter in sample A0-27 was blocking part of the microporosity.

4. Conclusions Results obtained indicate that chemical activation of olive-mill waste water with KOH produced activated carbons with much lower ash content, higher nitrogen surface area and much better developed porosity than in the case of either its chemical activation with H 3 PO 4 or its physical activation with CO 2 at 8408C.

Acknowledgements General de EnFinancial support by the Direccion Cientca, senanza Superior e Investigacion Project n8 PB97-0831, is acknowledged.

References
[1] Smisek M, Cerny S. In: Active carbon: manufacture, properties and applications, Amsterdam: Elsevier, 1970, pp. 10 48. [2] Mills GA. Alternate fuels from coal. Chemtech 1977;7(7):41823. [3] Wennerberg A, OGrady TM. US Patent 4082694, 1978. [4] Marsh H, Walker Jr. PL. The effects of impregnation of coal by alkali salts upon carbonization properties. Fuel Process Technol 1979;2(1):6175. [5] Marsh H, Yan DS, OGrady TM, Wennerberg A. Formation of active carbons from cokes using potassium hydroxide. Carbon 1984;22(6):60311. [6] Ehrburger P, Addoun A, Addoun F, Donnet JB. Carbonization of coals in the presence of alkaline hydroxides and carbonates: formation of activated carbons. Fuel 1986;65(10):14479. [7] Otowa T, Yamada M, Tanibata R, Kawakami M. In: Vansant EF, Dewolfs R, editors, Gas separation technology, Amsterdam: Elsevier, 1990, p. 263. [8] Otowa T, Tanibata R, Itoh M. Production and adsorption characteristics of MAXSORB: high-surface-area active carbon. Gas Sep Purif 1993;7:2415.

[9] Hu Z, Vansant EF. Chemical activation of elutrilithe producing carbonaluminosilicate composite adsorbent. Carbon 1995;33(9):1293300. [10] Ahmadpour A, Do DD. The preparation of active carbons from coal by chemical and physical activation. Carbon 1996;34(4):4719. [11] Jagtoyen M, Thwaites M, Stencel J, McEnaney B, Derbyshire F. Adsorbent carbon synthesis from coals by phosphoric acid activation. Carbon 1992;30(7):108996. [12] Jagtoyen M, Derbyshire F. Some considerations of the origins of porosity in carbons from chemically activated wood. Carbon 1993;31(7):118592. [13] Solum MS, Pugmire RJ, Jagtoyen M, Derbyshire F. Evolution of carbon structure in chemically activated wood. Carbon 1995;33(9):124754. [14] Molina-Sabio M, Rodrguez-Reinoso F, Caturla F, Selles MJ. Porosity in granular carbons activated with phosphoric acid. Carbon 1995;33(8):110513. [15] Molina-Sabio M, Caturla F, Rodrguez-Reinoso F. Inuence of the atmosphere used in the carbonization of phosphoric acid impregnated peach stones. Carbon 1995;33(8):11802. [16] Molina-Sabio M, Rodrguez-Reinoso F, Caturla F, Selles MJ. Development of porosity in combined phosphoric acid carbon dioxide activation. Carbon 1996;34(4):45762. [17] Jagtoyen M, Derbyshire F. Activated carbons from yellow poplar and white oak by H 3 PO 4 activation. Carbon 1998;36(78):108597. [18] Teng H, Yeh TS, Hsu LY. Preparation of activated carbon from bituminous coal with phosphoric acid activation. Carbon 1998;36(9):138795. [19] Benaddi H, Legras D, Rouzaud JN, Beguin F. Inuence of the atmosphere in the chemical activation of wood by phosphoric acid. Carbon 1998;36(3):3069. F. Cobalt catalysts sup[20] Moreno-Castilla C, Carrasco-Marn ported on activated carbons: preparation and behavior in the hydrogenation of carbon oxides. J Chem Soc, Faraday Trans 1995;91(19):351924. MA, Lopez-Garzon FJ. [21] Moreno-Castilla C, Salas-Peregrn Hydrogenation of carbon oxides by Ru / activated carbon catalysts obtained from Ru 3 (CO) 12 : effect of pretreatment on their dispersion, composition and activity. J Mol Catal A 1995;95(3):22333. F, Mueden A, Centeno TA, Stoeckli F, [22] Carrasco-Marn Moreno-Castilla C. Water adsorption on activated carbons with different degrees of oxidation. J Chem Soc, Faraday Trans 1997;93(12):22115. F, Mueden A. The [23] Moreno-Castilla C, Carrasco-Marn creation of acid carbon surfaces by treatment with (NH 4 ) 2 S 2 O 8 . Carbon 1997;35(1011):161926. F, Mueden A, Moreno-Castilla C. Surface[24] Carrasco-Marn treated activated carbons as catalysts for the dehydratation and dehydrogenation reactions of ethanol. J Phys Chem B 1998;102(46):923944. integral [25] Fiestas JA, Borja R. Aprovechamiento y depuracion Instituto de la grasa y sus Sevilla, Espana: del alpechn, derivados, CSIC, 1990. MV, Moreno-Castilla C, Rivera-Utrilla J, [26] Lopez-Ramon Hidalgo-Alvarez R. Activated carbons from a subbituminous coal: pore texture and electrokinetic properties. Carbon 1993;31(5):8159. [27] Bansal RC, Donnet JB, Stoeckli HF. In: Active carbon, New York: Marcel Dekker, 1988, pp. 11962.

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C. Moreno-Castilla et al. / Carbon 39 (2001) 1415 1420 F, Rivera-Utrilla J. Activated Toledo I, Carrasco-Marn carbon surface modications by nitric acid, hydrogen peroxide and ammonium peroxydisulfate treatments. Langmuir 1995;11(11):438692.

[28] Rouquerol F, Rouquerol J, Sing K. In: Adsorption by powders and porous solids. Principles, methodology and applications, London: Academic Press, 1999, pp. 123. MA, Joly JP, Bautista[29] Moreno-Castilla C, Ferro-Garca